JP3006908B2 - Leather powder-containing resin film, laminate having this resin film, and methods for producing these - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a leather powder-containing resin film, a laminate having the resin film, and a method for producing the same.
For example, synthetic leather, artificial leather, film, sheet, paint,
It can be used for ink etc.

[0002]

2. Description of the Related Art Conventionally, by attaching an appropriate resin to clothing materials such as cloth, the waterproofness and heat retention of clothing can be increased,
Improvement of moisture permeability, prevention of unevenness, etc., and improvement of comfort have been carried out.Also, by blending appropriate fillers in paint applied to various molded products, unevenness on the surface of the coating film Forming a shape or matte appearance is also performed.

[0003] Specifically, a molded article having a skin layer containing natural leather powder formed on the surface thereof (JP-A-63-233828), a resin film on a base cloth containing leather powder and gelatin particles. And a water-permeable waterproof cloth in which gelatin particles in the resin film are eluted with hot water to form pores.
JP-A-222954), a leather-like paint composed of a paint containing gelatin and leather powder (Japanese Patent Laid-Open No. 62-257974), a film prepared by mixing gelatin into a thermoplastic resin, and hot water to elute the gelatin. (Japanese Patent Application Laid-Open No. 63-152643) and the like have been proposed and implemented.

[0004]

Among the above-mentioned conventional examples, the molded article according to Japanese Patent Application Laid-Open No. 63-233828 can improve the texture such as dry touch feeling and the moisture absorption / desorption property, but cannot improve the moisture permeability. No remarkable improvement effect is seen. JP-A 1-222
The moisture-permeable waterproof cloth disclosed in Japanese Patent Publication No. 2954 can improve moisture permeability, but it is difficult to impart a dry touch feeling and moisture absorption / release properties. The film disclosed in JP-A-63-152633 can improve moisture permeability by dissolving gelatin to form fine pores. However, gelatin is easily absorbed by moisture, and it is inconvenient to handle due to secondary condensation. In addition, in a film containing gelatin (JP-A-63-152643) or a paint (JP-A-62-257974), it is difficult to handle. In addition, there is a disadvantage that non-uniform aggregated particles occur and a defective portion is easily generated. Further, gelatin has a high molecular weight and thus has low solubility in water, and stickiness occurs when it remains on the surface and absorbs moisture. The present invention provides a leather powder-containing resin film which has a good surface appearance (touch feeling) and can be used as a multifunctional material having moisture absorption / desorption, moisture permeability, air permeability, etc., a laminate having this resin film, and It is an object of the present invention to provide a method for producing the same.

[0005]

The leather powder-containing resin film according to the present invention has a structure in which leather powder is dispersed in resin to form a resin film, and voids are formed around the leather powder. It is characterized by. Since such a leather powder-containing resin film is made porous, it has good moisture permeability and an excellent surface touch feeling. In addition, the leather powder contained in the resin film gives appropriate moisture absorption / release properties. As the resin,
After processing into a film or coating, a resin is used that can elute at least the water-soluble substance exposed on the surface with water. Specific examples of such a resin include thermoplastic resins such as polyurethane and polyolefin [LLDPE
(Linear Low Density Polyethylene), PE, PP
Etc.], vinyl chloride, nylon, ethylene vinyl acetate and the like, and particularly preferred is polyurethane having excellent water permeability.

[0006] The leather powder is an animal leather fine powder (protein powder) having a fine and substantially uniform particle size. Specifically, free ions (Na ⁺ , eluted with water) having an average particle size of 7 μm or less (standard deviation σ ≦ 3 μm), a cortical content of 85 wt% or more, an impurity oil and fat content of 2 wt% or less, and water.
Leather fine powder having a total amount of Ca ²⁺ ) of 0.5 wt% or less is preferred. Further, it is preferable that the leather powder is manufactured from cow hide raw material. Such a leather powder is used for a raw material coarse pulverization process,
It can be produced through a degreasing step with a solvent, a swelling treatment step with steam, a classification step, and the like (Japanese Patent Application No. 2-1220).
01). The mixing ratio of the resin and the leather powder is such that the leather powder is 60 to 1 part by weight, preferably the resin 50 to 99 parts by weight,
50 to 10 parts by weight of leather powder for 90 to 90 parts by weight.

