JPH04298521A - Raised leather-like sheet excellent in resistance to dye fading and degradation and polyurethane composition suitable for its production - Google Patents

Abstract

PURPOSE:To provide a raised leather-like sheet dyed with a metal complex dye, made of very fine polyamide fibers and a polyurethane elastomer and having good dyeability and excellent heat resistance, washing fastness and resistance to dye fading degradation. CONSTITUTION:A raised leather-like sheet dyed with a metal complex dye and made of very fine polyamide fibers of an average fineness of 0.006 denier and a polyurethane elastomer prepared by mixing a polyurethane (A) comprising a polyol based on polytetramethylene glycol and a polyurethane compound (B) prepared by bonding 4,4'-butylidene-bis(3-methyl-6-t-butylphenol) to both the terminals of a polyurethane prepared by using polycaprolactone of an average molecular weight of 2000 as a polyol and using 4,4'-diaminodiphenylmethane as a chain extender through 4,4'-diphenylmethane diisocyanate in a ratio ((A)/(B)) of 90/10.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is characterized by its flexibility, hydrolysis resistance, oxidative decomposition resistance, dyeability, resistance to dye fading and deterioration, and in particular metal complex dyes caused by oxidative decomposition of polyether polyurethane. The present invention relates to a leather-like napped sheet material that has a napped surface made of ultrafine polyamide fibers that has excellent resistance to dye fading and deterioration and color development, and can be used in a wide range of applications such as clothing, interior decoration, shoes, bags, etc.

0002

[Prior Art] Conventionally, a polyamide ultrafine fiber base material is impregnated with a solution of a polymer mainly composed of polyether-based polyurethane elastomer and coagulated, and the surface of the base material is subjected to a nap treatment.The base material is then dyed to form a leather-like raised sheet. It is well known that it can be used as an object. In general, polyamide fibers such as 6-nylon are beautifully dyed with acid dyes, disperse dyes, metal complex dyes, etc., but when ultrafine fibers of 0.2 denier or less are used as in the present invention, color development occurs due to an increase in the amount of surface reflected light. Metal complex dyes are usually used because they have poor properties, and even when dyed using a highly concentrated dye bath, it is difficult to obtain a deep color with acid dyes and disperse dyes, and the fastness is also insufficient.

For example, by impregnating and solidifying a polyether polyurethane using polytetramethylene glycol as a polyol, and dyeing the base material with a raised surface treatment with a dye mainly consisting of a metal complex dye, hydrolysis resistance can be improved. The technology for obtaining suede-like artificial leather with good properties was published in 1984.
It is described in Japanese Patent Publication No. 9590 and Japanese Patent Publication No. 60-43475. In addition, polyurethane with polyoxyethylene chains has a high affinity with metal complex dyes and can be colored with deep color and high fastness, so polyurethane using polyoxyethylene glycol as a polyol and other polyols can be impregnated. Japanese Patent Publication No. 61-25834 discloses a technique for obtaining suede-like artificial leather with good color development and fastness by dyeing a base material whose surface has been coagulated and brushed with a dye mainly containing a metal complex dye. Japanese Unexamined Patent Publication 1986-30
3187 and JP-A-1-192884.

However, polyether polyurethane is generally known to have inferior heat resistance and light resistance to polyester polyurethane, and is susceptible to oxidative deterioration, and when light or heat acts on the polymer, Hydrogen is removed as a radical from the part of the polymer with the lowest bonding energy, and the generated radicals cause chain growth, causing chain cleavage of the polymer and a decrease in molecular weight and degree of polymerization, resulting in progressive deterioration and deterioration due to heavy metals. It is also known that it is promoted. Therefore, in a coexisting system of polyurethane and metal complex dye, when the ratio of polyether polyol increases,
A phenomenon in which more radicals are generated due to heat treatment, etc., accelerating the decomposition of polyurethane, and the generated radicals decompose metal complex dyes made of metal complexes such as chromium, cobalt, and nickel, causing discoloration. is recognized. On the other hand, in order to improve stability against heat, sunlight, and combustion gases in the atmosphere, various types of ultraviolet absorbers, radical chain inhibitors, peroxide decomposers, metal deactivators, etc. are added to polyurethane, either singly or in combination. How to mix it with,
Improvements were made in the method of bonding to polyurethane, and Japanese Patent Publications No. 63-58851, JP-A No. 61-231049, JP-A-64-85211, and JP-A-1-17
Many proposals have been made, such as in Japanese Patent Publication No. 4678 and Japanese Unexamined Patent Publication No. 2-22360. However, many stabilizers have poor affinity with polyurethane, and stabilizers mixed with polyurethane may migrate to the surface and fall off, or during the process of manufacturing sheet-like products.
For example, the effectiveness of the stabilizer may be reduced due to deterioration or shedding of the stabilizer due to chemical or physical effects during wet coagulation and solvent washing of polyurethane solutions, dyeing and finishing processes, etc., or discoloration due to deterioration of the stabilizer. This may lead to undesirable conditions such as Furthermore, if the fibers constituting the fiber sheet are ultrafine fibers with a large specific surface area, there is a limit to suppressing the discoloration and fading of dyes, due to yellowing and embrittlement of the fibers.

