JPS5845503B2 - Pearl Kannos Greta Dalchiyou Hikakujiyoushi Tobutsu Oyobi Sonoseizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dull leather-like sheet material with an excellent pearly feel and a method for producing the same.

More specifically, a pearl-like shine and three-dimensional effect can be obtained by applying a polymer solution containing a pearl pigment or a dye to a porous substrate, and then applying a polymer solution containing a matting agent. The present invention relates to a leather-like sheet product and its manufacturing method.

Leather-like sheet products obtained by finishing treatments such as coloring, embossing, fir or enamel processing are widely used for shoes, bags, zori, interior materials, etc.

The color of the surface of a leather-like sheet product is an important factor that influences its commercial value.

Carbon black is currently used to color the surface of leather-like sheets.
Inorganic pigments such as titanium oxide and barium sulfate, organic pigments and dyes such as fucrocyanine and anthraquino pigments are used.

When pigments are used as coloring agents, only cloudy products are obtained, so-called non-transparent products, but when dyes are used, products with sharpness and considerable commercial value can be obtained.

Therefore, recently, dye-colored products by methods such as coating with a polymer solution containing a dye or dyeing in an aqueous dye solution have become far more common than pigment-colored products.

However, now that natural leather, artificial leather, and synthetic leather have become extremely abundant, there is a strong demand for the development of products that are even more fashionable and luxurious in leather-like sheet materials, just like clothing. It's here.

As mentioned above, in order to produce a leather-like sheet product with a high-class feel, there are limits to coloring using only dyes as well as pigments.

Therefore, the inventors of the present invention investigated numerous finishing agents and a wide range of finishing methods, and found that by using sparkling pearl pigments, dyes, and matting agents under specific conditions, products with extremely high-class product value could be achieved. It has been found that products with high productivity can be obtained with high productivity.

Conventionally, methods have been proposed in which a general dye or pigment as described above is used in combination with a matting agent, but the vividness of the color and the matting effect are incompatible with each other.

In other words, it is not used very often because it is not possible to achieve mattness while maintaining the clarity of the color.

Similarly, using a method that uses a mixture of pearl pigments, dyes, and matting agents at the same time makes it difficult to obtain the desired color, which not only results in poor productivity but also increases the degree of matting and color. The sharpness of the image and the sparkling pearl effect are greatly impaired.

In the present invention, a pearlescent feel can be achieved by sequentially applying appropriate amounts of a polymer solution containing pearl pigment alone or a suitable amount of a pearl pigment and a dye, and a polymer solution containing an appropriate amount of a matting agent on the surface of a porous substrate. It is an object of the present invention to provide a leather-like sheet with a good and dull texture.

With the present invention, for the first time, a desired color can be easily obtained, and a leather-like sheet product with high productivity and high added value can be obtained.

This fact is a unique phenomenon when pearl pigments are used, and is truly surprising.

First, the base of the leather-like sheet product of the present invention is composed of a fiber aggregate and a polymer mainly composed of a polyurethane elastomer.

Fiber aggregates include single spun fibers such as cotton, rayon, nylon, polyester, polypropylene, polyacrylic acid l-IJ, mixed spun fibers or composite spun fibers of nylon, polyester, etc. and polystyrene, polyethylene, polypropylene, etc. Knitted fabrics, woven fabrics, non-woven fabrics, and felt are used.

Polyurethane elastomers are composed of soft segments such as polyethylene glycol, polyhexamethylene glycol, polyethylene adipate glycol, polyethylene adipate glycol, polycaprolactone glycol, etc. with a molecular weight of 500 to 4000, and ethylene glycol, butanediol, ethanolamine, hydrazine,
It consists of a chain extender such as 4°4'-methylenebis(2-chloroaniline) and a diisocyanate such as diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, etc.

The polyurethane elastomer contains fillers, pigments, softeners, antistatic agents, etc., as well as polymers with good compatibility in a solution state,
For example, polyvinyl chloride, polyvinyl formal, polymethyl acrylate, a copolymer of vinylidene chloride and acrylonitrile, a copolymer of vinyl chloride and vinyl acetate, etc. can be mixed as necessary.

The base of the leather-like sheet material can be obtained by combining the above-mentioned fiber aggregate or a fiber layer filled with a polymer mainly composed of polyurethane elastomer and a coating layer of a polymer mainly composed of polyurethane elastomer. It is desirable that at least one of the fiber layer or the coating layer has a porous structure in view of the texture, creases, physical properties, etc. of the polymer of the fiber layer or the coating layer.

The thickness or apparent specific gravity of the base layer varies depending on the purpose of use, but generally has a thickness of 0.3 m/m to 5 m/m and an apparent specific gravity of 0.3 m/m to 5 m/m.
A value of about 25 to 0.90 is desirable.

