JPS5966577A - Leather-like sheet having excellent 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 product that has excellent light resistance and hydrolysis resistance and a clear color tone, and is particularly applicable to automobile seats, reception chairs, etc. Long-term use of:
The present invention provides a leather-like sheet material that is suitable for high-end uses and has a luxurious feel. .

Traditionally, leather-like sheets in the polyurethane industry have been made of vinyl chloride.
Because the texture, feel, and appearance are better than that of
It has been used in large quantities as a material for clothing, gloves, belts, furniture, etc. However, for items that are used for a long period of time, such as 5 to 10 years, such as furniture such as reception chairs and office chairs, and car seats, leather-like sheet products manufactured using conventional polyurethane resins can be replaced with polyurethane resin. My friend, who has poor light resistance and poor water resistance, was unable to use it without much knowledge.

Polyurethane is made by combining polymeric disilane such as polyester or polyether with organic diincyanate and chain extension.
Polyurethane can be obtained by reacting with an active hydrogen compound as an agent, but for example, when an aromatic organic diisocyanate is used as the organic diisocyanate, the polyurethane obtained has poor light deterioration resistance, and the specific fC is yellowing due to light irradiation. It is known that it causes low strength and elongation, and crosslinking and hardening. Furthermore, when a polyester-based polymeric diol is used, the Ll and Nisdell bonds are hydrolyzed and deteriorated, causing the surface of the leather-like sheet to take on a sticky sound within a short period of time (J1 Table 111 Polyester-based polyurethane is used for leather-like sheet materials that require durability, as phenomena such as countless cracks appearing throughout the entire substrate and the peeling of the cut polyurethane resin layer from the substrate occur. It is not suitable for worship. Furthermore, although polyether-based polyurethane has excellent hydrolyzability, it is subject to significant oxidative deterioration and is easily degraded by ultraviolet rays and heat. Therefore, it has been extremely difficult to enter the field of polyurethane-based leather-like sheets that require high durability.

Conventionally, pigments, dyes, or colorants containing these as main components have been used to color polyurethane-based leather-like sheets. Compared to coloring with pigments, coloring with dyes has clearer hues, transparency, and deeper color tones; and advantages such as a wide variety of colors. The colored leather-like sheet material has a luxurious feel. However, on the other hand, leather-like sheets colored with dyes have problems such as color migration, fading, fading, and bleeding. In order to prevent these problems, it is extremely important to select a polyurethane resin and to add a layer of polyurethane resin during the production of leather-like sheet products. In general, polyurethane absorbs and traps certain types of dyes relatively well, but the 8 degree is not enough, specifically, the dye may migrate from the polyurethane layer to other polyurethane layers or other poly 7 layers, causing dye fading. 1. Avoid hot fading due to exposure to light or heat, and avoid serious defects such as φ.

Honko Meisho et al. mentioned above. Durability, light and heat? Hox
Uncertain about dye fastness against gas and dye migration prevention,
As a result of 7C &'J' tests on leather-like materials that have low surface properties and a commercial-grade feel even when wet, polyurethane with a certain percentage was used, and these polyurethanes
7 is laminated with a high degree of restraint order, and now it is 1, 1,, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 2, 1, 2, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 11 Poor child J
It was winter. .

In other words, the high non-gathering leather-like shift snout with a brightness of 1% is composed of a fibrous base (1) and a polyurethane coating layer (11), and is coated with 1% Vj, (II) Sky yJ > At least the (I=a,) layer and (gb) of F
4m little c? Furthermore, (11-a)) a leather-like sheet in which Q exists between (0 layer and (g) layer 9,
9, of course.

The (II-, a) middle is.

(1) 3E in the polycarbonate chain, a diol and a chain oxide structure i (-CHFIb0
-');.

Is it a mixed diol mainly composed of diols that hold the molecule? It is a block coelectrochemical diol that has as its main components a 1'7' nate chain and an ethylene oxide structure in the 7 molecules. Trade name of any one of -(diol, and +C in this polymeric digol)
The ratio of k12CH20-+1 units to the highest molecular diol is 0 to 5M, and the average molecular weight is 600 to 50 (
What is the range of JO? 56 molecular diols (However, ``2-11
is the number of repetitions).

(2) Aliphatic or alicyclic organic diisocyanate (Jl υ) or alicyclic organic diisocyanate (4) Hydrazine or dihydrazide.