[0005] In order to improve the abrasion resistance and heat resistance of polyurethane, a polyurethane in which a bisphenol compound as a chain extender was copolymerized in the main chain was disclosed in JP-A-61-14822.
This is proposed in Publication No. 2. However, this polyurethane cannot prevent dye fading and deterioration in coexistence with metal complex dyes.

[0006]

[Problems to be Solved by the Invention] The object of the present invention is to provide a metal complex dye consisting of an ultrafine polyamide fiber and a polyurethane elastomer, which has good dyeability and excellent heat resistance, washing fastness, and dye fading resistance. An object of the present invention is to provide a leather-like sheet-like material dyed with. Furthermore, polyurethanes and polyurethanes that are compatible with polyurethanes containing polyether polyols, which are suitable for the production of leather-like sheet materials, can improve fading resistance when used in combination, and do not deteriorate even when subjected to treatments such as dry cleaning. The object of the present invention is to provide such a composition.

[0007]

[Means for Solving the Problems] The present invention has an average molecular weight of 5
A polyurethane polymerized at a ratio of 1.8 to 2.0 moles of organic diisocyanate per 1.0 mole of polymer diol of 00 to 3000, with hindered phenol bonded to both ends via the organic diisocyanate. It is a polyurethane compound with excellent resistance to dye fading and deterioration, and is also characterized by mixing and stirring 1.8 to 2.0 mol of an organic diisocyanate to 1.0 mol of polymer diol with an average molecular weight of 500 to 3000, and then dissolving both ends of the compound. A polyurethane prepolymer of isocyanate is prepared, and if necessary, a low molecular weight compound having a molecular weight of less than 500 and two active hydrogen atoms is added in a molar amount equivalent to half or less of the isocyanate equivalent of the prepolymer to perform a chain extension reaction, and further A method for producing a polyurethane compound having excellent resistance to dye fading and deterioration, which comprises adding and polymerizing a compound having two phenol groups in one molecule in a molar amount corresponding to the isocyanate equivalent of the chain-extended prepolymer. be.

The present invention also provides a polyol containing a polyether polyol having an average molecular weight of 500 to 5000,
A polyurethane (A) consisting of an organic diisocyanate and a low molecular compound having a molecular weight of less than 500 and having two active hydrogen atoms, a polyol with a molecular weight of 500 to 3000, and an organic diisocyanate, and a hindered phenol is added to both ends of the molecule via the organic diisocyanate. The bonded polyurethane compound (B) and (A)/(B)=
5 to 30 parts of polyurethane mixed in a ratio of 75/25 to 95/5 and a solvent for the polyurethane mixed with water 9
It is a polyurethane composition consisting of 5 to 70 parts.

Furthermore, the present invention provides a leather-like napped sheet material made of ultrafine polyamide fibers with an average single fiber size of 0.2 denier or less and a polyurethane elastic polymer, and dyed with a dye mainly containing a metal complex dye. , a polyurethane (A) comprising a polyol containing a polyether polyol having an average molecular weight of 500 to 5000, an organic diisocyanate, and a low molecular compound having a molecular weight of less than 500 and having two active hydrogen atoms;
A polyurethane compound consisting of a polyol of 3,000 to 3,000 and an organic diisocyanate, with hindered phenol bonded to both ends of the molecule via the organic diisocyanate.
This is a leather-like napped sheet material having excellent resistance to dye fading and deterioration, characterized in that it is a polyurethane mixed with B) and (A)/(B) = 75/25 to 95/5.