The method for producing a leather powder-containing resin film according to the present invention comprises the steps of: coating a leather powder with a water-soluble substance; mixing the leather powder coated with the water-soluble substance with a resin; And a step of washing the formed resin film with water to elute the water-soluble substance. It is desirable that the water-soluble substance be such that a film is easily formed on the leather powder when the leather powder is coated. Specifically, there are protein-based compounds such as water-soluble collagen, gelatin, and water-soluble soybean proteins, and polysaccharide-based compounds such as starch and agar, but they are particularly excellent in water solubility and have low stickiness. Collagen is preferred. When this water-soluble substance is used as a powder, it is preferable that the water content is reduced to 1% by weight or less by drying at 100 ° C. or less. In addition, inorganic compounds such as NaCl can be used, but the film-forming ability is not as good as the above-mentioned substances.

[0008] The method of coating the leather powder with the water-soluble substance is roughly classified into a wet method and a dry method. The wet coating method is a method in which a solution obtained by dissolving a water-soluble substance in water is sprayed on leather powder and then dried. In the dry coating method, after blending a solid water-soluble substance and leather powder finely pulverized so as to have a particle size equal to or smaller than leather powder by a jet mill or the like, or feeding each separately, and mixing them in a high-speed air stream. There is a method of coating the surface of the leather powder with this water-soluble substance by collision. The smaller the coating amount is, the easier the coating is, but it is suitably up to about 60 wt% depending on the purpose.

By washing the formed resin film with water,
After the water-soluble substance is eluted, voids are formed around the leather powder to make it porous, thereby obtaining a leather powder-containing resin film having a reduced film thickness. When the resin film is washed with water, it is preferable that the water-soluble substance around the leather powder is completely eluted, but a part of the water-soluble substance may not be eluted and may remain. When the leather powder is continuously contained from the front surface to the back surface of the resin film via a water-soluble substance, after the water-soluble substance is eluted, a pore is formed from the front surface to the back surface of the resin film by a void. As a result, air permeability is also exhibited. When the formed film is washed with water, water at normal temperature may be used, but it is preferable to use heated water (hot water) in order to easily elute the water-soluble substance. For example, 10-
Wash for 20 minutes.

In the method for producing a leather powder-containing resin film, when the leather powder coated with a water-soluble substance is mixed with a resin, a solvent is also mixed and the resulting fluid mixture is formed into a film. Molding is preferable from the viewpoint of workability. The solvent to be used varies depending on the type of the resin. For example, in the case of polyurethane, dimethylformamide, methyl ethyl ketone, toluene, isopropyl alcohol, butyl acetate and the like, and a mixture thereof can be arbitrarily used. The mixing ratio of the leather powder and the water-soluble substance is
It is suitable to use 60 to 20 parts by weight of the water-soluble substance for 40 to 80 parts by weight of the leather powder. Such a production method can be used, for example, for producing a film by spray coating, flow coating, and roll coating. Further, in the case of polyvinyl chloride or polyolefin, it is possible to form a film by a molding method suitable for the resin such as calender molding or inflation molding after directly mixing and dispersing the resin and the coated leather powder without using a solvent. .

[0011] The leather powder-containing laminate according to the present invention comprises:
It has a base material and the leather powder-containing resin film, and the leather powder-containing resin film is formed on the base material. The substrate is, for example, a woven fabric, a knitted fabric, a nonwoven fabric, or the like. The leather powder-containing resin film may be formed directly on the base material, or may be formed via another resin film or the like. With such a laminate, for example, synthetic leather or artificial leather can be formed.