7L is substantially synthesized, and the ratio of 1 or the compound in (4) above to the compound in m1 (3) is small by molar.
? 1r polyurethane and this polyurethane, which were checked to have the following, 0.01 to 8: fflit%
4) within the range of ? It is formed from at least one dye selected from the group consisting of salt dyes, acid dyes, vat dyes, and sulfur dyes. In the layer, the (II-'b) jfi is □(5) polycarbonate di-, ru, having an average molecular weight in the range of 600 to 500.0, (6) aliphatic or alicyclic organic diisocyanate, (
7) aliphatic or alicyclic/organic diamine, and optionally (8) hydrazine or dihydrazide, and for the compound of item r2 above]
A polyurethane in which the molar ratio of the compound of 8) is 2.0 or less, and a dry film having a thickness of 50 μm made from this polyurethane is 100% at 20° C. and a tensile rate of 20 crn/min. % modulus [using an Instron 1'lv1M type universal tensile tester °C: L (resolution) with a size dumbbell is (15-X) ×, 5ky/c
rd, c However,
M:) IzO-4 sub'Mchi] larger than the (■
-a) 1 of 6d polyurethane before forming the layer L-'C
0:υ Timoji Tomoe 2S (1ll111 constant method, conditions are the same as above) A layer formed of polyurethane larger than 0:υ. , ' - Below, individual component costs and matters of the present invention will be specifically explained. ...: First, the fibrous substrate (1) constituting the present invention is made of, for example, entangled nonwoven fabric,
Fiber aggregates such as laminated non-woven fabrics, woven fabrics, and knitted fabrics, or their fiber bodies, are impregnated with a solution or dispersion of a polymer mainly composed of elastic polymers, and then condensed into a porous or non-porous structure. It was forced upon me. The fibers that make up the fiber aggregate include ordinary fibers, irregular cross-section fibers, high-shrinkage fibers, island-shaped fibers, metallic cross-section structure fibers, microfibril bundle fibers, and spiral-shaped fibers. and mixed fibers thereof are used. Microfibril bundle fibers and cylindrical fibers are made from special fibers with a sea-island cross-sectional structure spun from two or more types of polymeric substances with different solubility in solvents, and are dissolved in a single-component solvent. , obtained by removing debris. j゛That is, nuclear special N1. By dissolving and removing the sea component from the fiber, microfibril aggregate fibers are obtained, and by dissolving and removing the island component from the special fiber, a lotus-like fiber is obtained. In 2, the fiber and the coagulated polymer are in close contact with the tip (171, which is preferable). , polyvinyl chloride, polyamide, etc.

Next, the polyurethane handling layer (II-a) is formed from the polyurethane and dye as described above.
The polyurethane/diol used for the bottom base is the diol Q, the entire polycarbonate chain, the diol and the ethylene oxide structural unit +C112cth
o It is either a mixed diol containing frost/ol as a main component, or a block copolymer diol containing polycarbonate chains and ethylene oxide structural units as main components in the same molecule. However, the former is preferable in terms of performance and ease of handling raw materials. The polycarbonate chain is a group represented by +g-o-c-o (where R represents a divalent organic group and represents the degree of polymerization), but it is most common when R is a hexamethylene group. Polycanibonate chains in molecular diols have excellent hydrolytic and oxidative deterioration resistance (light resistance,
Since the material has a markedly excellent QC (heat deterioration resistance), polyurethane containing this material also has similar properties. The proportion of ethylene oxide structural units in the entire molecular diol used to synthesize the polyurethane constituting the dotted layer (■-a) is determined by the proportion of the ethylene oxide structural unit in the surface physical properties when wet and the dye that is unfavorable to photofading. In the case of synthetic leather with a small number of light-colored threads, if the light fastness is all important, a range of 0 to 5 kIk, % is good. When the amount exceeds 5% by weight, the dye retention is good, but for synthetic leather made of light-colored yarns that use less dye, the long-term light fastness acceleration test (persimmon, de-0-x
rr'eter 50' 0 hours or more) If you do this, fading will be more likely to occur (in the case of dark-colored synthetic leather with a large amount of dye, the light resistance will be low even if it exceeds 5 weight eIb): will not occur at all. ). Also, the degree of polymerization of the ethylene oxide chain + CH2CJJ20-In contained in the polymer diol! The number of 1 also slightly affects the durability, but it is 91 and 11.
If the average number of is less than 12, the resulting polyurethane has relatively low affinity with dye molecules, and even if dyes are added to such polyurethane, it will gradually degrade over time or as the temperature rises. The dye molecule is (lI=a)
When the dye migrates out of the layer, the dye fades in the leather-like sheet material, impairing the quality of the product. The average number of 11 is 1.
If it exceeds 00, the surface physical properties and water resistance of the resulting leather-like sheet material will be slightly poor, and C will also be slightly poor in terms of light resistance and the like. Especially if the average value of n is 1
The object of the present invention can be further achieved when the number is within the range of 5 to 80. Furthermore, the average molecular weight of high molecular diol is 60
0 to 5 (must be within the range of 10 (J), 60
If it is less than 0, the resulting Boliu I/Tan resin will have flexibility, resulting in poor texture, flexibility and surface properties of the leather-like sheet, while if it is more than 5000, it will be soft. If this happens too much, the elasticity is lost 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 (n-a) layer must be an aliphatic or alicyclic diisocyanate. The resulting polyurethane has poor light deterioration resistance, specifically causing negative light discoloration of leather-like sheets, deterioration of surface properties due to deterioration of the polyurethane, and furthermore, poor light fastness to coloring.