Next, a polymer solution mainly composed of a polyurethane elastomer containing a pearl pigment or a dye is applied to the porous substrate (pearl colored layer (A)).

The pearl colored layer (4) has a thickness of 0.2 μm or more as solid content.
10μ, preferably 0.4μ to 5μ.

The pearl pigment which is a component of the pearl colored layer (4) is 5% to 500% by weight, preferably 50% by weight based on the polymer.
The content must be from % to 300% by weight.

The amount of dye added to the pearl colored layer (4) varies depending on the desired color, but is 0% to 300% by weight based on the polymer.
, preferably 150% by weight or less.

If the thickness of the pearl colored layer is less than 0.2 μm, the pearlescent feel will be poor and it will be difficult to obtain the desired color no matter how much dye is selected as the coloring agent.

On the other hand, if it exceeds 10μ, the bending fatigue strength and the folding texture of the front tube will deteriorate.

Furthermore, if the pearl pigment content is less than 5% by weight, the pearlescent feel will be poor and there will be no commercial value.On the other hand, if it is more than 500% by weight, the stability of the polymer solution will be impaired, uneven coating will occur, and the adhesion will be poor. The elasticity and bending fatigue strength may decrease, and the surface wrinkles may become worse.

Furthermore, if the amount of dye in the pearl colored layer (4) exceeds 300% by weight, not only the physical properties of the leather-like sheet such as flexural fatigue strength and color fastness deteriorate, but also the pearlescent feel is extremely reduced.

Although the type of dye is not particularly limited, metal complex dyes are most suitable from the viewpoints of color development, migration resistance, light resistance, etc.

Since a dye is used as a coloring agent in the veil colored layer (4), it is desirable to use a polyurethane elastomer containing polyethylene glycol in the soft segment.

The pearl pigment used in the present invention is a sparkling powder pigment or a powder pigment dispersed in a suitable vehicle, such as mica coated with titanium oxide, or basic lead carbonate coated with a suitable solvent. metal powders such as aluminum, zinc, copper, copper alloys, etc., or pigments coated around these pigments with colored synthetic resins.

Among them, mica coated with titanium oxide with a particle size of 1μ.
Pearl pigments with a diameter of 70 μm are preferably used because various colors can be obtained by changing the coating thickness of titanium oxide.

In particular, the particle size is 5μ to 30μ and the specific gravity is 2 to 4, preferably 2.5.
A pearl pigment in which titanium oxide is coated on a mica of ~3.5 is effective because it has good dispersion stability in a polymer solution mainly composed of polyurethane elastomer and gives a clear pearly feel.

As such a pearl pigment, Ir1od manufactured by Merck
in RTi 100F.

Ir1odin RCo1or Ti 100 Me
Flamenco 5atina 100 manufactured by ar1
．． Flamenco palegold, Mear
There are lin Br111iant gold, etc.

If the particle size of the pearl pigment is less than 1 μm, only a silky luster will be strong and a proper pearly feel will be produced.On the other hand, if the particle size is more than 70 μm, only a metallic luster will be produced and the commercial value will be lost.

Next, a solution consisting of a polymer mainly composed of polyurethane elastomer and a matting agent is applied onto the pearl colored layer (4) (matting layer (B)).

The matte layer (B) has a thickness of 0.1μ to 10μ in terms of solid content.
, preferably 0.2μ to 5μ, and 1 to the polymer
It is necessary to contain from 5% to 500% by weight, preferably from 5% to 300% by weight of the matting agent.

The matting agent that imparts a dull tone to the leather-like sheet material of the present invention is used to adjust the surface gloss to a certain extent, and the above-mentioned pearl colored layer (4) and the matting layer (B) containing this matting agent The contrast gives a moderately dull tone.

If the thickness of the matte layer (B) is less than 0.1 μm, only the pearly feel will be emphasized and the dull tone will be lost.

On the other hand, if it is more than 10 μm, the pearlescent feel of the pearl colored layer (4) is almost hidden, the dull tone is emphasized, the pearlescent feel is impaired, and the bending fatigue strength and surface creases are deteriorated.

Furthermore, if the content of the matting agent is less than 1% by weight of the polymer mainly composed of polyurethane elastomer, the dull tone will be almost completely lost.

On the other hand, if it exceeds 500% by weight, not only the pearly feel will be severely impaired, but also the adhesion and creases will deteriorate.

The matting agents used in the present invention include those in which inorganic compounds such as silicon oxide and titanium oxide are dispersed in high molecular weight polymers,
Organic compounds include polyethylene wax, polycarbonate wax, polypropylene wax, and liquid paraffin.