[0010] The polyamide ultrafine fiber of the present invention has an average fineness of 0.
．． The fibers are 2 denier or less, preferably 0.005 to 0.1 denier, and can be derived from conventionally known polyamide ultrafine fiber-generated fibers made of two or more polymer components including polyamide. Here, the polyamide ultrafine fiber-generated fiber of the present invention includes polyamides such as 6-nylon, 66-nylon, 610-nylon, 10-nylon, 11-nylon, 12-nylon, and colloids containing these as main components. At least one type of polyamide selected from polymerized polyamides, etc.;
Other polymers constituting the ultrafine fiber-generating fibers have different solubility from polyamide, have a low affinity, and have a melt viscosity lower than that of polyamide under spinning conditions, or have a surface tension. At least one small polymer selected from polymers such as polyethylene, polypropylene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, polystyrene, styrene acrylonitrile copolymer, styrene ethylene copolymer, polyester, etc. It is. Also,
In the case of 6-nylon with a reduced terminal amino group concentration, polyurethane having a melt viscosity lower than that of polyamide under spinning conditions can also be used as the other polymer constituting the microfiber-generating fiber. Fibers made of polyamide and other polymers can be mixed at a predetermined mixing ratio and dissolved in the same dissolving system to form a mixed system and then spun, or ■ Fibers made of polyamide and other polymers are dissolved in separate dissolving systems and A method of spinning by forming a mixed system by repeating joining and dividing multiple times at the part, ■
By melting in separate melting systems and spinning with the fiber shape specified in the spinneret, the polyamide component accounts for 40 to 80% by weight in the fiber, and the polyamide ultrafine fiber component in the fiber is 5 or more. , preferably in the range of 50 to 800 polyamide microfiber-generated fibers. If necessary, the microfiber-generated fibers are subjected to ordinary fiber processing steps such as stretching and heat setting to obtain a fineness of 2 to 15 deniers, and an average fineness (calculated value) of the polyamide microfiber component of 0.2 denier or less, preferably 0.005 to 15 deniers. The fiber is 0.1 denier.

[0011] The fibers are opened with a card and passed through a web to form a random web or a cross-wrap web, and the resulting fiber webs are laminated to a desired weight and thickness. Next, the fiber web is subjected to a fiber entanglement treatment such as needle punching using a conventionally known method to obtain a fiber entangled nonwoven fabric. The number of needle punches is usually 200 to 2500 punches/
It is preferable that the fibers be sufficiently entangled with each other in terms of elasticity and fullness.

The fiber-entangled nonwoven fabric obtained here may be subjected to treatments such as solvent treatment, decomposition agent treatment, physical treatment, mechanical treatment, etc. for generation of polyamide ultrafine fibers, or after treatment to form polyamide ultrafine fibers or the like. After forming the bundled fibers, the fibers are impregnated with a solution or dispersion of a polyurethane-based polymer to solidify the polymer into a porous or non-porous structure. If the fiber structure is not made into ultrafine polyamide fibers or bundled fibers thereof, a treatment to make the fibers into ultrafine polyamide fibers is performed. As a result, a base material for a leather-like sheet is obtained, which is composed of a fiber structure mainly composed of polyamide ultrafine fibers and/or bundled fibers thereof, and a polymer mainly composed of polyurethane.

Next, the elastic polymer to be contained in the fiber-entangled nonwoven fabric is composed of a polymer diol containing a polyether polyol having a molecular weight of 500 to 5000, a low molecular compound having a molecular weight of less than 500 and having two active hydrogen atoms, and an organic diisocyanate. Polyurethane (A) consisting of
(A)/(B)= 75
It is a polyurethane mixed in such a manner that the ratio of

[0014] Polymer diols mainly composed of polyether polyols include, for example, polytetramethylene glycol, polypropylene glycol, polyoxyethylene glycol, etc., with polytetramethylene glycol and polyoxyethylene glycol being particularly preferred; The proportion of (A) in the total polyol is 35% or more, preferably 50%
That's all. If it is less than 35%, the desired effect of imparting hydrolysis resistance and improving dyeability will be small. Other polyols to be mixed with the polyether polyol include polyester polyols, polylactone polyols, polycarbonates, and the like, depending on the purpose. Examples of low molecular weight compounds having a molecular weight of less than 500 and having two active hydrogen atoms include ethylene glycol, 1,4-butanediol, hexamethylene glycol, 3-methyl-1,5pentanediol, cyclohexanediol,
Diols such as xylylene glycol, 1,4-bis(β-hydroxyethoxy)benzene, neopentyl glycol, ethylenediamine, hexamethylenediamine,
Examples include diamines such as 4,4'-dicyclohexylmethane diamine, isophorone diamine, and 4,4' diaminodiphenylmethane. Examples of organic diisocyanates include known aliphatic, alicyclic, and aromatic diisocyanates containing two isocyanate groups in the molecule, particularly 4,4'-diphenylmethane diisocyanate, P-phenylene diisocyanate, toluylene diisocyanate, 1,5-
Examples include naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like.

