JPH10108709A - Core material for shoes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a core material for shoes which has the hand of natural leather, flexibility and strength, is lighter than the natural leather, has excellent workability and has an antimicrobial function. SOLUTION: This core material 1 for shoes is formed to a moon shape consisting of regenerated leather paper formed by impregnating the regenerated leather paper base paper contg. tannin-tanned leather fibers formed by subjecting tannin-tanned leather to dry pulverizing with a synthetic resin. The regenerated leather paper base paper is formed by pulverizing the tannin-tanned leather scrap with a dry process pulverizing machine set with a clearance between a rotary blade and a stationary blade at 0.3 to 0.5mm at a peripheral speed of >=1,000m/min after adjustment to moisture of <=12wt.%, further sheeting the leather scrap fibers subjected to dry refining with a round hole screen of 0.5 to 1.5mm in diameter. This core material contains natural cellulose fibers and/or synthetic fibers, carries >=0.8wt.% chitosan, contains a foamable resin of 0.5 to 10wt.% per weight and carries 5 to 40wt.% synthetic resin having a glass transition temp. of -40 to +10 deg.C or is subjected to a pressure compression treatment of this resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shoe core material, and more particularly to a shoe core material such as a lug (counter) used for heels of shoes using recycled leather.

[0002]

2. Description of the Related Art In general, a core material for reinforcing a heel portion of a shoe is interposed between an outer skin and an inner skin. As shown in FIGS. 11 and 12, this core material is composed of a one-piece lug 20 conforming to the shape of the heel of the shoe.
Reference numerals 1 and 21 have a triangular shape in which upper edges 22, 22 are inclined rearward on the heel side from the bottom of the shoe to the top line (periphery of the hole into which the foot is inserted). Reference numeral 23 denotes a substantially V-shaped notch, which is formed in order to prevent the core material from overlapping at the portion.

[0003] The lunar type 20 is made of a raw hide called a tanned skin of an animal such as a cow, as well as cardboard, cardboard,
Conventionally, synthetic resin or cloth impregnated with glue has been used, but in order to improve the appearance of the heel and fit the foot most, it has been said that the slime is the best. .

[0004] However, the conventional slime is poor in elasticity, weak to heat, has a bad smell, collapses when stepping on the heel, and is difficult to return to its original state. There were drawbacks such as the oozing oil oozing out and soiling the inside of the shoe. In addition, shoes using numes are expensive.

Moreover, in the shoe manufacturing process, the outer skin and the inner skin are connected by sewing a top line, and then a lunar pattern is inserted between the outer skin and the inner skin of the heel to give a shape as a shoe. When shaping by applying heat treatment to a wooden mold (referred to as instep armor), since a thermosetting chemical adhesive is applied to the front and back surfaces of the lunar mold, the outer skin or inner skin is wrinkled after hot pressing, Sinking and sagging may occur.

[0006] The cause of such wrinkles, sink marks and sags is that the curvature of the inner skin that closely adheres to the wooden mold and the curvature of the outer skin that interposes the core material are different because the heel of the wooden mold is round. The outer skin is made of relatively hard skin material,
Since the endothelium is made of a softer skin material than the outer skin, it is considered that the elasticity of both is different, and that the same type of adhesive is used on both sides of the moon.

[0007] However, the wrinkles, sink marks and sags cannot be corrected with a trowel or other tools, and thus significantly impair the appearance of the shoe, and thus cause a loss that does not become a commercial product.

[0008] In addition, at the time of instep manufacture, the inner skin of the top line is projected outside the epidermis to leave a band-shaped ear portion, and a nail or a pin for fixing the ear portion to a wooden mold (with an ear stopper). After hot pressing, the ears must be cut off to shape the top line, but since the top line has the greatest effect on appearance, this work requires skilled craftsmanship And This work is an indispensable step in the current shoe manufacturing process. That is, when shaping with a wooden mold after instep manufacture, satisfactory shaping could not be performed unless a part of the outer skin or endothelium was fixed to the wooden mold.

Accordingly, there has been provided a shoe core material such as a lug to solve the above-mentioned drawbacks of the slime (Japanese Patent No. 1,052,7).
No. 44, JP-B-55-45120). Also,
A thermosetting adhesive having a different moisture content is applied to the front and back surfaces of a lunar mold made of rawhide, or an impregnated paper is attached to the back surface of a lunar mold made of rawhide and heat is applied to the front and back surfaces with different moisture contents. A shoe core material provided with a curable adhesive has been provided (Japanese Patent No. 1,948,871).
issue). Further, there has been provided a shoe core material formed by forming a lunar mold composed solely of impregnated paper and applying thermosetting adhesives having different moisture contents to both front and back surfaces (Japanese Patent No. 1,961).
7,930, Japanese Patent Publication No. Hei 6-93846).