The novel dull leather-like sheet material with excellent pearly feel of the present invention has the pearl colored layer (4) and the matte layer (4) on the base layer.
It is obtained by laminating B).

If the order of lamination of the pearl colored layer (4) and the matte layer (B) of the present invention is reversed, only the pearly feeling due to the pearl coloring factor will appear, and the three-dimensional dull pearly feeling that is the characteristic of the present invention will appear. cannot be obtained.

Therefore, in the dull leather-like sheet material with excellent pearly feel of the present invention, the desired color can be easily obtained by laminating the matte layer (B) on the pearl colored layer (4), resulting in an excellent product. .

In addition, the pearl colored layer (4) of the porous sheet material, the matte layer (
It is industrially advantageous to form B) by applying a string-like polymer solution as described above with a spray set or a gravure roll and drying it, but the method of applying it with a gravure roll is Particularly preferred from the viewpoint of uniformity and workability.

The leather-like sheet material of the present invention includes a porous substrate, a pearl colored layer (
4) and the matte layer (B) are created separately and then bonded together, such that each layer is discontinuous, or each layer is continuous.

The present invention will be specifically described below with reference to Examples.

Note that all percentages in the examples are based on weight.

Example 1 Polybutylene adipate glycol, diphenylmethane-4,4'-diisocyanate and
A 15% polyurethane elastomer with a nitrogen content of 4.2% consisting of 4-butanediol was impregnated with a solution of 3% titanium oxide and 82% dimethylformamide, and 75 g/- of the same solution was coated on top of this in terms of solid content. After being immersed in a coagulation bath containing 40% dimethylformamide and 60% water at a temperature of 40° C. for 30 minutes, solvent removal and drying were performed to produce a porous substrate.

Next, 8.47% of a polyurethane elastomer with a nitrogen content of 6% consisting of polyethylene glycol, diphenylmethane 4,4'-diisocyanate, and ethylene glycol was added on top of this, and Ne0Za manufactured by BASF was added as a coloring agent.
pOJGreen 1.17%, Neozapon-B
lue O, 09%, Lan manufactured by Sumitomo Chemical Co., Ltd.
y I -Ye I IowO, 33%, Lanyl
, Black 0.17%, Mer as pearl pigment
Ir1odin RTi1008.47% manufactured by Ck,
A pearl colored layer (4) was prepared by applying a solution of 28.04% dimethylformamide, 35.02% tetrahydrofuran, and 18.24% cyclohexanone to a thickness of 2.5 μm in solid content by gravure printing.

Further, on the pearl colored layer (4), 7.7% of a polyurethane elastomer with a nitrogen content of 6% consisting of polyethylene glycol, diphenylmethane-4,4'-diisocyanate, and ethylene glycol, and a small amount of silicon oxide as a matting agent are applied. Powder 1.61%, dimethylformamide 26.2%
, a solution consisting of 50.0% methyl ethyl ketone and 14.49% cyclohexanone was applied to a thickness of 2 μm in solid content by the same printing method as above to create a matte layer (B), and a leather-like sheet material (1) was obtained. I got it.

The leather-like sheet material (I) is composed of a base layer with a thickness of 1.51n7IL, a pearl colored layer (4) with a thickness of 2.5μ, a matte layer (B) with a thickness of 2μ, and a pearl colored layer (4) with a thickness of 2μ. ) contains 100% pearl pigment and 20.8% dye based on the polymer.
Matting agent (B) contains 20.9% silicon oxide based on the polymer.
It was included.

On the other hand, a polymer solution containing the same kind and amount of pearlescent pigment, dye, and matting agent as above was prepared, and this was applied to the same porous substrate as above in the same manner as above, with a solid content of 4. A leather-like sheet material (n) was obtained by coating 5μ.

Furthermore, the same porous substrate as the leather-like sheet material (I) was coated with the same pearl colored layer (4) as the leather-like sheet material (1), and then polyethylene glycol, diphenylmethane-4
, 4'-diisocyanate, and ethylene glycol with a nitrogen content of 7% was applied to a thickness of 2μ in terms of solid content by the same method as above to create a matte layer (B), and a leather-like sheet material ( Got the button.

Leather-like sheet: Product (I) included all the features of the present invention and had a dull tone with an excellent pearly feel.

In other words, when viewed under sunlight, it had a three-dimensional depth and sparkled.

Furthermore, in the shade, it had an oxidized silver-like luster, and when viewed from different angles, it took on a variety of colors, giving it a luxurious feel and extremely high commercial value.