The method for producing a leather powder-containing laminate comprises the steps of coating a leather powder with a water-soluble substance, mixing the leather powder coated with the water-soluble substance with a resin,
It is characterized by comprising a step of forming the mixture into a film on a substrate and laminating the same, and a step of washing the laminated body with water to elute the water-soluble substance. Examples of a method of laminating a film on a substrate include a method of directly coating or gravure coating the mixture on a substrate, and a method of dry laminating or wet laminating a film once formed on a substrate. And also in this method for producing a leather powder-containing laminate, when mixing the leather powder coated with a water-soluble substance with a resin, a solvent is also mixed together and the resulting fluid mixture is formed into a film. Is preferred from the viewpoint of workability.

[0013]

EXAMPLE 1 First, a horizontal single-track jet mill [STJ-400
Mold (trade name, manufactured by Seishin Enterprise Co., Ltd.) and a mean diameter of 5 μm from a Venturi nozzle in a high-speed jet mill fed at an air supply pressure of 7.5 kg / cm ² G
The raw leather powder is fed simultaneously with a 50 wt% aqueous solution of water-soluble collagen [Nutrilan-I (trade name), manufactured by Henkel Hakusui Co., Ltd.] using a differential pressure from a two-fluid nozzle. Leather powder obtained by coating the powder with a water-soluble collagen of 25 wt% as a solid content was obtained. In this leather powder, almost no increase in particle size due to re-aggregation was observed during storage. Next, 40 parts by weight of the leather powder coated with the water-soluble collagen and 60 parts by weight (solids weight) of a general type polyurethane (Resamine ME3612LP (trade name), manufactured by Dainichi Seika Kogyo Co., Ltd.) were mixed. Further, by adding an appropriate amount of a mixed solvent of dimethylformamide / methyl ethyl ketone, a flowable mixture whose viscosity was adjusted to have an appropriate flowability was prepared. At the time of this mixing, the leather powder was well dispersed, and no aggregation of the leather powder was formed. Thereby, the uniformity of the resin film was improved.

Next, as shown in FIG. 1, a coater [NO.
-AB (trade name), manufactured by Yasuda Seiki Seisakusho Co., Ltd.], and directly coat the fluid mixture on a 100 μm-thick nylon taffeta substrate 1 and then dry at 120 ° C. for 20 minutes. As a result, a laminate 3 in which the leather powder-containing resin film 2 was laminated on the substrate 1 was obtained. As shown in the figure, in this resin film 2, leather powder 5 coated with water-soluble collagen 4 is dispersed in polyurethane 6.
The component ratio in the resin film 2 is 60 parts by weight of polyurethane, 30 parts by weight of leather powder, and 10 parts by weight of water-soluble collagen. next,
As shown in FIG. 2, the laminate 3 is immersed in a hot water bath at 60 ° C. for 20 minutes to elute the water-soluble collagen 4, so that voids 7 are formed around the leather powder 5 and a porous resin film is formed. A laminate 3 having a thickness of 2 (10 μm in thickness) was obtained. The change in weight (9.9 wt%) after elution of the water-soluble collagen 4 substantially corresponded to the weight of the water-soluble collagen 4 coated on the leather powder 5. Therefore, almost all of the water-soluble collagen 4 in the resin film 2 was eluted.

Next, the laminate 3 was measured for moisture absorption, moisture permeability, and air permeability, and the surface appearance (touch feeling) was evaluated. The results are shown in Tables 1 and 2 below. The moisture absorption was measured by placing a sample at 23 ° C. and 30% RH to equilibrate, and then measuring the weight increase when the sample was placed at 30 ° C. and 80% RH. The moisture permeability is JIS-L1099.
4.1 Measured in accordance with the A-1 method. The air permeability is JIS-
L1099.6.27 Measured in accordance with Method A. The surface appearance was evaluated by examining the degree of unevenness and the degree of stickiness. In the same column, ○, Δ, and × indicate good, normal, and bad textures, respectively.