[0010]

However, since the impregnated paper as a core material for shoes as described above is finally paper, it is difficult to have the texture, flexibility and strength of natural leather. In particular, a lunar type made of leather is the best as a core material for high-grade leather shoes and the like.

Accordingly, the present inventors have focused on recycled leather as a part of the effective use of leather dust generated in the leather industry, and have focused on the current situation where the prior art has focused on the effective use of chrome-tanned leather. In view of the above, we have focused on the necessity of developing a method for effectively using tannin tanned shavings that does not pose a concern of chromium pollution in wastewater, even when used as a raw material for papermaking, and have conducted intensive studies.

As a result, the tanned tanned swarf has a tough fiber strength, and if the swarf fiber is made shorter to give papermaking aptitude, very excellent recycled leather paper base paper (or recycled leather paper)
Can be manufactured.

[0013] However, the tannin tanning swarf is not shortened by wet beating treatment used in a usual paper making process, since the fibers are only broken into warps and warps.

Therefore, the inventors of the present invention have conducted intensive studies on a dry pulverization method for tannin tanned shavings. As a result, the water content of the shavings raw material is adjusted to a predetermined range, and a predetermined shearing force is applied to the raw material. It has been found that a recycled leather base paper can be produced by using swarf fibers having excellent papermaking properties.

Therefore, the present invention provides a shoe having the texture, flexibility and strength of natural leather, lighter weight, superior workability, and antibacterial function than natural leather, using the above-mentioned recycled leather paper base paper. Provide a core material.

[0016]

A shoe core material such as a lug according to the present invention is obtained by impregnating a synthetic leather into a recycled leather paper base paper containing tannin tanned shaving fibers obtained by dry-milling tannin tanned shavings. The recycled leather paper base paper is made of recycled leather paper, and the tannin-tanned leather waste is treated with a water content of 1%.
After adjusting to 2% by weight or less, the peripheral speed is 1,000 m / min or more, and the clearance between the rotary blade and the fixed blade is 0.3 mm to 0.5.
mm, pulverize with a dry pulverizer, and further 0.5 mm
It is characterized by being composed of shaving fibers which are dry-selected with a round hole screen having a diameter of ~ 1.5 mm. The recycled leather base paper contains natural cellulose fibers and / or synthetic fibers, and the synthetic fibers in this case are heat-fusible fibers.

Also, the recycled leather paper base paper carries 0.8% by weight or more of chitosan, and contains 0.5 to 10% by weight of a foamable resin per weight of the recycled leather paper base paper. The glass transition temperature -4 on recycled leather paper base paper
It is characterized in that 5 to 40% by weight of a synthetic resin at 0 ° C. to + 10 ° C. is supported, or that the recycled leather paper is subjected to a compression treatment.

[0018] Further, the recycled leather paper is characterized in that a lump is stuck on at least one side thereof, and the regenerated leather paper is stuck with an impregnated paper on at least one side thereof. Nume on one side, impregnated paper on the other side,
It is characterized by being attached to each. In this case, the impregnated paper may be a base paper made of wood pulp alone, a base paper made of a mixture of wood pulp and shavings, or a base paper made of a mixture of wood pulp and shavings and synthetic fibers. The resin compound thus obtained is impregnated with resin by dipping resin processing and dried.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings. The shoe core material of the present invention is, as shown in FIG. 1, a core material 1 composed of a lug 2 having a shape along the heel of the shoe. This core material 1 is formed by punching recycled leather paper into the lunar mold 2 shown in FIG. 2, and presses and heats it into the shape of the heel with a wooden mold to form the curved inner surface 3 and the curved inner surface 3. The inner surface 4 is formed, and the curved inner surface 3 is sandwiched between the inner skin and the outer skin of the shoe such that the curved outer surface 4 is in contact with the outer skin at the time of forming the instep. As shown in FIG. 9, the periphery of the moon mold 2 is cut and polished with a band knife or edge filter to form a tongue piece 2a having a tapered cross section.