As for the chain extender, it is necessary to use aliphatic or alicyclic organic dibumin, and aromatic organic diamines have poor light deterioration resistance, etc., as in the case of the aromatic organic diisonoanates. The polyurethane coating layer of the present invention (I
In I-a'), since a polymeric diol containing polyethylene oxa-ide is used, the oxidative deterioration resistance is somewhat reduced, but in order to suppress this low oxidative deterioration resistance, the chain As a component of the extender, the molar ratio is 4.0 to human 2-f or dihydrazide/total diamine.
It is preferable to use it as shown below. Hydrazine/
By adding dihydrazide f:1, polyurekun has good heat resistance as well as light resistance, and further improves the light resistance and heat resistance fastness and properties of the dye arrangement. When it exceeds 4.0, the oxidative deterioration resistance of the leather-like notebook material is improved, but the hydrolysis resistance and blocking resistance are greatly reduced. .

The polyurethane coating *cti-a) of the present invention is a mixture of polyurethane obtained from the above-mentioned raw materials and dyes. Among these dyes, metal-containing complex dyes are particularly preferred from the viewpoint of preventing dye transfer. This is a dye in which a metal-containing mh salt dye and a metal atom/dye molecule form a complex salt in a ratio of 1=1 or 1:2, and usually have a sulfonamide group or a sulfonamide group in the molecule. Alkyl sulfone group, etc.'f
t, and has an overall negative load. The most common metal forming a complex salt is chromium, and other metals such as cobalt and copper are also used. 1; Type 2 metal-containing complex salt dyes are most preferred.

The polyurethane coating layer (II-&) is usually selected from among the pigments mentioned above, or by the method of adding at least one dye to the polyurethane solution and then removing the solvent from the polyurethane solution. However, the amount of dye to be blended is 0.000% relative to the polyurethane of the (, n-4) layer.
01 to 8% by weight. Moreover, in (II-, a), the thickness of the layer is preferably in the range of 1 to 500 μm.

In the leather-like sheet material of the present invention, the polyurethane coating layer (It
- polyurethane on top of a), a coating layer (It-,, b)
is formed. In this (n-bl) layer: by (II
-L) It becomes possible to prevent the dye within the layer from migrating to the outside of the layer, and the surface physical properties of the leather-like sheet material are improved, and furthermore, there are great advantages such as improved hydrolysis resistance. .

The polyurethane resin used for this polyurethane coating/*(n=b) can be obtained from the raw materials mentioned above,
To explain it in more detail, 1. First, as a polymeric diol, a polycarbonate diol having excellent hydrolysis resistance and oxidative deterioration resistance, and having a small crosslinker olephilicity and an average molecular weight in the range of 600 to 500 degrees, preferably 1.6-.

Hegyzandiol polycarbonate glycol is used.

