JP2813446B2 - Nubuck tone raised sheet and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention is applied to natural leather, which has a smooth texture and a good sweat-absorbing property such that the touch of the hand sucks sweat like natural leather. The present invention relates to a nubuck-like napped sheet having a similar solid feeling and depth of color, a matte-like appearance, and a nubuck-like appearance and touch of natural leather.

<Prior Art> Conventionally, as a nubuck-like raised hair sheet, (1) A skin layer on the surface after a wet solidification of a solution layer of a synthetic polymer or a dry foaming of a synthetic polymer to form a porous sponge layer. Has been proposed in which a portion of the fine pores is exposed by grinding and removing the fine pores. In addition, (2) Japanese Patent Publication No. Sho 60-4347 discloses a method in which an elastic polymer is applied to a fiber assembly such as a woven fabric, a knitted fabric, or a nonwoven fabric, and the surface is buffed with sandpaper or the like to shorten the hair length.
No. 5, JP-A-61-32432, and the like. However, in each case, the appearance and touch were close to suede of natural leather, and far from the nubuck appearance and touch of natural leather.

Also, many attempts have been made to reproduce natural leather-like appearance and texture by mixing natural leather powder, collagen, and the like into the coating layer of the leather-like sheet. For example, Japanese Patent Publication 63-2364
No. 4, JP-B-63-315677, and the like. These leather-like sheets simply contain leather powder or collagen powder having a large particle size, and there is no fiber nap on the surface, so the surface condition is the appearance and touch of nubuck tone of natural leather. Was far away.

<Problems to be Solved by the Invention> The present invention has good sweat-absorbing properties, the smooth texture of natural leather, and the profound feeling and depth of color with a smooth and natural touch similar to natural leather. The present invention provides a raised sheet having a nubuck-like appearance and touch of natural leather, which looks matte and dark.

<Means for Solving the Problems> The present invention relates to a nap sheet having a fiber nap on the surface of a fibrous sheet containing a polymer mainly composed of an elastic polymer in a fiber aggregate, wherein the surface portion of the nap sheet is mainly Non-fibrous, average particle size of 10 μm or less and apparent bulk density of 0.1 to 0.3 g /
A nubuck brushed sheet characterized by having a surface comprising a mixture of a collagen powder having a size of ³ cm3 and a polymer mainly composed of polyurethane and having no or few fiber naps and a region mainly including fiber naps. In addition, a non-fibrous average particle size of 10
μm or less and an apparent bulk density of 0.1 to 0.3 g / cm ³ A mixed solution or dispersion of a collagen powder and a polymer mainly composed of polyurethane is applied, embossed, and then the surface is brushed. This is a method for producing a nubuck tone raising sheet.

The fiber aggregate in the present invention mainly includes fibers such as woven fabric, knitted fabric or fiber entangled nonwoven fabric made of any fiber such as ordinary fiber, ultrafine fiber and / or bundled fiber thereof, and special porous fiber. It is particularly preferable that this is a non-woven fabric. The nonwoven fabric is used by three-dimensionally intertwining a fiber web with a needle punch or a high-speed fluid flow. Examples of the fibers used include, for example, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, and polyvinyl alcohol; chemical fibers such as regenerated cellulose; natural fibers; and fibers in a special form, for example, ultrafine fibers such as polyester, polyamide, and polyacrylonitrile. Fibers or fibers selected from multicomponent fibers that can be transformed into ultrafine fiber bundle fibers or special porous fibers by dissolving and removing at least one component are used. In particular, in the present invention, the fibers constituting the nap are preferably 0.5 dr or less, preferably 0.3 to 0.0001 dr ultrafine fibers. The ultrafine fibers form a multi-component fiber such as sea-island fibers by mixing or melting after mixing or melting at least two types of polymers having mutually different properties to form a fiber assembly, It is easily obtained by removing at least one component of the fiber. Alternatively, it can be obtained by splitting the fiber by mechanical or chemical action.

