JPS59100778A - Leather like sheet article having durability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a highly durable leather-like sheet material that is flexible and has a good texture, has excellent light resistance and hydrolysis resistance, and has a clear color tone. Leather that is suitable for long-term uses such as car seats and reception chairs, and has a classy color tone.

Traditionally, polyurethane-based leather-like sheets have a better texture, feel, and appearance than PVC leather, so they are used for shoes, bags, bags, etc.
It has been used by many companies as a material for clothing, gloves, belts, furniture, etc. However, for items that will be used for a long period of time, such as 5 to 10 years, such as board furniture such as reception chairs and office chairs, and car seats, 7" CL leather-like sheets are manufactured using conventional polyurethane handles. However, since the light resistance and hydrolysis resistance of poly-1-cretane were poor, 1i+iJ could not be used for a long period of time.

Polyurethane is obtained by reacting a polymeric diol such as a polyester or polyether with an organic diisocyanate and an active hydrogen compound as a chain extender. When used, the polyurethane obtained has poor light deterioration resistance, and specifically, it is known that light irradiation causes yellowing, decrease in strength and elongation, and crosslinking hardening.

In addition, when a polyester-based polymer diol is used, the ester bonds are degraded by the hydration molecules ('l), and the surface of the leather-like sorted material becomes sticky in a short period of time, or may be severely damaged. Because of this, polyester-based polyurethane is used for leather-like sheet materials that require durability, such as numerous cracks appearing on the entire surface or peeling of the polyurethane resin layer laminated to the base. In addition, polyether-based polyurethane has excellent hydrolyzability and oxidative deterioration, and is easily degraded by ultraviolet rays and heat.Therefore, polyurethane is used in fields that require high durability. It was extremely difficult to develop leather-like sheet products.

Conventionally, pigments, dyes, or colorants containing these as main components have been used to color polyurethane leather-like sheets. Coloring with dyes has the advantage of being clearer and more transparent than coloring with pigments, providing a more consistent color tone, as well as being available in a wide variety of colors.
Therefore, the leather-like sheet material colored by the dye has a high-class feel. However, on the other hand, leather-like sheets colored with dyes have problems such as color migration, discoloration, fading, and bleeding. The lamination processing method of polyurethane resin is extremely M-absorbing. In general, polyurethane relatively absorbs and captures certain dyes, but the extent of this is not sufficient. For example, Dryke IJ
- The dye may be easily removed by washing or washing, the dye may migrate from the polyurethane layer to another polyurethane layer or another polymer layer, causing dye fading, and furthermore, the dye may fade significantly due to exposure to sunlight or heating. It has a fatal flaw.

The present inventors conducted an H/H test on a leather-like sheet material that has the above-mentioned soft and good texture, excellent dyeing fastness, and high quality 14V resistance to dye migration. ]
As a result, by using a specific polyurethane and laminating these polyurethanes in a specific order, we completed a high 1# leather-like sheet product that has all of the above required performances to a high degree.

That is, the leather-like material of the present invention, which is flexible, has a good texture, and has high durability, has the following structure.
With such a structure, all of the performance requirements listed in item L of the present invention can be achieved.

That is, the present invention provides a fibrous substrate (I), a bonding layer (Ill
), a colored layer (Ill) and a surface coating layer (IV) are sequentially laminated in a leather-like sheet material in which the bond) vI
(1) - Compounds (a), (b) and (e) (a
)° A polymeric diol mainly composed of polycarbonate diol, (b) an aliphatic frozen or alicyclic diisocyanate, and (e) a low-molecular active hydrogen compound containing a compound represented by the following general formula (1), HNR2- Rt -NHR3...Medium...(1) (However,
R1 is an alkylene group having 2 to 12 carbon atoms, R2,
Either one of Ra is a hydroxyethyl group or a hydroxypropyl group, and the other is a hydrogen atom and has 1 to 1 carbon atoms.
10 alkyl groups.