A polyurethane having a polyether chain as a soft segment can be used with a polyurethane having a polyether polyol or a polyether polyol as a soft segment, or other polymers such as acrylic, Compared to cellulose threads and amide-based polymers, it has extremely low dye affinity and extremely high dye transfer prevention properties. For example, use polytetra, methylene glycol, or polypropylene glycol, which have good hydrolysis resistance, and use inoporo or diisocyanate T4 as an organic resin or soyanate, and use isophoroidiamine as a chain extender and the effect as an oxidative deterioration prevention agent. Polyurethanes synthesized using hydra and gin have good light resistance and hydrolysis resistance. Even though 7J triurethane using polyester is laminated with polyurethane coated with good glaze retention property (II-a), unexpectedly, the anti-pigment transfer property is rather poor and has the opposite effect. If the polyurethane used as the soft segment is laminated on (Ij-a)Id, then (Ij-a)
The mulberry retention property of the layer t-a,) is greatly improved.

In the present invention, +C$C1'LlO,,- of the (II-a) layer
'%, 'JpH8 is as low as 0 to 5:jJjt%, so the retention of dyed rice 1 is considered to be poor. Therefore, the (II-1)) layer is essential, especially the (lITb) layer of polyurethane. 10
0%, Moji, Yuras dye retention, surface properties, NOX resistance
In order to have a large effect on gas deterioration, and to be comprehensively satisfied from the point of view of concentration, it is necessary to +Cll2C)hO-4 by ■spear(,I[-1
3) The hardness of the layer must be changed to 0, i.e. (n-
b) Layer 1 - 20 cm of 50 μ thick dry film made from the constituent polyurethane at 20°C;
The 100% modulus at 1 tension speed [measured with a No. 3 dumbbell using an Instron i' M M fJ-fi HP tensile tester] is (1,5='X) X 5
kg/lnj I: However, - ``a) 1 of the polyurethane constituting the entire layer.
'00'% modulus (measurement method and conditions are the same as above)
NUx gas fading and dye retention can be achieved by determining the polyurethane raw materials or their proportions so that they are more
I-11) It is particularly effective to have a layer r,
II-a') Dye trapping ability of layer [+Cj-12CII20
-1i1 content] has good NOx resistance, fading resistance, and dye retention. Because of the seven (II-a,
) layer +C1hCH2<) The lower the i conjugate, the more (
'II-b) Increase the 100% modulus of the layer, (I
It is better to minimize the difference from the 100% modulus of layer I-a).

In addition, since it is essential that the polyurethane used in this (II-b) layer has the ability to prevent dye migration, the 1% molecular diol is a dye-philic group, such as an ethylene oxide structural unit + CI It is important to have substantially no -4°C.

(II-b) The organic diisocyanate used for synthesizing the polyurethane for M is an aliphatic or alicyclic diisocyanate, and the chain extender is an aliphatic, aliphatic, or alicyclic diisocyanate. If necessary, hydrazine or dihydrazide, which is a diamine in the system, is used in combination as part of the chain extender, but in that case, the molar ratio of hydrazine or dihydrazide to the 7h diamine must be 2.0 or less. is important. 2. - If it exceeds 0, the oxidative deterioration resistance will improve, but the ability to prevent dye migration, hydrolysis resistance, and blocking resistance will decrease significantly. When diisocyanate and diamine components other than aliphatic or alicyclic are used, the light deterioration resistance is significantly lowered and the (la) layer discolors. That is, polyurethane containing an aromatic diisocyanate or diamine gold phase is decomposed by light, and the radicals generated by this decomposition attack the dye molecules present in the (na) layer.
As a result, the dye molecules are decomposed and denatured, resulting in fading.

Polyurethane coating layer (II-a) and (ub)i
Typical examples of the 11r aliphatic or alicyclic organic diisocyanes used in 1. Easy cyclo-＼
Gysylmethane diisono, -(water-added MDx), ingropylidene bis(4-cyclohexyl isocyanate), inphorone diiso-7anate, lysine diiso/i=-i:, water-added xylyleyrein cyanate, cyclohexyl isocyanate, etc. It will be done. Typical examples of the aliphatic or alicyclic organic diamines include enale/ditemin, heglymethylene diamine, inphoron diamine, ``4'', 4'-diaminodicyclohexylmethane, piperazine, cyclohexylene diamine, etc. In addition, hydrazine or QJ dihydrazides include hydrazine, hydrazine water A11,
N,N'-dimenal hydrazide/adipate dihydrazide, sebacic acid dihydrazide, glutaric acid dihydrazide, isofucric acid dihydrazide, β-semi-rubazidopionic acid dihydrazide, etc.
□The polyurethane coating layer (n-b) is usually formed by a method of removing the solvent from the polyurethane liquid d, and is
b) The thickness of the layer C is preferably in the range of 1 to 100μ.