On the other hand, since the leather-like sheet material (II) was coated with a solution containing a pearl pigment, a dye, and a matting agent, the desired color was not completely produced, and the color clarity and pearl feel were quite poor.

Furthermore, although the leather-like sheet material (Il[) had a sufficient pearl feel, it had a low commercial value as a dull pearl product because of its luster.

The above results are summarized in Table 1.

Example 2 12% polyurethane elastomer with a nitrogen content of 4.4% consisting of polyethylene adipate glycol, diphenylmethane-4,4'-diisocyanate, 1,4-butanediol, 2% brown pigment, 3% water and 83% dimethylacetamide. % solution was applied to a polyethylene sheet at a solid content of 65 fl/rn, and then dimethylacetamide 4
5%-55% water, immersed in a coagulation bath at 35°C for 30 minutes.

Next, this was peeled from the polyethylene sheet, solvent removed and dried, and then adhered to a polyester woven fabric to produce a porous substrate.

The porous substrate was coated with polyethylene braylol/polyethylene adipate glycol 4/1, diphenylmethane-
5.61% polyurethane elastomer with a nitrogen content of 5% based on diisocyanate consisting of 4,4'-diisocyanate and ethanolamine, 30% Irgalan Red O manufactured by Ciba Geigy as a coloring agent, Sumitomo Chemical Co., Ltd. Lanyl YelJow 0 manufactured by
．． 60%, Merck's Ir1od as pearl pigment
in RTi 100F 14.82%, dimethylformamide 26.78%, tetrahydrofuran 31.66%
A pearl colored layer (4) was prepared by applying a solution of 20.23% cyclohexanone to a thickness of 2.5 μm in solid content by a conventional spray method.

Then, on top of this, the same polyurethane elastomer 6 as above was applied.
．． 8%, polyethylene wax 0.7% as a matting agent,
Dimethylformamide 21.0%, toluene 32.0%,
A solution consisting of 739.5% methyl ethyl keto was applied to a thickness of 1.5 μm in solid content (matte layer B) by the same method as above to obtain a leather-like sheet material (IV).

The leather-like sheet material (1) consists of a base layer with a thickness of 0.9 mm, a pearl colored layer (4) with a thickness of 2.5 μm, and a matte layer (B) with a thickness of 1.5 μm. (4) contained 264% pearl pigment and 16% dye based on the polymer, and the matte layer (B) contained 10.3% polyethylene wax based on the polymer.

On the other hand, on the same porous substrate as used for the leather-like sheet material (IN), a porous substrate was formed by reversing the layering order of the pearl colored layer (4) and the matte layer (B) in the leather-like sheet material 4. A matte layer (B) is applied on top of the matte layer (B), and a pearl colored layer (
4) was applied to produce a leather-like sheet material (■).

Comparing leather-like sheet materials (IV) and (V), (IV) according to the present invention is a porous substrate-pearl colored layer (4)-matte layer (B), and the comparative amount (V) is a porous Substrate - Matte layer (
B) - Pearl colored layer (4).

The leather-like sheet material ■ had an orange-tinged pearlescent color, a moderately dull tone, and a three-dimensional luster, and its commercial value was high.

However, the leather-like sheet material (■ indicates the pearl colored layer (4) and the matte layer (B) although the composition within each layer is the same.
), the layering order was different, so the color was orange and had a sufficient pearlescent feel, but the product value was low because it could only produce a flat luster rather than a dull tone.

This result shows that the lamination order of the pearl colored layer (4) and the matte layer (B) is important in determining the value as a product.

Claims (1)

[Scope of Claims] 1. A porous substrate consisting of a fiber aggregate and a polymer mainly composed of polyurethane elastomer, and a polymer mainly composed of polyurethane elastomer, and 5% to 50% by weight based on the polymer.
0% to 30% by weight based on 0% by weight pearl pigment and polymer
A pearl colored layer (A) with a thickness of 0.2μ to 10μ consisting of 0% by weight of dye, a polymer mainly composed of polyurethane elastomer, and a matting agent of 1% to 500% by weight based on the polymer A dull leather-like sheet material with an excellent pearly feel, characterized by sequentially laminating matte layers (B) having a thickness of o, iμ to 10μ. 2 5% to 500% by weight of the polymer on the surface of a porous substrate obtained by impregnating and/or applying a polymer solution mainly composed of polyurethane elastomer to a fibrous material and coagulating it wet or dry. A solution of a polymer mainly composed of a polyurethane elastomer containing a pearl pigment of A dull leather-like sheet material with an excellent pearly feel characterized by applying a solution of a polymer mainly composed of polyurethane elastomer containing ~500% by weight of a matting agent to a solid content of o, iμ to 10μ. manufacturing method.