A polymer mainly composed of polyurethane synthesized from a hydroquine ethyl group or a hydroxypropyl group, or a crosslinked polyurethane that is cured by further reacting this polyurethane with an aliphatic or alicyclic polyisocyanate. The colored layer (Ill) is a layer consisting of a combination of diols and ethylene oxide structural units (-CH2CH20%) consisting mainly of polycarbonate chains (dL (e), (lead (dj)). Mixed diols mainly composed of diols, or block copolymer diols containing polycarbonate chains and ethylene oxide structural units as main components in the same molecule, <e
) Aliphatic or cycloaliphatic diisocyanates, (fJ
Polymers mainly composed of aliphatic or alicyclic diamines and, if necessary, polyurethanes synthesized substantially from hydrazine or dihydrazide, as well as metal-containing anchor ring dyes, acid dyes, vat dyes, Sft The surface coating layer (IV) is made of at least one layer of dyes selected from the group consisting of chemical dyes, and the surface coating layer (IV) is made of the following compounds (h), (i), (j) and (second (h)). polycarbonate diol (i) aliphatic or alicyclic diisocyanate, (j) aliphatic or alicyclic organic cyabane, and optionally (auxiliary) a polymer mainly composed of polyurethane synthesized substantially from hydrazine or dihydrazide; It is characterized by being a layer.

The following general formula (2) is used to synthesize the polyurethane constituting the bonding layer (former) (where R4 and R5 are each a hydrogen atom and have 1 to 1 carbon atoms.
It is either an alkyl group, a hydroxyethyl group, or a hydroxypropyl group, but cannot be a hydrogen atom at the same time. ), the fold abrasion resistance of the resulting leather-like sheet material is further improved.

Each component of the present invention will be specifically explained below.

First, the fibrous substrate (1) constituting the present invention is a fiber aggregate such as an entangled nonwoven fabric, a laminated nonwoven fabric, a woven fabric, or a knitted fabric, or a polymer mainly composed of an elastic polymer is added to these fiber aggregates. It is impregnated with a solution or dispersion of coalescence and coagulated into a porous or non-porous structure. The fibers constituting the fiber aggregate include ordinary fibers, irregular cross-section fibers, high-shrinkage fibers, sea-island cross-section structure fibers, bimetallic cross-section structure fibers, microfibril bundle fibers, ridge-like fibers, and mixed fibers thereof. It will be done. Microfibril bundle fibers and rod-like fibers are obtained by dissolving and removing one component of a special fiber having a sea-island cross-sectional structure spun from two or more types of polymeric substances having different compatibility with solvents with a solvent. That is, by dissolving and removing the sea component from the special fiber, microfibril bundle fibers can be obtained.
By dissolving and removing the island component from the special fiber, a lotus-like fiber can be obtained. In the substrate for leather-like sheet materials, it is preferable that the fibers and the coagulated polymer not be in complete contact with each other. Polymers included in the fiber aggregate include polyurethane elastomer, polyvinyl chloride, and polyamide.

Next, the polyurethane bonding layer (1) is formed from polyurethane as described above, but the polymeric diol used to synthesize the polyurethane is a diol mainly composed of polycarbonate chains, and what is the polycarbonate chain? 1 (a group represented by -R-0-C-0% (where R represents a divalent organic group and p represents the degree of polymerization), but it is most preferable that R is a hexamethylene group. Since the polycarbonate chains in the polymeric diol are extremely excellent in hydrolysis resistance and oxidative deterioration resistance (light resistance, heat deterioration resistance), polyurethanes containing them will also have similar properties.

In addition, the organic diisocyanate used in the synthesis of the polyurethane constituting the bonding layer (UJ) must be aliphatic or alicyclic, and polyurethanes obtained by using other organic diisocyanates, such as aromatic organic diisocyanates, It is inferior in light deterioration resistance, and specifically causes light yellowing of leather-like materials, deterioration of surface properties due to deterioration of polyurethane, and also has poor light-blocking dye fastness.

Regarding the chain extender, it is necessary to mainly use aliphatic or alicyclic organic cyabane, and aromatic organic diamines have poor light deterioration resistance, etc., as in the case of the aromatic organic diisocyanates mentioned above. . However, when the above polycarbonate diol is used as the soft segment, an aliphatic or alicyclic diisocyanate is used as the organic diisocyanate, and a common aliphatic or alicyclic diamine is used as the chain extender, and the bonding layer (1) is In order to make a resin with the required softness, if the hardness of the resin is lowered, the polyurethane synthesized from it is extremely susceptible to crystallization of the soft segment and becomes extremely hard at room temperature. However, only when the chain extender of the present invention is used, a very flexible polyurethane can be obtained, and if synthetic leather is produced using this polyurethane, the texture will be extremely soft and the bending resistance will be significantly improved. Become.