In the same table, the preservability and operability (dispersibility) of the leather powder for other examples are also shown. The preservability of the leather powder was evaluated by observing whether or not the leather powder coated with the water-soluble collagen became large in particle size due to reaggregation during storage.
In the same column, △, Δ, and × indicate that reaggregation does not occur, occurs slightly, or occurs in order. The operability was evaluated by observing the dispersibility (the difficulty of forming aggregates) of the leather powder when the leather powder coated with the water-soluble collagen was mixed with the resin. In the same column, ○, Δ, and × indicate good, normal, and defective resin films, respectively.

Examples 2 to 5 In the same manner as in Example 1, the laminate 3 according to each Example was manufactured. However, in each of the examples, the conditions were partially changed as follows. That is, in Example 2, the coating amount of the water-soluble collagen was 40 wt%, and the amount of the leather powder coated with the water-soluble collagen was 50 parts by weight. In Example 3, the coating amount of the water-soluble collagen was 50 wt%, and the amount of the leather powder coated with the water-soluble collagen was 60%.
Parts by weight were used. In Example 4, the coating amount of the water-soluble collagen was 50 wt%, and the amount of the leather powder coated with the water-soluble collagen was 40 parts by weight.

In Example 5, a highly moisture-permeable polyurethane [Heimlen NPU-5 (trade name), manufactured by Dainichi Seika Kogyo KK] was used as the resin. For the laminate 3 according to each example, the moisture absorption, moisture permeability, and air permeability were measured in the same manner as in Example 1, and the surface appearance (touch feeling) was evaluated. The results are shown in Tables 1 and 2 below. The amount of water-soluble collagen eluted after hot water washing and the thickness of the resin film after hot water washing are also shown in the same table.

Example 6 First, a two-component polyurethane paint (manufactured by Cashew Co., Ltd.) was used as a paint, and the leather powder (water-soluble collagen) according to Example 3 was added to 50 parts by weight of polyurethane as a main component. Were mixed so that the coating amount was 50 parts by weight), and 10 parts by weight of a curing agent and an appropriate amount of a thinner as a solvent were further added to prepare a fluid mixture whose viscosity was adjusted. Next, using a spray gun [W61 (trade name), manufactured by Iwata Coating Machine Co., Ltd.], this fluid mixture was applied to a square (150 mm square) untreated polypropylene resin plate, and then dried. And the coating was dried and solidified at 80 ° C. for 20 minutes. Next, after the coating film was peeled off from the resin plate, the coating film was washed with hot water in the same manner as in the above example to elute water-soluble collagen. Since the coating film was not adhered to the polypropylene resin plate, the coating film could be easily removed. This coating film was measured for moisture absorption, moisture permeability and air permeability in the same manner as in Example 1, and the surface appearance (touch feeling) was evaluated. The results are shown in Tables 1 and 2 below. The elution amount of water-soluble collagen after hot water washing and the thickness of the coating film after hot water washing are also shown in the same table.

Comparative Examples 1 to 6 Laminates according to Comparative Examples were manufactured in the same manner as in the above Examples. However, in each comparative example, conditions were partially changed as follows. That is, in Comparative Example 1, a general-type polyurethane [resamine
ME3612LP (trade name, manufactured by Dainichi Seika Kogyo KK)] was directly coated on a nylon taffeta substrate to a thickness of about 20 μm. In Comparative Example 2, in the method of manufacturing a laminate of Example 2, leather powder not coated with water-soluble collagen was mixed with polyurethane. In Comparative Example 3, instead of the leather powder coated with water-soluble collagen, gelatin [manufactured by Nitta Gelatin Co., Ltd., molecular weight 100,000] was re-ground by a jet mill in the method for producing a laminate of Example 3. The mixture having an average particle size of 3.7 μm was mixed with 30 parts by weight of polyurethane.