The fiber assembly includes polyurethane, acrylic polymer,
A fibrous sheet containing a polymer mainly composed of at least one kind of elastic polymer selected from the group of elastic polymers such as synthetic rubber such as acrylonitrile-butadiene copolymer and styrene-butadiene copolymer. . The method of incorporating a polymer mainly composed of an elastic polymer may be either an emulsion or a solution of the polymer. In addition, a method of coagulating and depositing the polymer can be employed by any method such as a dry method and a wet method, but a mixed solution of a solvent and a non-solvent of an elastic polymer is obtained in terms of a balance between flexibility and a sense of fulfillment of the obtained raised sheet. The wet coagulation method of solidifying into a porous structure is excellent.

When a multi-component fiber is used as a constituent fiber, it is treated with a solvent or a decomposer of one component of the multi-component fiber before or after impregnating and coagulating the polymer mainly composed of the elastic polymer. To transform into ultrafine fibers or bundles thereof.

The collagen used in the present invention is an average particle size obtained by treating and purifying animal skin, bones and tendons with an enzyme or the like, extracting polymeric collagen fibers, causing a cross-linking reaction between the collagen fibers, and then crushing. 2 to 10 μm, apparent bulk density 0.1 to
Was 0.3 g / mc ^3, preferably close-packed bulk density 0.4 to 0.6 g /
A non-fibrous collagen powder of cm ³ , such as CX240 and CX260 manufactured by Showa Denko. If the average particle size of the collagen is larger than 10 μm, a rough feeling appears on the surface and a fine smooth surface cannot be obtained, and a natural leather-like smooth and natural touch cannot be obtained. Moreover, when the apparent density is more than 0.3 g / cm ^3, there is no feeling that the bulkiness touched the hand becomes small sweat and smooth as sucking texture and good sweat resistance, such as natural leather collagen particles It is difficult to obtain a nubuck-like appearance and touch, and the durability is also reduced. On the other hand, when the apparent bulk density is less than 0.1 g / cm ³ , the strength of the collagen particles decreases and the strength of the coating film decreases. Therefore, in order to obtain a natural leather texture and a smooth finished surface, the average particle size of collagen is 10μ.
m or less, an apparent bulk density is preferably in the range of 0.1 to 0.3 g / c ^3. In the present invention, the apparent bulk density is determined according to JIS K 6721.

The weight ratio of the collagen powder to the polyurethane-based polymer is in the range of 1: 1 to 2: 1. If the amount of the collagen powder is small, the characteristic of collagen such as sweat absorption and a smooth touch cannot be obtained, and if the amount of collagen is large, the collagen powder cannot be sufficiently fixed by the polymer, and the film strength is reduced. The texture also worsens.

In the present invention, the polyurethane mixed with the collagen powder is a polymer diol having an average molecular weight of 500 to 2500, for example, at least one selected from the group of polyester diol, polyether diol, polyester ether diol, polycaprolactone diol, polycarbonate diol and the like. And a polymer diol of an organic polyisocyanate such as an aromatic diisocyanate, an aromatic triisocyanate, an alicyclic diisocyanate, an aliphatic diisocyanate having a cyclic group, and triphenylmethane
Polyurethane obtained by reacting at least one organic polyisocyanate selected from the group of 4,4 ', 4 "-triisocyanate with a low molecular compound having at least two active hydrogen atoms as a chain extender. The polyurethane is preferably soft having a 100% modulus of 20 to 60 kg / cm ² so as not to impair the texture of the napped sheet.

A polymer composition mainly composed of collagen and polyurethane is applied to the surface as a dispersion in which collagen is dispersed in a polymer solution. Colorants such as dyes and pigments, stabilizers, antistatic agents, leveling agents, and the like are added to the coating solution depending on the purpose. As a method of applying, for example, a roll application method using a roll having a notch, a smooth surface roll, or the like, a coating method, a spray coating method, a surface contact method, or the like is used. A preferred coating method is a roll coating method because of the uniformity of coating.

The coating amount is 3 to 30 g / m ² in terms of the weight of the dried collagen,
Preferably in the range of 5 to 15 g / m ^2. Since the coating amount of collagen whole less surface than 3 g / m ² is not covered with the collagen powder, whole does not become徽目fine matte surface, also can not be obtained touch and smooth. When the amount of the applied collagen is large, the appearance is not significantly deteriorated, but the film strength is reduced, and the collagen powder is easily dropped off, resulting in poor durability.