The polyol having a molecular weight of 500 to 3000 constituting the polyurethane compound (B) includes polycaprolactone diol, poly(β-methyl-δ), which has relatively good hydrolysis resistance and good heat deterioration resistance. Examples include polylactone glycols such as valerolactone diol, or polycarbonate glycols such as polypentamethylene carbonate diol, polyhexamethylene carbonate diol, and polynonane-1,9/2-methyloctane-1,8 carbonate diol. Further, examples of low molecular weight compounds having a molecular weight of less than 500 and having two active hydrogen atoms include the above-mentioned compounds, including ethylene glycol, 1,4-butanediol, 1,4-bis(β-hydroxyethoxy) Particularly preferred are benzene and 4,4'-diaminodiphenylmethane. Further, examples of the organic diisocyanate include the above-mentioned diisocyanates, but 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, and the like are preferable. Further, as the hindered phenol compound, a compound having two phenol groups in one molecule is preferable, for example, a compound having the general formula

[0016]

[Chemical formula 1]

(Here, R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and R1 and R2 each represent an alkyl group having 1 to 5 carbon atoms.) For example, (I -1): 4,4'-butylidene-bis-(3-methyl-6-t-butylphenol), (I-2): 4,4'-ethylidene-bis-(2-methyl-6-t-butylphenol) ), (I-3): 2,2'-methylene-bis-(3-methyl-6-t-butylphenol), (I-4): 2,2'-methylene-bis-(4-methyl-6 -t-butylphenol), (I-5): 2,2'-methylene-bis-(4-ethyl-6-t-butylphenol), (I-6): 4,4'-methylene-bis-(2 , 6-di-t-butylphenol), (I-7):2,2'-butylidene-bis-(4-t-
butyl-6-methylphenol), or general formula

[0018]

[Case 2]

(wherein R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R1 and R2 each represent an alkyl group having 1 to 5 carbon atoms), for example, (II -1): 2,2'-thio-bis-(4-methyl-
6-t-butylphenol), (II-2): 4,4'-thio-bis-(3-t-butyl-5-methylphenol), (II-1): 4,4'-thio-bis- (3-methyl-
6-t-butylphenol), or general formula

[0020]

[Chemical formula 3]

(Here, R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is a t-butyl group, a sec-butyl group, or a neopentyl group.) For example, (
III-1): 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8
, 10-tetraoxaspiro[5,5]undecane, (
III-2): 3,9-bis{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8, 1
0-tetraoxaspiro[5,5]undecane, (II
I-3): 3,9-bis{2-[3-(3-iso-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8
, 10-tetraoxaspiro[5,5]undecane, (III-4):3,9-bis{2-[3-(3-neopentyl-4-hydroxy-5-methylphenyl)propionyloxy]-1, 1-dimethylethyl}-2,4
,8,10-tetraoxaspiro[5,5]undecane, (III-5):3,9-bis{2-[3-(3-t
-butyl-5-ethyl-4-hydroxyphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,
8,10-tetraoxaspiro[5,5]undecane,
etc.

[0022] The content of these phenolic compounds is 0.05 to 1.00 per 1 g of solid content of the polyurethane compound (B).
It is preferred to use a combination of 0.10 to 0.80 mmol, preferably 0.10 to 0.80 mmol. If it is less than 0.05 mmol, the antioxidant effect will be small, and even if it is added in large quantities, the stabilizing effect will not be affected.
It is desirable that the amount is 0.00 mmol or less.

The polyurethane compound (B) is synthesized using 1.0 mole of polyol melted under normal pressure or dissolved in an organic solvent such as dimethylformamide.
Organic diisocyanate equivalent to 8 to 2.0 mol, preferably 1.9 to 2.0 mol, was mixed and stirred, and heated to 40 mol.
The reaction is carried out at a temperature of ~120°C for 30 to 120 minutes to produce an intermediate product having isocyanate groups at substantially both ends (the first
Next, if necessary, a chain extender having a molecular weight of less than 500 in a molar amount equivalent to half or less of the residual isocyanate equivalent of the first prepolymer is added to the obtained first prepolymer and mixed and stirred. , 30 ~ at a temperature of 30℃
The reaction was carried out for 60 minutes, and then the obtained intermediate product (second
This is carried out by adding, mixing and stirring a phenolic compound in a molar amount equal to or more than the residual isocyanate equivalent of the second prepolymer to the second prepolymer, and reacting at a temperature of 30° C. for 60 to 180 minutes. Here, the phenolic compound is added in an amount equivalent to zero reactive diisocyanate groups in the final product.

