JPH02251682A - Colored artificial leather - Google Patents

Abstract

PURPOSE:To provide the subject artificial leather consisting of a fibrous aggregate and polyurethane elastomer, rich in both deep color tone and dense color feeling, having a surface layer colored with a colorant of hue with specified relation to that of the substrate layer. CONSTITUTION:A substrate layer consisting of a fibrous web made up of ultrafine fiber is impregnated with a polyurethane composition liquid incorporated with a colorant except for black so as to be >=3 in the coloring concentration K/S-value at the maximum absorption wavelength, and coated with a polyurethane liquid containing a second colorant with the hue on color ring >=3 away from the color tone of the former colorant or falling at a complementary color (e.g. consisting of either white pigment, silver pigment or gold pigment) to form a surface layer, thus obtaining the artificial leather rich in both deep color tone and dense color feeling with the surface hue superposed on the substrate color tone.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to artificial leather having a surface coating layer, which imparts depth and dark color to the surface color. be.

<Prior Art> Conventionally, artificial leather, which is a field of leather-like sheet materials, has been colored in various colors and patterned in various tones as products are diversified.

However, the base sheet that is processed in large quantities has a white base layer.
It is a simple coloring such as thermal coloring or blue tinting, and the surface layer is not colored too much, but the coloring is done exclusively by the finishing layer applied to the surface of the surface layer. Conventionally, artificial leather is colored using a base sheet colored in a similar color to the surface color tone. For example, leather in which colored synthetic resin layers of different tones are formed on fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics to a thickness of 2J11 or more is disclosed in JP-A No. 49-6Q801, JP-A No. 43-4670, and JP-A No. 43-4670. 61・=1
No. 08776, Japanese Patent Publication No. 59-22823, 1 & Artificial leather having a fibrous base layer and a porous layer, the base layer is a colored layer with a colored pigment added, and the surface layer contains no or only a small amount of coloring agent. JP-A-58-65 discloses an artificial leather that has a colored layer and is given decorative properties by heat embossing.
This method has been proposed in Japanese Patent Publication No. 074, Japanese Patent Application Laid-open No. 60-239572, Japanese Patent Publication No. 59-32299, Japanese Patent Publication No. 61-42019, etc.

<Problems to be Solved by the Invention> In conventional artificial leathers, the coloring is merely on the surface, and in the case of artificial leathers that are given decorative properties, the coloring of the base layer or the coloring of the lower layer is not visible on the surface. Since the composition is not based on the premise of improving the surface color tone or deep color feeling, the color tone is the raw color tone of the colorant itself, and the color tone may not be sufficiently complex or ambiguous on the surface.

The object of the present invention is to provide the first artificial leather that has a color tone that cannot be obtained by blending a colorant (not a natural color tone), and has a deep color feeling.

<Means for Solving the Problems> The present invention provides a base layer containing an elastic polymer mainly composed of polyurethane in a fiber composite;・In artificial leather consisting of a surface layer of an elastic polymer mainly composed of silica, the hue on one color wheel is 3 or more compared to the hue of the colored base layer.
:Characterized by having a surface layer colored with a coloring agent in a distant or complementary color? : Colored artificial leather.

The present invention also provides an artificial leather comprising an elastic polymer mainly composed of polyurethane in the fiber aggregate, and a base layer and a surface layer of the elastic polymer mainly composed of polyurethane.
When the base layer is colored with a coloring agent other than black, the coloring density K/S value (K is the absorption coefficient and Sl is the scattering coefficient) is determined by the Kubelker-Munk equation at the maximum absorption wavelength.

(hereinafter the same) is 3 or more, and the surface layer is colored with a coloring agent that is 1° complementary color with no hue on the color wheel that is 3 or more away from the hue of the base layer. It is a colored artificial leather characterized by:

Furthermore, the present invention provides that the base layer containing an elastic polymer mainly composed of polyurethane in the fiber aggregate is colored with a coloring agent other than black, and the coloring density K/S value is 3 or more, This is a colored artificial leather characterized in that the surface layer is mainly made of an elastic polymer and has a surface layer colored with a white pigment, a silver pigment, or a gold pigment.