The leather-like sheet material Q of the present invention has a fibrous base (1), a polyurethane coating layer (1-a), and (11) essential components.
-b) k, but in addition to these, for example <n-
&) Between the layer and the substrate (1), a polymeric diisocyanate component or a rigidisocyanate component consisting essentially of a polycarbonate polyol is added to an aliphatic or alicyclic organic polyisocyanate.
A polyurethane coating layer < n = (! > ) may be provided, which allows the dye in the (■-a) layer to be transferred to the substrate (1
), and as a result, a leather-like sheet material with extremely good dye retention properties can be obtained.

In other words, all of these laminated polyurethane resins have good light resistance, heat resistance, NOx gas resistance, etc., so they are resistant to light, heat,
'Dye fading does not occur at all even with NOx gas, and furthermore, it has good dye retention property against solvent chemicals, so it is superior to conventional leather-like sheet materials in terms of dye fading and surface properties when wet. You can see the groundbreaking Mukai'2 in comparison. .

The polyurethane e1 used in the polyurethane coating layer (IL-(!')) is typically synthesized by the following methods.Hegizamethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate is used as the polyincyanate component. ), 4.4'
-Produced by reacting isocyanates such as dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, and cyclohexane isocyanate, or these diisocyanates with polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol. Polyisocyanates with trifunctional or higher functional isocyanate terminals are used, and polycarbonate-based polyols or polyurethanes having at least two or more U) groups in the molecule are used, or polycarbonate diols and aliphatic or fatty acids are used. Breposit Nia T having a terminal isocyanate group from a cyclic organic diisocyanate is textured and then chain-extended with an aliphatic or alicyclic diamine. Similarly, if necessary, hydrazine, hydrazine, or hydrazide may be used in combination as a chain extender.The thickness of (l-(ri#) is usually in the range of 1 to 5.00 .mu.m.

, and polyurethane coating layer (C) and u (1I-a)
As for the layer, it also occurs in the form of a dry non-film, and the layer structure has a
Even if fortune-telling, texture, appearance, volume, resistance to shaving,
It is preferable to have a foamed structure rather than one with folds and wrinkles, as it gives a more luxurious feel. These (ll=a) layers of reeds,
(,]1.;b,) layer % (II-C,,) layer ■=
4. ．． ) Even if N contains stabilizers, additives, or even polymers that do not damage the dye,
In order to foam and form a layer, various foaming agents are mixed with polyurethane resin and heated to decompose the foaming agent, or polyurethane resin is dissolved in a water-miscible solvent for mold release properties. A method of obtaining a sponge sheet by coating it on top, spreading it, dipping it in water and coagulating it, using a foaming machine to foam a high-yellow polyurethane emulsion and then coating it on a releasable support. Foam, heat, bush 2 Vh j Sea urchin drying method, A 6 "is 7', method using urethane 7 ohm manufacturing technology by Yotsuto method, and y% Rio □.
・A method is known in which a foamed layer is formed by heating a compounded solution consisting of an organic polyisocyanate, a blowing agent, and an M-organic solvent, and generating bubbles by volatilizing the solvent and decomposing the foaming agent, and many other methods. may be produced by any method.

Furthermore, since the leather-like sheet material of the present invention has a light color with a small amount of dye in the (If-8) layer, when it is made into a leather-like sheet material, the color, embedding, and unevenness of the substrate (1) The spots will appear to have disappeared, but this is due to the 7m polyurethane coating.
(n-(It is preferable to cover it up with titanium oxide), and for light-colored yarns that are disadvantageous to dye fading, especially for Yang Kai, which requires strict durability, it is preferable to use a color similar to the dye. A pigment having (■-C
) It is preferable to add it to the layer to hide it from the viewpoint of improving the appearance and imparting the light resistance of madder. □,
...As a method for obtaining a leather-like sheet material of the present invention, an <n-'='> layer is formed on a substrate (1) or on a support having a (n-'b') layer structure. After drying, dye the layer by immersing it in the dye solution to form layers (11-b') on the dyed material. It is also possible to use the method of gluing (1) together, etc. It is generally preferable to use this method, especially when vat dyes or sulfur dyes are used as the dye.