In the present invention, polyurethane is prepared by mixing the polyurethane compound (B) obtained as described above with respect to polyurethane (A) in a ratio of (A)/(B) = 75/25 to 95/5. organic solvent solution of elastomer,
For example, dimethylformamide, dimethylacetamide,
It is mixed with dimethyl sulfoxide, etc., and if necessary, colorants such as pigments, coagulation regulators, light stabilizers, etc. are added.
A nonwoven fabric is impregnated and wet-coagulated according to a conventional method, and for sheet products that require ultra-fine treatment of fibers, a polyamide ultra-fine fiber treatment is performed to obtain a porous sheet-like product. If the proportion of the polyurethane compound (B) is greater than 25%, the stabilizing effect such as anti-oxidation will increase, but the physical properties of the polyurethane will decrease, resulting in poor texture, wrinkle resistance, and surface strength. , it is unsuitable for the purpose of the present invention because of its inferior stabilizing effects such as oxidation prevention.

Furthermore, this sheet-like material is divided into slices in the thickness direction to a desired thickness as necessary, and then at least one side of the sheet-like material is subjected to a napping treatment, a coloring treatment, and a softening treatment. A leather-like raised sheet material is obtained by raising the fibers on the surface. Further, the dye for dyeing the fiber nap sheet may be either a 1:1 type metal complex dye or a 1:2 type metal complex salt dye, but the latter dye is preferred. It is not necessary to use a particularly limited dyeing machine, and a wince dyeing machine, a jigger dyeing machine, a jet dyeing machine, a pad steam dyeing machine, etc. can be used. The dyeing method is not particularly limited and may be carried out according to a conventional method. After drying the dyed leather-like raised sheet material,
Product finishing treatments such as brushing, hair conditioning, rolling, and application of various stabilizers are performed to obtain a soft dyed product.

[0026]

[Function] The leather-like raised sheet dyed with the metal complex dye obtained by the method of the present invention is made of a polyether-based polyurethane elastic material containing a polyurethane compound bonded with specific hindered phenol groups and a polyamide ultrafine material. It is composed of fibers and has a texture and appearance similar to natural leather. Compounds with hindered phenol groups do not fall out of the system during wet coagulation or solvent extraction, and are durable even after long-term use. It exhibits properties with little discoloration or deterioration. In addition, it does not fall off when dry-cleaning or washing, and has good dyeability, making it especially suitable for clothing, shoes, interior decoration, etc., and has a leather-like napped sheet form with excellent heat resistance, washing fastness, and resistance to dye fading and deterioration. You can get things.

[0027]

[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 (Production Example of Polyurethane (A)) Polytetramethylene glycol (hereinafter abbreviated as PTMG), polybutylene adipate (hereinafter abbreviated as PBA), and polyoxyethylene glycol (hereinafter abbreviated as PBA) each having an average molecular weight of 2000. 674 parts of mixed diol (mixing ratio, 65:20:15) (hereinafter abbreviated as PEG), 26 parts of ethylene glycol (hereinafter abbreviated as EG), and 251 parts of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) was reacted in 1500 parts of dimethylformamide (hereinafter abbreviated as DMF) to obtain a prepolymer having residual isocyanate groups. Next, the chain was elongated with 49 parts of 4,4'-diaminodiphenylmethane (hereinafter abbreviated as MBA) and diluted with DMF to obtain a polyurethane DMF solution with a viscosity of 325 poise at 30°C and a concentration of 25% (composition solution A-1). ).

Reference Example 2 (Manufacturing Example of Polyurethane (A)) Mixed diol of polyhexane carbonate (hereinafter abbreviated as PHC) and PEG (mixing ratio, 60:40), each having an average molecular weight of 2000, 674 parts and 26 parts of EG. and M.D.I.
251 parts were reacted in 1500 parts of DMF to obtain a prepolymer containing residual isocyanate groups. Next, the chain was elongated with 49 parts of MBA, diluted with DMF, and the viscosity at 30°C was 35%.
A polyurethane DMF solution of 2 poise and a concentration of 25% was obtained (composition solution A-2).