The nubuck fluffed sheet of the present invention can be obtained whether the surface of the fibrous sheet to which the composition liquid of the polymer mainly composed of collagen powder and polyurethane is applied is either the raised surface or the non-raised surface. However, in order to obtain a better nubuck feeling, it is preferable to raise the surface of the fiber by raising the hair in advance before applying the composition liquid.

The method of raising the hair before applying the composition liquid can be performed by a conventionally known method, and can be performed using a sandpaper, a sand cloth, a sand net, a sand roll, a brush, a needle cloth, a grindstone, or the like. It is preferable to use sandpaper from the viewpoint that uniform nap is easily obtained.

At first glance, the surface coated with a polymer solution composed mainly of collagen powder and polyurethane has a smooth surface, but when observed under magnification with an electron microscope or the like, the surface is not smooth, but the entire surface is coated with collagen powder. Fine irregularities derived are observed. The fine irregularities are important for the touch of the nubuck sheet of the present invention, the solid feeling and the color depth, and the ratio of the polymer mainly composed of polyurethane to the collagen powder is high, and the valleys of the irregularities are heavy. An object almost buried by the union is inferior in touch and appearance.

The surface of the sheet coated with the composition liquid of the collagen powder and the polymer and dried is subjected to a raising treatment. Brushing treatment after application of the composition liquid,
Rather than uniformly raising the entire surface, it is to be a surface in which the fiber nap portion and the collagen coating portion with almost no nap are mixed, and after imparting an uneven pattern to the surface by embossing or rubbing treatment, It is preferable to perform a raising treatment on the surface. The fiber nap portion and the non-nap portion are not clearly separated in a pattern shape, and it is preferable that the nap portion and the non-nap portion are mixed and integrally mixed to obtain a nubuck feeling more similar to natural leather.

The method of raising the brush after application of the composition liquid can be performed using a sandpaper, a sand cloth, a sand net, a sand roll, a brush, a needle cloth, a grindstone, or the like in the same manner as the raising before the coating, but the collagen powder applied to the surface is Brushing must be avoided under such a strong condition as to remove all of the surface, and if a collagen composition solution is applied to the surface of the brushed surface in advance, lightly brush or clean using a sandpaper or brush with a gentle action. Hair is preferred.

In the production of the nubuck fluffed sheet of the present invention, ordinary dyeing treatment, kneading treatment, treatment with various treatment agents such as an antistatic agent and a softening agent can be performed at any stage of the above-mentioned steps. Dyeing treatment after application of the collagen composition solution is particularly preferable because collagen is stained and the color depth is increased. Dyeing method, using metal complex salt dye, acid dye, disperse dye, etc., Wins dyeing method, Jigger dyeing method,
It is dyed by a high-temperature high-pressure dyeing method (circular) or the like.

The napped sheet obtained by the present invention has good sweat-absorbing properties, has a smooth texture of natural leather, and has a profound feeling and depth of color with a smooth and natural touch similar to natural leather, and a matte. The brushed sheet has a nubuck-like appearance and touch of natural leather that looks dark and dark.

The napped sheet of the present invention, sports shoes, shoe uppers such as men's and women's shoes, lining materials, stopper materials and bags,
Suitable for use in bags, clothing, gloves, etc.

<Examples> Next, embodiments of the present invention will be described with specific examples, but the present invention is not limited to these examples.
The parts and percentages in the examples relate to weight unless otherwise specified.

Example 1 As a fibrous sheet, a 20% DMF solution of polyethylene adipate-based polyurethane containing a blue thread coloring agent was impregnated into an entangled nonwoven fabric of multicomponent fibers containing 6-nylon as a dispersion medium component and polyethylene as a dispersion component, A sheet in which polyurethane was contained in a porous state in a nonwoven fabric of ultrafine fiber bundle fibers obtained by dissolving and removing polyethylene after coagulation in a 40% DMF aqueous solution was used. The surface of the fibrous sheet was raised with sandpaper to obtain a fiber raised surface. 30% polyester-ether polyurethane on the surface of the fiber nap.
% DMF solution 100 parts, average grain size 7μm, apparent bulk density 0.2g
It was applied and dried so that 20 g / m ² by / cm roll coating method using a gravure roll added and the composition was collagen powder 40 parts of ^3. Next, the surface coating layer was heated and embossed with a satin embossing roll to obtain a leather-like sheet.