The lunar mold 2 is not limited to a single piece of recycled leather paper, but may have a layered structure composed of two or three laminated sheets. Recycled leather paper base paper contains tannin tanning shaving fiber obtained by dry-milling tannin tanning shavings.
After the adjustment, the peripheral speed is set to 1,000 m / min or more, and the clearance between the rotary blade and the fixed blade is set to 0.3 mm to 0.5 mm.
It consists of slurry-dried and descaled shaving fibers with a round-diameter screen having a diameter of mm. This recycled leather paper base paper may contain natural cellulose fibers and / or synthetic fibers, in which case the synthetic fibers are heat fusible fibers.

Further, this recycled leather paper base paper may carry 0.8% by weight or more of chitosan, in which case it has antibacterial properties. Furthermore, the recycled leather paper base paper may contain a foamable resin in an amount of 0.5 to 10% by weight per weight, and in that case, it exhibits flexibility and lightness. Also,
The glass transition temperature of the recycled leather paper base paper is -40 ° C to +10.
Recycled leather paper is made by carrying 5 to 40% by weight of a synthetic resin at 5 ° C., but by this treatment, mechanical strength, punching property, embossing property and branding property can be imparted. When the recycled leather paper is subjected to a pressure compression treatment, the density and smoothness are improved, the rigidity is reduced, and the texture of the leather is increased.

Further, as shown in FIGS. 3 and 4, the lug 2 made of recycled leather paper has a glue 5 or an impregnated paper 6 made of synthetic resin and paper adhered to at least one side with an adhesive 7.
One side to be attached is curved inner surface 3 or curved outer surface 4 as necessary.
Or both of them. Further, instead of the lump 5 or the impregnated paper 6, it may be made of recycled leather paper itself. The lump 5 or the impregnated paper 6 or the recycled leather paper in place of them have improved local toughness or abrasion resistance. As the adhesive 7, for example, polysol or the like is used.

The combined wall thickness of the lunar mold 2 and the impregnated paper 6 or an alternative recycled leather paper is about one half of the conventional lunar wall thickness.
It is. Then, as shown in FIG. 10, the peripheral portion of the lug 2 is cut and polished from the peripheral portion of the lump 5, the impregnated paper 6 or the regenerated leather paper as a substitute, as shown in FIG. Is formed as a tongue piece 2a. Therefore, the sham 5 or the impregnated paper 6 or the recycled leather paper in place of them is smaller than the lunar mold 2.

Nume 5 is a raw hide tanned by a conventional method, and impregnated paper 6 is a base paper made of wood pulp alone, a base paper made of wood pulp and shavings, or a mixture of wood pulp and shavings and synthetic fibers. The base paper thus obtained is impregnated with resin by a dipping resin process into a compounded resin mainly composed of SBR synthetic latex or acrylic resin, and a lumber is formed from the impregnated paper that has been dried. A single base paper may be obtained by impregnating an SBR-based synthetic latex compounding agent with a resin by dipping resin processing, and laminating a dried impregnated paper. Therefore, the lunar mold 2 in this case has substantially the same configuration as that of FIGS. In addition, the component ratio is wood pulp (mainly virgin) 8
5 to 60 percent of the resin 15
Percent to 40 percent.

The shavings are, of course, natural materials, but shavings made of wastes that are discarded as scraps in the fields of shoes, leather bags and other skin materials are used. It is crushed and fibrillated (collagen fiber). The mixing ratio of this swarf may be any number within the range of 10 to 90% of wood pulp,
Desirably, the ratio of pulp to wood is 50% or more.
The results of the test showed that the lunar mold obtained from the base paper mixed with the shavings had excellent moldability and was easy to fit on the foot.

Although the synthetic fibers are not limited to any kind, waste materials which are discarded as scraps like swarf are used, and the scraps are defibrated and used. The synthetic fiber has an upper limit of 15% relative to wood and shavings, preferably 5 to 8%. A base paper obtained from the base paper mixed with the synthetic fibers showed good permeability of the impregnated resin agent and a uniform resin during the resin processing, as a result of an execution test.

FIGS. 5 to 8 show modified examples of the core material 1. 5 and 6 are modifications of FIGS. 1 and 2, and FIGS. 7 and 8 are modifications of FIGS. The lugs 2 of these cores 1 are formed with inverted triangular cut edges 12 at both ends. That is, the edge 13 of the edge portion 12
However, contrary to the above-mentioned conventional example, it is inclined rearward on the heel side.
Other configurations are the same as the previous example. By forming such an edge portion 12, wrinkling does not occur on the inner skin on the arch side of the foot at the time of instep making.