That is, the present invention provides a method for manufacturing artificial leather consisting of a base layer containing an elastic polymer mainly composed of polyurethane in a fiber aggregate and a surface layer of an elastic polymer mainly composed of polyurethane. Add a coloring agent other than black to the polymer solution or dispersion at the maximum absorption wavelength after coloring.
The solution or dispersion of the surface layer-forming elastic polymer is added in an amount such that the S value is 3 or more, and the solution or dispersion of the surface layer-forming elastic polymer is colored with a hue that is 3 or more hues away on the color wheel from the hue of the colored base layer. A sheet obtained by adding a coloring agent or complementary coloring agent, a white pigment, a silver pigment, or a golden pigment, and solidifying a solution or dispersion of an elastic polymer to which the colorant has been added. This is a method for producing colored j-artificial leather, which is characterized by finishing a shaped article.

The base layer constituting the artificial leather of the present invention has a fiber aggregate selected from the group of polyester fibers, polyamide fibers, polyolefin fibers, polyacrylic fibers, polyvinyl alcohol fibers, regenerated cellulose fibers, etc. At least 1 fiber selected from these fibers, or an ultrafine fiber-generating multicomponent fiber made of one type of polymer such as polyester, polyamide, polyester 17 fin, or polyvinyl alcohol.
These are fabrics such as woven fabrics, knitted fabrics, non-woven fabrics, etc. made of IIA fibers, or fabrics such as fiber napped woven fabrics or knitted fabrics. Preferably, using a fiber entangled nonwoven fabric obtained by forming a fiber web using ultrafine fiber-generating multicomponent fibers and subjecting it to fiber entanglement treatment, before or after containing the elastic polymer, Nonwoven fibers are treated with solvents, decomposers,
Alternatively, it can be subjected to any of the splitting treatments and used as a fiber B intertwined nonwoven fabric of ultrafine reed bundled fibers made of ultrafine fibers with a semi-fiber average age of 0.2 denier or less. or,
Ultra-fine # of less than 0.8 denier obtained by spinning and stretching! A far entangled nonwoven fabric obtained by forming a fiber web with ρ and subjecting it to fiber entanglement treatment can also be used.

The weight of the fiber aggregate is determined by the method of the artificial leather, but generally it is 1! The amount ranges from 50 to 500 g/.

J: The polyurethane contained in the aggregate and the polyurethane constituting the surface layer have an average molecular weight of 850
0=3000 at least one polymer diol selected from the group of polyester diols, polyether diols, polyester diols, polylactone diols, polycarbonate diols, aromatic diisocyanates, aromatic triisocyanates, ~1 - at least one type of organic polyisocyanate selected from the group such as alicyclic diisocyanate, aliphatic diisocyanate having a cyclic group, and a diol as a chain extender;
It is a polyurethane obtained by reacting at least one compound selected from the group of low-molecular compounds having at least 2 fA of active hydrogen atoms, such as diamine, hydrazine, and dioxyamine, in a desired composition ratio. A preferred polyurethane has a viscosity of 0 at 30°C of a 10% polyurethane solution dissolved in N,N-dimethylformamide.
゜s=i.

It is Poise polyurethane.

The coloring agents used for coloring the elastic polymer are inorganic pigments, organic pigments, and pigments made from metal powder, but inorganic pigments and 1. In addition to the usual coloring pigments, there are C types that contain extender pigments. In addition, as Ariiso pigments, -1 Japanese pigments, azo pigments, acid dyes 1 to 1, basic dye lakes, vat dye pigments, isoindolinone pigments,
There are pigments selected from mordant dye pigments, quinacridone dyes, phthalocyanine pigments, etc., but any dye may be used as long as it causes less IK loss during the manufacturing process of artificial leather.

The amount of the colorant added varies depending on the coloring property of the colorant used, and the color density 1c/S determined by the Kubelker-Munk equation at the maximum absorption wavelength of the colored base layer.
value (where K is the absorption coefficient and S is the scattering coefficient) is 3
The above amount of colorant is preferably added in a range of 3 to 15. Generally, the amount of colorant is 5N% based on the elastic polymer.
This is the amount above.

When the K/S value is less than 3, although it is colored, it does not have a deep color that dominates the color of the surface coating layer. Furthermore, the coloring properties vary depending on the processing method of the artificial leather. For example, if an elastic polymer solution containing a coloring agent is coagulated by a wet coagulation method, color development is poor, but if it is coagulated by a dry coagulation method, color development is good. For this purpose, when producing a colored base layer by the tunnel coagulation method, the fiber aggregate is impregnated with an elastomeric polymer solution mainly composed of polyurethane containing a small amount of coloring agent, and then treated in a non-solvent of the polymer. and wet coagulation,
To the base layer obtained by drying, a colorant is added to an elastic polymer liquid dissolved in a solvent that does not attack the base material or dispersed in a dispersant to form a polymer composition liquid, and then impregnated into the base layer. ,
When coagulated by a dry coagulation method, a substrate layer with good color development can be obtained with a small amount of colorant.