To explain the resin used as the bonding layer in more detail, first, it is a polymeric diol with excellent hydrolysis resistance and oxidation resistance, and has an average molecular weight of 1)j, 600 to 5000.
polycarbonate diol, preferably in the range of 1,6
-Hexanethiol polycarbonate glycol is used. Typical examples of aliphatic and alicyclic organic diisocyanates include hexamethylene diisocyanate, methylchlorohexane diisocyanate (water-added Tl
)I), 4゜4'-dicyclohexylmethane diisocyanate (water added M'DI), inpropylidene bis(4
-cyclohexane diisocyanate), inphorone diisocyanate, lysine diisocyanate, aqueous xylylene diisocyanate, cyclohexane diisocyanate, and the like.

The chain extender represented by the general formula (1) used in the present invention includes N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)propylenediamine,
N-(2-hydroxypropyl)ethylenediamine, N
-(2-hydroxypropyl)propylene diamine, N
~(2-hydroxypropyl)butylenediamine, N
, N'-bis(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)propylenediamine, N,N'-bis(2-hydroxypropyl)ethylenediamine, N,N/-bis(2 -Hydroquinepropyl)propylenediamine, N,N/-bis(
2-hydroxypropyl)hexamethylenediamine, N
-Methyl-N'-(2-hydroxyethyl oligoethylenediamine, N-propyl-N'-(2-hydroxypropyl)propylenediamine, N-hexyl-N'-(2-
hydroquine propyl) hexamethylene diamine, and the like.

In addition, as a polymerization terminator represented by general formula (2), di-
Examples include n-butylamine, isobutylamine, hequinylamine, di-n-ethylamine, monoethanolamine, isopropanolamine, jetanolamine, diisopropanolamine, and the like.

In addition, in order to further improve the light resistance and heat resistance of the polyurethane of this bonding layer (■), hydrazine or dihydrazide may be used as a part of the chain extender. Polyurethane may be used as it is, but in order to further improve performance such as solvent resistance, surface properties, and durability, it is preferable to use it in combination with an aliphatic or alicyclic polyisocyanate for reaction curing. That is, in the case of a two-component polyurethane, the polyisocyanate components include hexamethylene diisocyanate, inphorone diisocyanate, methylcyclohexane diiso7anate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate,
(7) Isocyanate-terminated polyisone obtained by reacting iso/anates such as chlorohexane diisocyanate or these diisocyanates with glycerin, trimethylolpropane, trimethylolethane, pentaerythritol%' (7) Polyhydric alcohols and water You can use Anate. Note that (11) the thickness of the layer is usually in the range of 1 to 500 μm.

Next, the colored layer (Ill) is formed from the above-mentioned polyurethane and dye, but the polymeric diol used to combine the polyurethane is a diol mainly composed of polycarbonate chains and an ethylene oxide structure. It is either a mixed diol mainly composed of a diol containing 20% of units + CHzC1, or a block copolymer diol whose main components are a polycarbonate chain and an ethylene oxide structural unit in the same molecule, but the performance The former is preferable in terms of the availability of raw materials.The polycarbonate chain is a group represented by (-R-0-C-09,
represents a divalent organic group, p represents the degree of polymerization, and R
Most preferably, is a hexamethylene group. Since the polycarbonate chain in the island molecule diol has extremely excellent hydrolysis resistance and oxidative deterioration resistance (light resistance, heat deterioration resistance), polyurethane containing this chain also has similar properties. Furthermore, the proportion of ethylene oxide structural units in the total polymeric diol used to synthesize the polyurethane constituting the colored layer (m) is within the range of 0 to 50% by weight, but the ethylene oxide content is very small. In some cases, the resulting polyurethane has a low affinity for dye molecules, and therefore the effects aimed at by the present invention in terms of color fastness, dye migration prevention, and dye coloring properties are small. On the other hand, if the strength exceeds 50, the polyurethane obtained will easily swell in water, and the strength in wet conditions will be significantly reduced, and the polyurethane will be more susceptible to oxidative deterioration, resulting in poor light resistance and heat resistance. In addition, the mechanical properties such as strength and elongation become poor, the interface physical properties of the leather-like sheet material deteriorate, and furthermore, the dye fastness when wet and the surface physical properties deteriorate.