Furthermore, in the leather-like sheet material of the present invention, on the polyurethane coating layer (■) to increase the surface strength, the colored glossy gold W〃Arizu A' tacked polymer layer, and further between each polyurethane coating layer ( n-a) A polymer layer or the like that does not cause decomposition or modification of the dye contained in # may be inserted as an f* layer.

Next, a typical cross-sectional layered structure of the leather-like sheet material of the present invention will be explained with reference to the accompanying drawings.In FIGS. 1 and 2, 1 is a fibrous base (1)%2. - 3 and 4 represent the polyurethane coating layer (II).

Referring to Figure 1, [Polyurethane coating layer ■ is polyoxyethylene polycarbonate polyurethane layer containing dye (il' = 'a'): 2 and...9 Polyurethane layer is polyurethane layer containing dye. (II□-b) = 3, and in Fig. 2, the polyurethane coating layer ■ is further made of... polycarbonate thread polyurethane layer (
■□-c): It has 4ft.

The following is a detailed explanation of the first embodiment ψ based on an example.

In addition, the biohydrolyzability of the example refers to the stickiness of the surface caused by leaving the obtained leather-like sheet material in an atmosphere with a homogeneous humidity of 9'5% and a temperature of 70°C (jungle test conditions) for 10 hours. Cracks, peeling of memory 1-, and dye fading (presence or absence of dye transfer and adhesion when wet) were investigated. In addition, the light resistance is 5o'o at 63℃ ambient air under makeup.
This is a graph of dyeing and fading when exposed to light using a carbon arc lamp for an hour.Also, the heat resistance is measured by treating the dye in an oven at 120°C for 50 hours and examining the fading of the dye after burning. . NOx gas resistance refers to the color fading of the dye when left in a 50 p'pm NOx gas atmosphere for 24 hours. Judgment was made using If the fastness is 5th grade, there is no fading at all, and as you go down to 4th grade, 3rd grade, or 2nd grade, the fastness decreases, and 1st grade is a case where the fastness is likely to be fake and is defective.

Also, the dye migration property is 5 crn・x! Prepare a white polyurethane sheet of the same size as a test piece of i cm size, and place the white polyurethane sheet on top of the test piece,
A glass plate (size 1.0cm x 1cm x 3cm) was used, and a load of 7kf was applied (press bonded for 24 hours in an open environment at 70°C, as a result of which the dye from the test piece was transferred to the white polyurethane sheet). β is a judgment of the degree of migration.
Ru. The determination was made based on the level of contamination on the gray scale gold scale, grades 1 to 5. The surface properties and the surface properties when wet with water were tested using a tapered abrasion tester with a load of M, 1, and 1,000 times of friction, and then using a fold tag tester (Custom type) with a load of 2 and 3,000 times of friction. This is the result of observing the degree of surface wear in the case. In measuring the surface properties when wet, the sample was immersed in water at 30° C. for 24 hours, then rolled with a nip roller, and then the taper and cast were measured. If there is no change, it is indicated by ○, if it is slightly scratched, it is indicated by Δ, if it is scratched so much that the base is visible, it is indicated by
A test piece the size of an? Prepare a sheet and rub the bones with water so that they are in contact with each other.A load of 3 kf is applied to this.
Be strong, 7? It was determined whether there was a sticky sound when peeled after leaving it for 24 hours at ℃.0 In addition, in the example, the polymeric diol used as the raw material for the polyurethane that was used once again, with diisocyanate. Although compound 2 and the chain extender are shown using abbreviations, the relationship between the abbreviations and the compounds is as follows.

Abbreviation Compound 1) EG Polyethylene ether glycol PB
A ff1lJ Butylene adipate glycol I
PLII Inholoncy,/Cyanate) h2M
DI Synchlohexylmethane-4, diisocyanate [1)l Hexamethylene diisocyanate Abbreviation Compound H12DAM '4,4'-Diaminodicyclohexylmethane 1-LM Hydrazine Q Hitlerd AI)H Adipic acid dihydrazide 11) M Isophthalic acid dihydrazide EG
Ethylene glycol TMP) Limeterol propane Examples 1 to 15
．． Comparative Examples 1 to 14 Polyurethane coating layers (II-b), (1
1-a) layer, optionally (II-
(2.00μ for a foam layer) using a knife coater, and while it still has some tackiness, it is pasted on the base (I) (cotton layer blanket) and dried by heating. After that, the release paper was peeled off and the dyed leather-like sheet material was prepared. Table 1 shows 7 points.
), lil: 'type 2-containing genus 4 + tl staining 1t no I', r
Hrcym G'AL? (', JI-'a)
It is added in double % to the polyurethane of H.