On the other hand, the surface layer is colored with a coloring agent whose hue is three or more hues away from the base layer or a complementary color, a white pigment, a silver pigment, or a golden pigment. The surface is colored with any pigment. In addition, the "color wheel" as used in the present invention refers to primary colors, secondary colors, and tertiary colors.
A color wheel is used, which is made up of 12 next colors as basic colors.

[Hue 1 with three or more hues on the color wheel] is a hue that is 17 or more hues away from a certain hue on the color wheel, and is 4th or more. It is no secret that the hue on a color wheel composed of higher-order colors is 3 or more mh. In the present invention, by using colorants with different hues for coloring the surface layer, it is possible to obtain a deep bed of different colors in the surface coloration that cannot be obtained by mixing colorants. If the hue of the base layer and the hue of the surface layer are close to each other, the effect of imparting a deep tone or improving color development cannot be obtained. The depth of the color tone of the surface layer can be determined from a light color to a dark color based on the product design. The surface layer is obtained by adding a colorant to a polyurethane solution or dispersion and coagulating it by either a wet coagulation method or a dry coagulation method.

The colored artificial leather obtained in the present invention can be surface-finished as necessary, such as by adding a coloring agent to the extent that does not damage the base material, applying a finishing agent such as a clear finishing agent or a matte finishing agent, embossing, etc. The product is processed through processing, rubbing, etc.

The colored artificial leather obtained in the present invention is an artificial leather that has a deep color tone and a deep color feeling that cannot be obtained with a raw colorant on the surface. This artificial leather is used for clothing, accessories, supplies,
It is used for bags, shoes, etc., but is especially suitable for sports clothing, shoes, etc.

Effect〉 In artificial leather consisting of a base layer containing an elastic polymer mainly composed of polyurethane in the fiber aggregate and a surface layer of an elastic polymer mainly composed of polyurethane, the base layer is light-colored with a coloring agent outside the harness. The surface layer is colored with a coloring agent whose hue on the color wheel is three or more away from the coloring hue of the base layer, a white pigment, a silver pigment, or a gold pigment. By forming a surface layer, the color tone of the surface overlaps with the color tone of the base, giving a deep color tone and a deep color feeling that cannot be obtained with a raw colorant.

<Examples> Next, embodiments of the present invention will be described using specific examples, but the present invention is not limited to these examples. Note that parts and percentages in the examples are by weight unless otherwise specified.

Example 1 A fibrous web was made from ultrafine fibers made of polyethylene terephthalate and polyethylene, short fibers of multicomponent fibers, and subjected to fiber entanglement treatment to obtain a fiber entangled nonwoven fabric with an average basis weight of about 600 g/m''. As a nonwoven fabric impregnating liquid, a composition liquid containing 18% polyethylene adipate polyurethane, 5% inorganic yellow pigment, 1% coagulation regulator, and 76% dimethyl formamide (hereinafter abbreviated as DMF) was prepared. Tetramethylene ether/polyethylene adipate (60:40) polyurethane 20%, inorganic blue pigment 6% (difference on color wheel 5), coagulation regulator 1.6
%, and a composition solution containing DMF of 72.4% was prepared.

First, a fiber-entangled nonwoven fabric was impregnated with an impregnating liquid, and then a coating liquid was applied in an amount of 150 g/m'', and the fabric was treated in a 50% DMF aqueous solution to solidify the polyurethane to obtain a sheet-like article.

This sheet-like material was treated in heated toluene to dissolve and remove the polyethylene of the multi-component fibers, thereby producing polyethylene terephthalate ultrafine fiber bundles. The surface of the obtained sheet-like material was coated with a polycarbonate-based polyurethane clear ink containing a light stabilizer, and heated and embossed to make it into artificial leather.

The obtained artificial leather has a base layer colored yellow,
The /S value at the maximum absorption wavelength was 9.7, and although the surface was colored blue, the bottom part had a yellow-greenish tone, and the color tone had a deep tone. This artificial leather was suitable for use in sports shoes.

Example 2 Nonwoven fabric impregnating liquid contains 18% polyethylene adipate polyurethane, 5% inorganic blue pigment, 1% coagulation regulator,
A composition solution containing 76% DMF was prepared and used as a surface coating solution.
20% polycaprolactone polyurethane, 6% inorganic red pigment (difference on color wheel 5), coagulation regulator 1.3%, DM
A composition solution containing F72.7% was prepared.