Furthermore, the average molecular weight of the polymer diol is 600 to 5000.
If it is less than +600, the resulting polyurethane resin will have flexibility, resulting in poor texture, flexibility and surface properties of the leather-like sheet. On the other hand, the polyurethane resin becomes soft, loses its elasticity, and the strength and elongation of the polyurethane resin decreases, resulting in extremely poor surface properties when made into a leather-like sheet.

In addition, the organic diisocyanate used in the synthesis of the polyurethane constituting the (In) layer must be aliphatic or alicyclic, and if other organic diisocyanates, such as aromatic organic diisocyanates, are used, The resulting polyurethane has poor light resistance, and specifically causes light yellowing of leather-like sheets, deterioration of surface properties due to deterioration of the polyurethane, and also has poor light fastness.

As for the chain extender, it is necessary to use an aliphatic or alicyclic organic diamine, and aromatic organic diamines have poor light deterioration resistance as in the case of the aromatic organic diisocyanates mentioned above. Since the colored layer (IIυ) uses a polymeric diol containing polyethylene oxide, the oxidative deterioration resistance will be somewhat reduced. For hydrazine trenches, it is preferable to use dihydrazide in a molar ratio of 4.0 or less to the cyanide.Using hydrazine or dihydrazide improves the heat resistance in addition to the light resistance of polyurethane. Furthermore, the light resistance and heat resistance of the dye formulation are improved.If the amount of hydrazine or dihydrazide used exceeds 4.0, the resistance to oxidation and deterioration of the leather-like sheet is improved, but the resistance to water addition is improved. Degradability and blocking resistance are greatly reduced.

The colored layer (III) is made by blending dyes with polyurethane obtained from the above-mentioned raw materials, and the dyes blended include metal-containing complex dyes, acid dyes, vat dyes, and sulfur dyes.
is preferable in terms of improved light resistance and dye retention (dye transfer prevention, washing fastness, dry cleaning fastness). Among these dyes, metal-containing complex dyes are particularly preferred. A metal-containing complex salt dye is a dye in which a metal atom and a dye molecule form a complex salt in a ratio of 141 or 1:2, and usually have a sulfonamide group or an alkyl sulfone group in the molecule. Therefore, it has a negative charge as a whole. The most common metal forming a complex salt is chromium, and other metals such as cobalt and copper are also used. 1:2 type metal-containing complex salt dyes are most preferred.

The colored layer (41) is usually formed by adding at least one dye selected from among the above-mentioned dyes to a polyurethane solution [~ and then removing the solvent from the polyurethane solution, but The amount thereof is 1 to 70% by weight, preferably 2 to 25% by weight, based on the polyurethane.The thickness of the layer (1) is preferably 1 to 500μ.

In the leather-like sorted product of the present invention, a polyurethane surface coating layer (JJ) is formed on the colored layer (II).

This (■) layer makes it possible to prevent the dye in the U> layer from migrating out of the layer, improves the surface properties of the leather-like sheet, and eliminates dye fading due to NOx gas, solvents, and chemicals. Furthermore, there are great advantages such as improved hydrolysis resistance.

The polyurethane resin used for this polyurethane surface coating layer (IV) can be obtained from the raw materials mentioned above, but to be more specific, it is a polymeric diol that has excellent hydrolysis resistance and oxidative deterioration resistance. A polycarbonate diol having a low dye affinity and an average molecular weight in the range of 600 to 5,000, preferably 1,6-hexanesiol polycarbonate glycol, is used.