Reference Example 3 (Production Example of Comparative Polyurethane) 674 parts of mixed diol of PBA and PEG (mixing ratio, 85:15) each having an average molecular weight of 2000, 26 parts of EG and 251 parts of MDI were reacted in 1500 parts of DMF. Seshime,
A prepolymer containing residual isocyanate groups was obtained. Next, M.B.
A polyurethane DMF solution having a viscosity of 328 poise at 30° C. and a concentration of 25% was obtained by chain elongation in A49 part (composition solution A-3).

Example 1 (Production example of polyurethane compound (B)) 220 parts of polycaprolactone glycol (hereinafter abbreviated as PCL) having an average molecular weight of 2000 and 55 parts of MDI were added to D
The mixture was reacted in 413 parts of MF at 50°C for 60 minutes with stirring to obtain a primary prepolymer having residual isocyanate groups. After cooling this to 30°C, the amount of residual isocyanate groups was measured, and separately from this, MBA10.1
part (0.49 molar equivalent based on the remaining isocyanate group)
A solution was prepared by dissolving and adjusting the solution in 252 parts of DMF, which was added to the above first prepolymer solution and reacted at 30° C. for 45 minutes to obtain a second prepolymer with residual isocyanate groups. Furthermore, the amount of residual isocyanate groups is measured, and then, separately from this, 4,4'-butylidene-bis(3-methyl-
6-t-butylphenol) [hindered phenol compound (I-1)] 38.5 parts (1.02 molar equivalent to the remaining isocyanate group) and 1.5 parts of triethylamine were dissolved in 305 parts of DMF to prepare a solution. Then, it was added to the second prepolymer solution and reacted at 30° C. for 3 hours to obtain a DMF solution of a polyurethane compound with a solid content of 25%. The concentration of residual isocyanate groups in the final product was measured, and the number of reactive diisocyanate groups was zero, indicating that the compound contained 0.31 mmol of the hindered phenol compound per 1 g of solid content of the polyurethane compound (composition solution B).
-1).

Example 2 (Production example of polyurethane compound (B)) 110 parts of PHC having an average molecular weight of 1000 and 55 parts of MDI were reacted in 248 parts of DMF at 50° C. for 60 minutes with stirring to form a polyurethane compound containing residual isocyanate groups. A primary prepolymer was obtained. After cooling this to 30°C, the amount of remaining isocyanate groups was measured, and separately from this, 40.7 parts of hindered phenol compound (I-1) (1.02 molar equivalent to the remaining isocyanate groups) and triethylamine were added. A solution prepared by dissolving 1.5 parts in 369 parts of DMF was prepared, added to the above second prepolymer solution, and reacted at 30°C for 3 hours to obtain DM of a polyurethane compound with a solid content of 25%.
A F solution was obtained. The concentration of residual isocyanate groups in the final product was measured, and the number of reactive diisocyanate groups was zero, indicating that the compound contained 0.51 mmol of the hindered phenol compound per 1 g of solid content of the polyurethane compound (composition solution B- 2).

Example 3 (Production example of polyurethane compound (B)) The hindered phenol compound (I-
1), 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8
, 10-tetraoxaspiro[5,5]undecane [hindered phenol compound (III-1)],
Otherwise, a DMF solution of a compound to which a hindered phenol compound was bound was obtained in the same manner as in Reference Example-1. The concentration of residual isocyanate groups in the final product was measured, and the reactive diisocyanate groups were zero, indicating that the hindered phenol compound (III-
This is a compound in which 0.28 mmol of 1) is bound (composition solution B-3).

Reference Example 4 (Preparation of impregnating solution) Polyurethane compound composition solutions B-1 to B-4 or hindered phenol compound I-1,
III-1 was mixed with the solid content of polyurethane (A) in the ratio shown in Tables 1 and 2, and alcohol-modified silicone was added as a coagulation regulator at a solid content of 3% based on the polyurethane (A). The polyurethane (A) was diluted to have a solid content concentration of 13% (impregnating liquid in Table 1) and 8% (impregnating liquid in Table 2) to obtain an impregnating liquid.