[0028]

EXAMPLES The present invention will be described more specifically below with reference to examples relating to recycled leather paper base paper. In each of Examples and Comparative Examples,% means% by weight.

(Manufacture of Tannin Tanning Fiber) Example 1 Tannin tanned cow skin having a water content of 8% was subjected to a peripheral speed of 1,200 m /
The mixture was pulverized with a rotary cutter (mesh mill HA2542, Horai Co., Ltd.) having a clearance of 0.4 mm between the fixed blade and the rotary blade and a screen hole diameter of 0.6 mm to produce shaving fibers.

At this time, the production rate of the shaving fiber was checked, and the fiber length (average fiber length and fiber length distribution, the same applies hereinafter) and freeness of the obtained shaving fiber were measured.

Example 2 Skin fibers were produced in the same manner as in Example 1 except that the screen hole diameter was set to 1.4 mmφ.

At this time, the production rate of the shaving fiber was checked, and the fiber length and freeness of the obtained shaving fiber were measured.

Example 3 Dust fibers were produced in the same manner as in Example 1 except that the water content was changed to 2%.

At this time, the production rate of the shaving fiber was checked, and the fiber length and freeness of the obtained shaving fiber were measured.

Reference Example 1 Dust fibers were produced in the same manner as in Example 1 except that the water content of the tannin tanned cow dander was changed to 12%.

At this time, the production rate of the shaving fiber was checked, and the fiber length and freeness of the obtained shaving fiber were measured.

Reference Example 2 Dust fibers were produced in the same manner as in Example 1 except that the peripheral speed was 800 m / min.

At this time, the production rate of the shaving fiber was checked, and the fiber length and freeness of the obtained shaving fiber were measured.

Reference Example 3 Dust fibers were produced in the same manner as in Example 1 except that the clearance was 0.6 mm.

At this time, the production rate of the shaving fiber was checked, and the fiber length and freeness of the obtained shaving fiber were measured.

Comparative Example 1 Dust fibers were produced in the same manner as in Example 1 except that the clearance was 0.2 mm.

At this time, the production rate of the shaving fiber was checked, and the fiber length and freeness of the obtained shaving fiber were measured.

Comparative Examples 2 and 3 Dust fibers were produced in the same manner as in Example 1 except that the screen hole diameters were changed to 0.4 mmφ and 2.0 mmφ.

At this time, the production rate of the shaving fiber was checked, and the fiber length and freeness of the obtained shaving fiber were measured.

The production rate check and the measurement of the fiber length and the freeness of the shaving fibers obtained in Examples 1 to 3, Reference Examples 1 to 3, and Comparative Examples 1 to 3 were performed as follows.

(Check of Production Rate) The production rate of the scrap fiber was checked by measuring the production weight of the scrap fiber per unit time processed by the rotary cutter.

(Measurement of Freeness) 3 g of absolutely dry shavings fiber
It was weighed, suspended in 1 liter of water at 20 ° C., and left for 1 hour to absorb the shaving fibers. After that, according to the usual method, TAPP
It was measured by a freeness tester (Canadian Standard Freeness Tester, manufactured by Tozai Seiki Co., Ltd.) based on I Standard T227.

(Measurement of Fiber Length Distribution) After water absorption treatment of the shaving fibers in the same manner as in the above-described freeness measurement, the fiber length distribution of the shaving fibers (24 mesh on, 150 mesh pa)
ss) is based on TAPPI standard T233,
It was measured by a Bauer Macnet type sieve tester (manufactured by Tozai Seiki Co., Ltd.).

(Measurement of Weight Average Fiber Length) The weight average fiber length of the fiber was measured using a Kajaani fiber length distribution measuring instrument FS-200 (manufactured by Valmet Automation).

Table 1 shows the results of each measurement.

[0051]

[Table 1]

(Properties of Tannin Tanned Dust Fiber)
60% by weight of the shaving fibers obtained in Examples 1 and 2, Reference Example 3 and Comparative Example 2 and 40 ml of NBKP having a freeness of 600 ml.
% By weight, the raw material concentration was adjusted to 0.15% by weight, and the state of dispersion of the raw materials was observed.
/ M ² was prepared and the tensile strength of the sheet was measured. The formation was visually observed.