Polyurethanes whose soft segments are polyols with polycarbonate chains have extremely high dye affinity compared to polyurethanes whose soft segments are other polyester polyols or polyether polyols, or other polymers such as acrylic, cellulose, or amide polymers. Although it is small, its ability to prevent dye migration is extremely strong. For example, polytetramethylene glycol or polypropylene glycol, which has good hydrolysis resistance, is used as an organic diisocyanate, and isophorone diison is used as an organic diisocyanate. Polyurethanes synthesized using hydrazine have good light resistance and hydrolysis resistance. Even if polyurethane using a small amount of polyester is laminated on top of the colored layer (III), which has good dye retention, surprisingly, the dye migration prevention property will be rather poor and the opposite effect will occur, but the present invention When a polyurethane having polycarbonate polyol as a soft segment is laminated on layer (III) as shown in FIG.

In addition, since it is essential that the polyurethane used in this (■) layer has improved dye migration prevention properties, the polymeric diol substantially immobilizes dye-affinity groups, such as ethylene oxide structural unit +CH2CH2O,1ili-. 4
L, r”k) is important.

(PJ) The organic diisocyanate used to synthesize the polyurethane for 'I- is an aliphatic or alicyclic diisocyanate, and the chain extender is l]i
It is a rib-based or alicyclic diamine. If necessary, hydrazine or dihydrazide is used in combination as part of the chain extender, but in this case, the molar ratio of hydrazine or dihydrazide to the organic diamine must be 2.0 or less. Although the oxidative deterioration resistance is improved, the ability to prevent dye migration, hydrolysis resistance and blocking resistance are greatly reduced. When diisocyanate and diamine components other than aliphatic or alicyclic components are used, the light deterioration resistance is significantly lowered and the CIll) layer is discolored. That is, polyurethane using diisocyanate or diamine with an aromatic group is decomposed by light, and the radicals generated by this decomposition attack the dye molecules present in the (I[i) layer, and as a result, the dye molecules decompose. It will be denatured and discolored.

Typical examples of aliphatic or alicyclic organic diiso/anates used in the colored layer (11) and surface coating layer (IV) include hexamethinone diisocyanate, methylcyclohexane diisocyanate (water-added TDI), 4.4
'-dicyclohexylmethane diiso/anate (water added Ml) I), isopropylidene bis(4-7 chlorohequinyl iso7anate), isophorone diamine anate, lysine diinocyane), water bombarded xylylene diisoane 1-, Schiff's Coheginan Diison I, -t, etc. Also, typical examples of aliphatic / cycloaliphatic cyanide: i:, ethylene cyan, etc. , hexamethylene diamine, isophorone diamine, 4.4'
-diaminodicyclohexyl/lumethane, piperazine, cyclohexylene cyagon, etc. Examples of pure hydrazine or dihydrazides include hydrazine, hydrazine water + U product, N,N'-dimethylhydrazine, adipic acid dihydrazide, sebacic acid dihydrazide, glutaric acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide propionic acid hydrazide, etc. .

The polyurethane surface coating layer (IV) is usually formed by a method of removing the solvent from a polyurethane solution (the thickness of the edge layer is preferably in the range of 1 to 100 μm).

The leather-like sheet material of the present invention has a fibrous base (I), a bonding layer (■), a colored layer (11), and a surface coating layer (11) as essential components.
IV), but with a durable and flexible bonding layer (
1) is between the fibrous substrate (1) and the colored layer (portion 1), which prevents the dye in the layer (■1) from migrating to the substrate, resulting in extremely good dye retention. A leather-like sheet product is obtained.That is, the upper and lower surfaces of the (Ill) layer made of polyurethane with high dye affinity are covered with the (II) layer and (■) layer with low dye affinity and dye permeability, respectively. By covering, a leather-like sheet material with good dye retention without dye fading due to physical dye migration can be obtained.Furthermore, all of these laminated polyurethane resins have good light resistance, heat resistance, etc. The dye does not fade at all even when exposed to light or heat, and it also has good dye retention when exposed to solvents and chemicals, so it is revolutionary compared to conventional leather-like sheet materials in terms of dye fading. You can see the improvement.

The bonding layer (II) may be in the form of a dry film or a foamed structure, but a foamed structure is preferred in terms of texture, appearance, volume, bending resistance, bending strength, etc. It has a luxurious feel and is desirable. Also, these (n, 1
The layers (1) and (PJ) may contain stabilizers and additives that do not damage the dye contained in layer (II), such as polymers.