The leather-like sheet was dyed by a win dyeing method, lightly buffed with sandpaper, and further rubbed to obtain a napped sheet.

The obtained napped sheet has good sweat-absorbing properties, has the smooth texture of natural leather and has a smooth and natural touch similar to natural leather, and also has a nubuck-like appearance and touch of natural leather It was very similar.

This napped sheet was a suitable material for shoe uppers such as sports shoes, men's and women's shoes, lining materials, stopper materials, bags, bags, and clothing.

Examples 2 to 4 and Comparative Examples 1 to 5 In the same manner as in Example 1, the amount of the collagen powder to be added to the polyurethane solution and the amount of the composition solution applied were changed to similarly obtain a napped sheet. Table 1 shows the amount of the collagen powder added, the amount of the composition solution applied, and the properties of the obtained napped sheet.

The napped sheet according to the present invention has good sweat absorption, has a smooth texture of natural leather, a smooth and natural touch similar to natural leather, and further has a nubuck-like appearance and touch of natural leather. Was very similar to

The napped sheet of the present invention was inferior in sweat absorbency, texture, touch and the like.

The napped sheet of Comparative Example 1 was the same as a conventional napped suede, lacked the smooth texture and sweat absorption properties of natural leather, had a suede-like appearance and touch, and was far from nubuck. Further, the napped sheet of Comparative Example 5 has a large roughness tube on the surface due to a large average particle size of collagen, lacks the smooth texture of natural leather, and has a very different appearance from the nubuck tone. Met.

Example 5 As a fibrous sheet, a 20% dimethylformamide (DMF) solution of polyethylene adipate polyurethane was impregnated into an entangled nonwoven fabric of multicomponent fibers containing polyethylene terephthalate as a dispersion component and polyethylene as a dispersion medium component.
After coagulation in a 0% DMF aqueous solution, polyethylene was dissolved and removed to obtain a sheet in which polyurethane was contained in a porous state in a nonwoven fabric of ultrafine fiber bundle-like fibers. A 30% DMF solution of polyester polyurethane 100
A part of the composition was added with 50 parts of collagen powder having an average particle size of 5 μm and an apparent bulk density of 0.25 g / cm ³ by a roll coating method using a gravure roll so as to be 20 g / m ² and dried. Then, using a pear-skin pattern embossing roll, at a temperature of 15
After embossing by heating at 0 ° C. and dyeing by a high-temperature and high-pressure method, buffing was carried out lightly with sandpaper and rubbing treatment was performed to finish a napped sheet.

The obtained napped sheet has a moderate waist, has a nubuck-like surface and has a smooth feel, and when sports shoes and men's and women's shoes are manufactured, both have excellent moldability and shape retention. The sensation and color tone were in harmony in a well-balanced manner and had high commercial value.

<Effect of the Invention> The napped sheet of the present invention has a good sweat-absorbing property, and has a smooth texture of natural leather and a profound feeling and depth of color with a smooth and natural touch similar to natural leather. It is a raised sheet with a nubuck-like appearance and touch of natural leather that looks matte and dark in color.

Claims (3)

(57) [Claims] 1. A napping sheet having fibrous nap on the surface of a fibrous sheet containing a polymer mainly composed of an elastic polymer in a fiber assembly, wherein the nap sheet has a non-fibrous surface and an average particle diameter of 10 μm. Below and apparent bulk density 0.1-0.3g /
A nubuck brushed sheet characterized by having a surface comprising a mixture of a collagen powder having a size of ³ cm3 and a polymer mainly composed of polyurethane and having no or few fiber naps and a region mainly including fiber naps. . 2. A non-fibrous average particle size is formed on the surface of a fibrous sheet containing a polymer mainly composed of an elastic polymer in a fiber assembly.
A nubuck tone characterized by applying a composition liquid of a collagen powder having a size of 10 μm or less and an apparent bulk density of 0.1 to 0.3 g / cm ³ and a polymer mainly composed of polyurethane, embossing and then raising the surface. A method for manufacturing a napped sheet. 3. The method for producing a nubuck fluffed sheet according to (2), wherein a composition liquid is applied after forming fibrous fluff on the surface of the fibrous sheet.