In Comparative Example 4, leather powder having an average particle size of 5 μm was replaced with a leather powder having an average particle size of 5 μm in the method for producing a laminate of Example 4 by a jet mill instead of the leather powder coated with water-soluble collagen. Gelatin having a size of 3.7 μm [manufactured by Nitta Gelatin Co., Ltd., molecular weight 100,000] was mixed with 20 parts by weight of polyurethane. In Comparative Example 5, only the highly moisture-permeable polyurethane [Heimlen NPU-5 (trade name), manufactured by Dainichi Seika Kogyo Co., Ltd.] was applied on the nylon taffeta base material in the method of manufacturing the laminate of Example 5. Direct coating was performed to a thickness of 20 μm. In Comparative Example 6, in the method for producing a coating film of Example 6, the coating film was not subjected to a hot water washing treatment. For the laminate or the coating film according to each comparative example, the moisture absorption, moisture permeability, and air permeability were measured in the same manner as in the example, and the surface appearance (touch feeling) was evaluated. The results are shown in Tables 1 and 2 below. The elution amount of water-soluble collagen after hot water washing and the thickness of the resin film or coating film after hot water washing are also shown in the same table. Also,
In the same table, the storability and operability (dispersibility) of the leather powder for Comparative Examples are also shown.

[0022]

[Table 1]

[0023]

[Table 2]

Discussion of Examples and Comparative Examples According to Example 1, since the leather powder coated with water-soluble collagen was used in the production of the laminate, the resulting laminate was particularly resistant to moisture permeability and surface appearance (touch). Feeling) and air permeability. According to the second embodiment, the first embodiment
In comparison, the effect of increasing the coating amount of water-soluble collagen in the production of the laminate is offset by the increase in the thickness of the resin film, and the resulting laminate has improved moisture permeability and air permeability. Although slightly reduced, the moisture absorption was improved and had the same excellent surface appearance. According to Example 3, the amount of water-soluble collagen coating and the amount of comparative powder added were increased in the production of the laminate as compared with Example 2, so that the obtained laminate had improved moisture permeability and air permeability. The moisture absorption and the surface appearance were almost the same.

According to Example 4, the amount of water-soluble collagen coated in the production of the laminate was the same as that of Example 3, but the amount of the leather powder added was reduced. Although the moisture permeability and the air permeability were slightly reduced, the overall properties were the same as those of Example 2. According to Example 5, since the highly moisture-permeable polyurethane was used as the resin, the obtained laminate had excellent moisture permeability and air permeability, and also excellent moisture absorption and surface appearance.
According to Example 6, the obtained coating film had substantially the same surface appearance and multifunctionality as the laminate of Example 3.
Therefore, when the multifunctional laminate obtained according to the present example is used as a material for an automobile interior material, furniture, a bag, clothing, a steering wheel cover, or the like, the surface is not sticky and a leather-like material similar to pores is used. Because it has a surface, it becomes familiar to human skin (good surface touch feeling).

On the other hand, according to Comparative Example 1, since the obtained laminate does not contain leather powder, it has low moisture absorption and moisture permeability, has no air permeability, and has no stickiness. There was a feeling and the surface appearance was inferior. According to Comparative Example 2,
In the obtained laminate, the moisture absorption and the surface appearance were almost the same level as in Example 2 because the leather powder was not coated with the water-soluble collagen, but the moisture permeability was low because it was not made porous. Low and not breathable. According to Comparative Example 3, since the gelatin was used instead of the leather powder coated with the water-soluble collagen in the production of the laminate, the amount of elution by washing with hot water was small. Compared with No. 3, the moisture absorption and moisture permeability were low, there was no air permeability, and when it was touched with a wet finger, the remaining gelatin was sticky and the surface appearance was inferior. In Comparative Example 3, the ground gelatin was easily re-condensed by moisture, and the storage stability was poor. In addition, when a polyurethane solution containing gelatin is diluted with a solvent to disperse gelatin, some re-agglomeration occurs, and if the aggregates are not removed, they tend to appear as defects in the resin film.