In order to form a foam ring, there are two methods: mixing various foaming agents with polyurethane resin and heating to decompose the foaming agent, or coating polyurethane resin dissolved in a water-miscible solvent on a releasable support. The method of obtaining Suhonji sheet by soaking it in water and coagulating it is to foam the polyurethane emulsion of Takanobu using a foaming machine. A method of obtaining the product by coating it on a releasable support and drying it without crushing the foam, or a method of using urethane foam manufacturing technology by the One Yosoto method, or a method of using ItCits, polyol, inorganic boryson anate 1 There are many other known methods such as heating a compounded solution consisting of a blowing agent and an organic solvent to form a foam layer by volatilizing the solvent and generating bubbles by decomposing the blowing agent. You can stay there.

Furthermore, in the leather-like sheet material of the present invention, the fibrous substrate (
I) A polymer layer containing pigments and titanium oxide to hide the color spots and irregularities of 1) and improve light resistance, and a polyurethane surface layer layer 2 to increase surface strength and color gloss. Furthermore, a polymer layer that does not cause decomposition or modification of the eastern side contained in layer (2) may be inserted or laminated between each polyurethane coating layer.

Next, what is a typical section of the leather-like sheet material of the present invention? ii The laminated structure will be explained with reference to the attached drawings. In FIG. 1, 1 is a fibrous base (1), 2.3 and 4 are bonding layers (I), respectively.
I), a colored layer (■), and a surface coating layer.

The present invention will be specifically explained below using Examples.

In the examples, needle hydrolyzability refers to the surface plating, surface cracks, and coating layer that occur when the obtained leather-like sheet material is left in an atmosphere with a relative humidity of 95°C and a temperature of 70°C (Jungle test conditions are 10 weeks). peeling, dye fading (presence or absence of dye transfer when wet), etc. Light resistance was measured using a fade meter to determine dye fading when exposed to a carbon arc lamp in an atmosphere of 63°C for 1000 hours. In addition, heat resistance is measured by checking dye fading after being treated in an open environment at 120°C for 500 hours.Chemical resistance is measured by checking dye fading after being immersed in ethanol for 1 hour at room temperature. These fastnesses were determined using a gray scale for fading and a gray scale for contamination.Those with a 5th grade fastness showed no fading at all, and the fastness decreased from 4th grade to 3rd grade to 2nd grade. Grade 1 is when the fastness is extremely poor.

In addition, the transferability of Eishina was 5 (, w ( , thickness 3 sheets) and placed in a 70℃ oven for 24 hours with a load of 71q.
The sample was pressed for a period of time, and the degree of transfer of dye from the test piece to the white polylanthanum sheet was determined. 1"
A gray scale for contamination was used to determine which grade from 1 to 5 it corresponded to. The surface properties were measured using a taper type abrasion tester at a load of 1,000 times of friction, and using a fold abrasion tester (Custom type) at a load of 2,000 times of friction.
These are the results of observing the degree of surface wear after multiple treatments.

The bending resistance is the result of testing at room temperature using a bending tester with a stroke of 111 (maximum: 3 on, shortest: 1 (m) and a bending frequency of 8,600 times/hour. If there is no scratch, it is marked with ◯, if there is a slight scratch, it is marked with △, and if the base is scratched to the extent that it is visible, it is marked with ×.The soft texture was judged by touch.

Good ones are marked with ○, slightly hard ones with Δ, and very hard ones with X.

In addition, in the examples, the polymer diol, diisonanate compound, and chain extender that were the raw materials for the polyurethane used were indicated using abbreviations, but the relationship between the abbreviations and the compounds is as follows.O Examples 1 to 12 , Comparative Examples 1 to 11 Sequential polyurethane surface coating ff1 (IV) on release paper,
The colored layer (■) and the bonding layer (n) each have a dry thickness of 10 μm.
, 20μ, 40μ (100μ for foam layer) using a knife coater to coat the polyurethane solution to form a bonding layer (
While II) was still sticky, it was pasted onto the substrate (■) (Tetron-7-Yonne fabric), heated and dried, and the release paper was peeled off to obtain a dyed leather-like sheet. . The raw materials for each polyurethane used in the ([V) layer, (■) layer and (n) layer are shown in Table 1 and Table 2.3.