Examples 4 to 7, Comparative Examples 1 to 5 Island components are 6
- 50 parts of nylon, 5 parts of highly fluid polyethylene with a sea component
Using staple fibers of ultrafine fiber bundle fiber generation type multicomponent fibers (hereinafter referred to as multicomponent fibers) with a single yarn fineness of 4.5 denier and 51 mm consisting of , apparent density 0.160
A fiber entangled nonwoven fabric with an average basis weight of 600 g/m2 was prepared. The nonwoven fabric is heated to melt and heat-fix the sea component polyethylene to give an apparent density of 0.295 g/cm3.
It was made into a fiber entangled nonwoven fabric with both sides smoothed. A sheet obtained by impregnating the fiber-entangled nonwoven fabric with the impregnating liquid prepared above, removing the excess impregnating liquid on the surface, coagulating in a coagulating bath of 30% DMF aqueous solution, and coagulating polyurethane into a porous structure by washing with water. I got something like that. This sheet-like material is treated in hot toluene to dissolve and remove the polyethylene component of the multicomponent fibers, further washed, treated with a cationic treatment agent dispersion, and dried.
6-A fibrous sheet with a basis weight of approximately 490 g/m2 containing porous polyurethane in an entangled nonwoven fabric of nylon ultrafine fiber bundle fibers (average ultrafine fibers 375/bundle determined by microscopic observation, average single fiber fineness 0.006 denier) I got it. This sheet-like material was divided into two parts at the middle of the thickness, and the divided surfaces were buffed with sandpaper to adjust the thickness to 0.56 mm. Furthermore, the surface during coagulation was treated with an emery buffing machine to form a raised surface, and then dyed and finished using a green metal complex dye to obtain a raised sheet with an average basis weight of 195 g/m2.

[0036] Table 1 shows the evaluation results of the raised sheet-like properties such as hydrolysis resistance, heat deterioration resistance, and dye fading resistance. The raised sheet material according to the present invention had a soft texture and moderate stiffness. In addition, hydrolysis resistance and heat deterioration resistance were each evaluated by the following methods. ◎ No change in appearance or strength retention ○ Slight discoloration or fading, but strength retention is 70% or more △
Discoloration and fading are large, but strength retention is 70% or more × strength retention is less than 70% Hydrolysis resistance: 3 weeks treatment at 70°C and 95% RH Heat resistance: 3 weeks dry heat treatment at 130°C Resistance to dye fading and deterioration 1
The sheets were subjected to dry heat treatment at 00° C. for up to 40 days and evaluated based on the number of days the dye started fading (there is no practical problem if it is 30 days or more).

[0037]

[Table 1]

*1: Addition ratio of solid content of polyurethane compound (B) or hindered compound (I-1, III-1) to solid content of polyurethane (A).

Comparative Examples 6 and 7 In Example 4, the impregnating liquid was mixed with a polyurethane compound (B
) The mixing amount of composition liquid B-1 was increased so that the solid content of polyurethane (A) was 40% (total solid content of polyurethane (A) and polyurethane compound (B) 1).
A raised sheet-like material was obtained in the same manner except that (8.2%). The resulting raised sheet material had excellent heat resistance and resistance to dye fading and deterioration, but had a high polyurethane content and a hard texture. On the other hand, the raised sheet material impregnated with a composition solution obtained by diluting the impregnating solution so that the total solid content of all polyurethane was 14.5% had a soft texture, but was inferior in wrinkle resistance and surface strength. It was something.

Examples 8 to 10, Comparative Examples 8 to 10 Mixed diol of PTMG, PCL, and PEG each having an average molecular weight of 1500 (mixing ratio, 65:25:10) 548 parts, 1
, 95 parts of 4-butanediol and 357 parts of MDI to give a nitrogen content of 4.0 based on isocyanate groups.
% thermoplastic polyurethane pellets were obtained. The thermoplastic polyurethane and the terminal amino group concentration are 1.5 x 10-5
Using eq/g of 6-nylon as a spinning raw material, melt-spinning was carried out by combining, dividing, and integrating polymer streams extruded from separate extruders so that the polyurethane stream was 25 parts and the 6-nylon stream was 75 parts. The number of Shimamoto is 50 (
A polyurethane multicomponent fiber with a fineness of 10 denier was obtained. The obtained multicomponent fiber was heated to 80℃
The fibers were stretched three times in hot water and heat-set to obtain fibers with a fineness of 3.5 dr. After applying an oil agent to this fiber, it was mechanically crimped and cut into fiber lengths of 51 mm to obtain staple fibers.