According to Comparative Example 4, in the production of the laminate, a mixture of leather powder and gelatin was used instead of leather powder coated with water-soluble collagen. The amount of eluted by washing with hot water was small, and the obtained laminate had low moisture permeability and no air permeability as compared with Example 4, and had a sticky feeling due to the residual gelatin when touched with a wet finger, resulting in a surface having a sticky feeling. The appearance was also poor. Further, in Comparative Example 4, similarly to Comparative Example 3, there was a problem regarding the storage stability and dispersibility of the ground gelatin.

According to Comparative Example 5, since the leather powder coated with water-soluble collagen was not mixed in the production of the laminate, the obtained laminate had low moisture absorption, no air permeability, and no surface. The adhesiveness of the resin itself appeared and the surface appearance was poor. However, the moisture permeability was considerably good because the high moisture permeable type polyurethane was used as the resin. According to Comparative Example 6, in the production of the coating film, the water-soluble collagen was not eluted and removed, so that it was not made porous, and the obtained coating film was almost the same in moisture absorption as compared with Example 6. However, the water vapor permeability is very low and there is no air permeability. In addition, when sweat adhered, the remaining water-soluble collagen was eluted and stickiness occurred, resulting in poor surface appearance.

[0029]

According to the leather powder-containing resin film of the present invention and the laminate having the resin film, the surface appearance (touch feeling) is obtained.
And can be used as a multifunctional material having moisture absorption / release properties, moisture permeability, air permeability and the like. The production method according to the present invention can produce such a leather powder-containing resin film and a laminate having the resin film.

[Brief description of the drawings]

FIG. 1 is a process chart of a method for producing a laminate having a leather powder-containing resin film according to one embodiment of the present invention.

FIG. 2 is a process chart of a method for manufacturing a laminate having a leather powder-containing resin film according to the same example.

[Explanation of symbols]

 Reference Signs List 1 base material 2 leather powder-containing resin film 3 laminate 4 water-soluble collagen which is water-soluble substance 5 leather powder 6 polyurethane which is resin 7 void

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI C14B 7/04 C14B 7/04 (56) References JP-A-3-5110 (JP, A) JP-A-63-152484 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) D06N 3/00-3/18 B32B 5/18 B32B 7/02 B32B 27/20 B32B 27/24 C08J 9/26 C14B 7 / 00-7/06

Claims (6)

(57) [Claims] 1. A leather powder-containing resin film, wherein leather powder is dispersed in a resin to form a resin film, and voids are formed around the leather powder. 2. A leather powder-containing resin, comprising: a base material; and a resin film in which leather powder is dispersed in a resin to form a resin film, and a void is formed around the leather powder. A leather powder-containing laminate, wherein a film is formed on the substrate. 3. A step of coating a leather powder with a water-soluble substance, a step of mixing the leather powder coated with a water-soluble substance with a resin, and forming the mixture into a film. Washing with water to elute the water-soluble substance. 4. A step of coating a leather powder with a water-soluble substance, a step of mixing the leather powder coated with a water-soluble substance with a resin and a solvent, and then forming the fluid mixture into a film. Washing the treated resin film with water to elute the water-soluble substance. 5. A step of coating a leather powder with a water-soluble substance, a step of mixing the leather powder coated with the water-soluble substance with a resin, and forming the mixture into a film on a substrate and laminating the mixture. And a step of washing the laminated laminate with water to elute the water-soluble substance. 6. A step of coating a leather powder with a water-soluble substance, mixing the leather powder coated with the water-soluble substance with a resin and a solvent, and forming the fluid mixture into a film on a substrate. And laminating the laminated body with water to elute the water-soluble substance.