Moreover, ammonium bicarbonate was used as a blowing agent.

The colored layer Cm) contains Ir, a 1:2 type metal-containing complex dye,
Brown BL (III) layer polyurethane L/p
5% by weight was added to 7 children. Also, Example 15
In this case, 5olarRed S, an acidic dye, was used in place of Ir, Brown BLK.

The durability, color fastness, east migration, surface properties, texture (softness), and other physical properties of the resulting leather-like articles were compared, and the results are shown in Tables 2 and 3. As is clear from the light, the leather-like sheet material of the present invention is soft and has a good feel, and has outstanding durability, dye retention, and dye fastness.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of the leather-like article of the present invention, in which 1 is a fibrous substrate, 2 is a bonding layer, 3 is a colored layer, and 4 is a surface coating layer. Patent Defu Co., Ltd. Kuraray Patent Attorney Kendai Honda

Claims (1)

[Claims] 1. Fibrous base, bonding layer (1), colored layer (III)
In a leather-like sorted material in which an entrance coating layer (■) is sequentially laminated, the bonding layer (formerly the following compound (a)), (
bJ and (C) (a) Polymer diol mainly composed of polycarbonate diol (b) Aliphatic or alicyclic diisocyanate, and (C)-F low-molecular active hydrogen containing a compound represented by general formula (1) Compound, 1fNR2-R1-NHRs (
1) (However, R1 is an alkylene group having 2 to 12 carbon atoms, one of Rz and Ra is a hydroxyethyl group or a hydroquinepropyl group, and the other is a hydrogen atom,
It is either an alkyl group having 1 to 10 carbon atoms, a hydroxyethyl group, or a hydroxypropyl group. ) or a crosslinked polyurethane that is cured by further reacting this polyurethane with an aliphatic or alicyclic polyisocyanate, and the colored layer (Ill) is a layer composed of the following compound: (d), (e), (f) and (g) (ψ Mixed diols consisting mainly of diols mainly containing polycarbonate chains and diols containing ethylene oxide structural units (-CH2CHz (J→h), or the same A block copolymer diol whose main components are polycarbonate chains and ethylene oxide structural units in the molecule (
e) aliphatic or cycloaliphatic diiso7anate, (fJ
Consists of aliphatic or alicyclic cyanine, and (g) a polyurethane-based polymer essentially synthesized from hydrazine or dihydrazide, as well as metal-containing complex dyes, acid dyes, vat dyes, and sulfur dyes. A layer formed from at least one dye selected from the group, and the surface coating layer (TV) is a layer formed from at least one dye selected from the group -17 compound (h)
, (i), (j) and (3)(h) polycarbonate diol, (i) aliphatic or cycloaliphatic diisocyanate, (j) aliphatic or cycloaliphatic organic diamine, and optionally (k) hydrazine or 1. A leather-like sorted material characterized by having a layer consisting of a polymer mainly composed of polyurethane synthesized substantially from dihydrazide. 2 One of the low-molecular active hydrogen compounds used in the synthesis of the polyurethane constituting the bonding layer (11) is represented by the following general formula (2) (wherein R4 and R5 are each a hydrogen atom, and each has 1 to 1 carbon atoms.
IO is either an alkyl group, a hydroxyethyl group, or a hydroxypropyl group, but cannot be a hydrogen atom at the same time. ) is the leather-like article described in the range 1 of the line f+h. 3. Bonding layer (leather-like sorted material described in Claims 1 or 2 JA in which titanium oxide or pigment has been excluded) 4. Used in the synthesis of polyurethane constituting the colored layer (1) (-CH2C) in the polymeric diol
A leather-like sheet material according to any one of claims 1 to 3, in which the ratio of L20% units is O to 50% by weight and the vertical width is 0 to 50% by weight. 5. Claims 1 to 4, wherein in the polyurethane constituting the M color layer (III), the molar ratio of the compound (g) to the compound (f) is 4.0 or less.
Leather-like sorted material according to any of the above. 6. In the polyurethane constituting the coating layer (IV), the molar ratio of the compound (barrel) to the compound (g) is 2.0 or less in terms of molar ratio, according to any one of claims 1 to 5. The leather-like article described.