[0041] Next, the obtained staple fibers were 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 punched from both sides of the fiber web at a total punch density of 980 punches/cm2. The fiber entangled nonwoven fabric was made by needle punching and impregnated with a 7.5% aqueous solution of polyvinyl alcohol to achieve a target reduction rate of 150%.
After squeezing and drying to obtain a nonwoven fabric with a stable shape, the impregnating solution prepared in Reference Example 4 and having the composition shown in Table 2 was applied to an impregnating rate of 200%.
The polyurethane in the fiber was dissolved in an atmosphere at a temperature of about 45° C., and then the polyurethane was coagulated by immersion in a 30% DMF aqueous solution, and the polyvinyl alcohol was removed by washing with hot water. One side of the obtained fibrous sheet is sliced to a thickness of 1.0 mm, and the surface side upon coagulation is subjected to a napping treatment to create a suede-like sheet, which is then dyed with a yellow metal complex dye and rubbed to form a product. did. Table 2 shows the evaluation results of the dye fading resistance after repeating the dry cleaning treatment five times using this raised sheet material and Parkrene. The raised sheet material according to the present invention had a firm and flexible texture with little shedding of fuzz, and was excellent as a suede-like sheet for clothing.

[0042]

[Table 2]

*1: Addition ratio of solid content of polyurethane compound (B) or hindered compound (I-1, III-1) to solid content of polyurethane (A).

[0044]

[Effects of the Invention] As explained above, the leather-like raised sheet material of the present invention can be produced by using a polyurethane compound bonded with a compound having a specific hindered phenol group. Compounds with hindered phenol groups do not fall off from polyurethane during the processing process, and when used for clothing, shoes, interior decoration, etc., they are less likely to fall off from products during dry cleaning or washing, so it will last for a long time. It suppresses oxidative decomposition of polyurethane elastic polymers containing polyether-based polyols, and prevents fading and deterioration of dyes in ultrafine polyamide fibers dyed with metal complex dyes, resulting in less discoloration, discoloration, and deterioration. is demonstrated.

Claims (5)

[Claims] Claim 1: 1 mol of organic diisocyanate per 1.0 mol of polymer diol having an average molecular weight of 500 to 3,000.
．． 8 to 2.0 moles are mixed and stirred to form a polyurethane prepolymer with isocyanate at both ends, and a compound having two phenol groups in one molecule is added and polymerized in a molar amount corresponding to the isocyanate equivalent of the prepolymer. A method for producing a polyurethane compound with excellent resistance to dye fading and deterioration. 2. 1 mol of organic diisocyanate per 1.0 mol of polymer diol having an average molecular weight of 500 to 3,000.
．． 8 to 2.0 moles are mixed and stirred to form a polyurethane prepolymer with isocyanate at both ends, and a low molecular compound having a molecular weight of less than 500 and two active hydrogen atoms is added in a molar amount equivalent to less than half of the isocyanate equivalent of the prepolymer. A dye with excellent resistance to fading and deterioration, characterized by carrying out a chain extension reaction and further polymerizing by adding a compound having two phenol groups in one molecule in a molar amount corresponding to the isocyanate equivalent of the prepolymer subjected to the chain extension reaction. A method for producing a polyurethane compound. 3. 1 mol of organic diisocyanate per 1.0 mol of polymer diol having an average molecular weight of 500 to 3,000.
．． A polyurethane compound having excellent resistance to dye fading and deterioration, which is a polyurethane polymerized in a proportion of 8 to 2.0 moles, and has hindered phenol bonded to both ends via the organic diisocyanate. 4. A polyurethane (A) comprising a polyol containing a polyether polyol having an average molecular weight of 500 to 5000, an organic diisocyanate, and a low molecular compound having a molecular weight of less than 500 and having two active hydrogen atoms.
and a polyurethane compound (B) consisting of a polyol with a molecular weight of 500 to 3000 and an organic diisocyanate, with a hindered phenol bonded to both ends of the molecule via the organic diisocyanate (A)/(B) = 75/25~
A polyurethane composition comprising 5 to 30 parts of polyurethane mixed at a ratio of 95/5 and 95 to 70 parts of a solvent for the polyurethane that is mixed with water. 5. Consisting of ultra-fine polyamide fibers with an average single fiber size of 0.2 denier or less and a polyurethane elastic polymer,
In a leather-like raised sheet dyed with a dye mainly consisting of a metal complex dye, the polyurethane has an average molecular weight of 50
A polyurethane (A) consisting of a polyol containing a polyether polyol having a molecular weight of 0 to 5000, an organic diisocyanate, and a low molecular weight compound having a molecular weight of less than 500 and having two active hydrogen atoms, and a polyurethane (A) consisting of a polyol having a molecular weight of 500 to 3000 and an organic diisocyanate. A polyurethane compound (B) with a hindered phenol bonded to the terminal via an organic diisocyanate is (A)/
(B) A leather-like raised sheet material having excellent resistance to dye fading and deterioration, characterized in that it is a polyurethane mixed in a ratio of 75/25 to 95/5.