In Example 15, Ir, Br 11G
I also replaced L with the acidic dye 5olar Red S. In addition, in the (I[-C) layer, i'1
02 (rutile type) and pigment were used.

The durability, color fastness, dye migration, surface properties, and other physical properties of the 41 sheets of leather to be chewed were compared, and the results are shown in Tables 2 and 3. It is clear from the table that the sheet material of the present invention has outstanding durability, dye retention, and dye fastness.

[Brief explanation of the drawing]

Figures 1 and 2 show one part of the leather-like sheet's proboscis of the present invention.
1 is an Ir plane view, and FIG. 1 is a diagram when the polyurethane coating layer is composed of two layers, and FIG. 2 is a diagram when the polyurethane coating layer is composed of three layers. LJV applicant RiRa Co., Ltd. Representative patent attorney Ken Honda

Claims (1)

[Claims] 1. Consisting of a fibrous base and a polyurethane coating layer (II), and the polyurethane coating layer (■) includes at least the following (, 11-a) layers and (,, II r , lb )
The layer (II-a) is composed of the layer (1) and the layer (II-a).
■-1,b) In the leather-like sheet material existing between the layers, the layer ('II-,a) is composed of (1) mainly composed of polycarbonate chains, diionyl and ethylene carbonate. Id structural unit −←Cf(2C
HzO-'l, a mixed diol mainly consisting of a gold-containing diol, or a block copolymer diol containing a polycarbonate chain and ethylene oxide (iq) as the actual component in the same molecule. is any polymeric diol with an average molecular weight of 600 to 5000, and the proportion of hQ units in this polymeric diol is 0 to 51t% based on the total polymeric diol. Polymer diols within the range (however,
The above n is the number of repetitions). (2) Aliphatic or alicyclic organic diisocyanate-1, (
8) Substantially synthesized from an aliphatic or alicyclic organic diamine, and, if necessary, (4) hydrazine or dihydrazide, and the above (4) for the chemical/metallic compound of (8) above.
) polyurethane which satisfies the molar ratio of the compound of 4.0 or less, as well as metal-containing complex salt dyes, acid The fc layer is formed from at least one dye selected from the group consisting of dyes, vat dyes, and sulfur dyes, and the ([-=1)) layer has (5) an average molecular weight in the range of 600 to 500σ. polycarbonate diol, (6) aliphatic or cycloaliphatic organic diincyate, (
7) Aliphatic or cycloaliphatic organic diamine, and optionally (8) ε-dolazine or dihydrazide. Substantial synthesis from! 9L5 and the molar ratio of the compound (8) to the compound (l) above is 2.0.
The following polyurethane: tan, 61, from this polyurethane □. Manufactured thickness: 5? μ's,, dry method 74. ~20℃・
The 100 stroke modulus at a tensile speed of 20 cm/min [measured with a No. 3 dumbbell using an Instron T M M type CJ1 tension tester] is '(''1 '5-X)
x 5 kg/eril ['However, X is (11-a
) / All 1 used in the synthesis of polyurethane that makes up soap
The width of the molecular diol □ is longer than (-C[bC)L+O+n weight%], and the 100 timothy 2s (measured Method, medicine jacket 'n previous grandchild and Naoki ) formed from larger polyurethane! A leather-like sheet material having excellent durability with all the characteristics of 1,' □. 2. Between the polyurethane 4I layer ('II-a'') and the base layer (1), a polyurethane coating layer (■ -c
) The leather-like sheet material according to claim 1, wherein the temperature is .degree. ),,... 3. Titanium oxide on polyurethane layer (1-C)
1-4' %rf Leather according to claim 2 to which pigments and pigments have been added! sheet thing. 4. Claim 1, wherein the dye contained in the polyurethane coating layer (II-+a') is a metal-containing complex dye.
The leather-like sheet material according to any one of items 1 to 3.