Next, the nonwoven fabric of Example 1 was impregnated with the impregnating composition liquid, and the coating composition liquid was applied at a target amount of 500 g/m''.
The polyurethane was coagulated into a porous structure by treatment in a 40% MF aqueous solution to obtain a sheet-like product. This sheet-like material was finished in the same manner as in Example 1 to obtain artificial leather.

The obtained artificial leather has a base layer colored deep blue, an S value of 5.2 at the maximum absorption wavelength, and a deep red-red color tone with a slightly blackish bottom part on the surface. there were.

Comparative Example 1 In the production of the artificial leather of Example 2, a composition liquid similar to that of Example 2 was prepared using 6% of a purple pigment (difference on the color wheel: 2) as a coloring agent as a surface coating liquid. The liquid was applied to obtain a sheet-like product, which was then finished to make artificial leather.

The surface of the obtained artificial leather had a dark purple color close to that of a quince color, and had no cool color tone.

Example 3 Average basis weight 3 of entangled nonwoven fabric of nylon-6 ultrafine fiber bundles containing polyethylene adipate polyurethane
Polyurethane emulsion (concentration 40% > 10
0 parts, 5 parts of azo type stock pigment, 0.5 parts of penetrant, and 60 parts of water were impregnated, squeezed to give a coating rate of 117%, and dried to give a reddish-orange sheet (A). I got it. This sheet-like material has a N/S value of 6.2.

The negative surface of the sheet material (A) is smoothed, and the polyurethane solution to be applied to the smooth surface contains 18% polycaprolactone polyurethane, 5% titanium oxide, and 1.3% coagulation regulator.
%, DMF 75.7% polyurethane composition liquid was adjusted,
This polyurethane composition liquid was applied in an amount of 440 g/m'' and coagulated in a 40% DMF aqueous solution to form a surface layer.Then, a finishing agent containing titanium oxide was applied to the surface using a gravure method, and embossing was performed. It was made into artificial leather.

This artificial leather has a reddish white color on the bottom, giving it a unique warmth.

Example 4 As a surface coating polyurethane solution, 12% polycarbonate polyurethane, 5% azo blue-green pigment (a hue complementary to the hue of the sheet material in Example 3), and 0.5% light stabilizer. A polyurethane composition liquid consisting of 82.5% organic solvent was prepared, and this polyurethane composition liquid was applied to the smooth surface of the sheet material (A) obtained in Example 3 by a roll coating method in an amount of 25 g/cm2 as solid content. After applying, dry
It was embossed and made into artificial leather.

This artificial leather had a deep blue-green color with a reddish undertone, giving a sense of warmth.

Example 5 A polyurethane composition containing 10% polycarbonate polyurethane, 6% gold metal pigment, 0.5% light stabilizer, and 83.5% organic solvent was prepared as a surface coating polyurethane solution. The smooth surface of the sheet material (A) obtained in Example 3 was coated with a solid content of 28 g/m'' by a roll coating method, dried, and embossed to obtain artificial leather.

The silver color of this artificial leather became even more dazzling, giving it a darker feel.

<Effects of the Invention> The artificial leather of the present invention has a hue relationship between the base layer and the surface layer.
The hue of the surface layer is a primary color, a secondary color,
By coloring with any one of the following colorants, white pigments, silver pigments, and gold pigments, whose hues on the color wheel consisting of tertiary colors are three or more hues or complementary colors,
The color tone of the surface overlaps with the color tone of the base, resulting in artificial leather with cool, dark, and warm tones that cannot be obtained with raw colorants.

Claims (3)

[Claims] (1) In artificial leather consisting of a base layer containing an elastic polymer mainly composed of polyurethane in the fiber aggregate and a surface layer of an elastic polymer mainly composed of polyurethane, the color ring corresponds to the hue of the colored base layer. 1. A colored artificial leather characterized by having a surface layer colored with a coloring agent whose top hues are three or more hues apart or complementary colors. (2) The color density K/S value (K is absorption coefficient, S is scattering coefficient, and the same applies hereinafter) obtained by the Kubelker-Munk equation at the maximum absorption wavelength when the base layer is colored with a colorant other than black. The colored artificial leather according to claim 1, wherein is 3 or more. (3) The base layer containing an elastic polymer mainly composed of polyurethane in the fiber aggregate is colored with a coloring agent other than black, and the color density K/S value is 3 or more, and the base layer is mainly composed of polyurethane. A colored artificial leather characterized in that the surface layer of an elastic polymer has a surface layer colored with a white pigment, a silver pigment, or a gold pigment.