(Measurement of Tensile Strength) The tensile strength of the hand-made sheet was measured according to JIS-P-8113.

The shape of the sample used for the measurement was 15 sheets for each sheet.
mm (width) x 150 mm (length), the length between both grips at the beginning of the test was 100 mm, and the pulling speed was 20 mm / min.

Table 2 shows the results.

[0056]

[Table 2]

(Evaluation) As is clear from Table 1, in Reference Example 1, although the water content of the shavings is high and the passage through the screen is poor, the production rate decreases, but the properties of the shaving fibers are good.

In Reference Example 2, since the peripheral speed of the rotary cutter is low and the shearing force is small, the fiber length is long, and in particular, the length of 24 mesh on increases.

In Comparative Example 1, since the clearance between the fixed blade and the rotary blade was small, the fiber length was too short, and the performance of the shaving fiber was inferior.

In Reference Example 3, since the clearance between the fixed blade and the rotary blade was too large, the shearing force was small, and the fiber length was long. For this reason, 24 mesh on increases as it is, and the papermaking property is inferior.

Comparative Example 2 is not desirable because the screen holes are small, the production rate is reduced, and the fibers are shortened.

In Comparative Example 3, the perforations of the screen were too large, and the fibers became long. In particular, the 24 mesh on component increases.

In contrast to these Reference Examples and Comparative Examples, Examples 1 to
No. 3 has a high production rate and the length of the shavings fiber is similar to wood pulp. Further, the fiber length distribution is 24 mesh on, 150
Both of the mesh pass portions are small and good.

Accordingly, the shaving fiber produced according to the present invention has a fiber length of about 1 mm to 2 mm, which is close to the fiber length of wood pulp, has a small content of long fibers and short fibers, and has a high drainage. Having.

As is clear from Table 2, the hand-made sheet of Reference Example 3 has a poor sheet formation and a low tensile strength because the fiber length of the shaving fibers is too long.

Comparative Example 2 has a low tensile strength due to a large amount of short fibers.

On the other hand, in Examples 1 and 2, the formation of the sheets was good.
A good sheet was obtained with high tensile strength.

(Prototype Production of Recycled Leather Paper Base Paper) Example 4 The tannin tanned whisk fibers produced in Example 1 after water absorption were used, and 60% of whisk fibers, 20% of heat-fusible fiber, and N
BKP 20% (freeness 600 ml) was blended to make a papermaking raw material, and 0.2% of a dry paper strength agent was used as a papermaking chemical.
%, And 0.3% of a wet paper strength enhancer was added to make a recycled leather base paper.

The heat-fused fibers and the chemicals used are as follows.

1. The heat fusible fiber is Chisso EA842 (registered trademark: manufactured by Chisso Corporation) fiber diameter 3 denier, fiber length 3
Use mm.

2. For papermaking chemicals, dry paper strength enhancer is Polystron PS191 (registered trademark: manufactured by Arakawa Chemical Industries, Ltd.), and wet paper strength enhancer is Euramine P-5600.
(Registered trademark: Mitsui Toatsu Chemical Co., Ltd.) is used.

Table 3 shows the quality of the obtained recycled leather base paper.

[0073]

[Table 3]

From Table 3, it can be seen that the tannin tanned shaving fiber of Example 1 according to the present invention has a good base paper formation because the raw material is well dispersed and has a high tensile strength and is suitable as a raw material for recycled leather paper base paper. You can see that.

The recycled leather paper base paper and the method for producing the same are not limited to the above embodiments.

(Slurry of Tannin Tanned Dust Fiber)
Next, an embodiment of the method for making a slurry fiber of the present invention will be described. In the following Examples and Comparative Examples,% means% by weight, as in the above Examples.

Example 5 The density of the shaving fiber produced in Example 1 was adjusted to 3.0% by a variable speed stirrer, and the peripheral speed of the stirring blade of the stirrer was 50 m / m.
The mixture was disintegrated for 5 minutes and a stirring time of 5 minutes to produce a slurry of shavings fiber.

At this time, the rotational running length of the tip of the stirring blade is 25.
0 m. The freeness of the obtained swarf fiber slurry was measured, and the state of dispersion of the swarf fiber and twist were checked to evaluate the suitability as a papermaking raw material.

Example 6 A scrap fiber slurry was prepared and evaluated in the same manner as in Example 5, except that the peripheral speed of the stirring blade of the stirrer was set to 500 m / min.

Example 7 A scrap fiber slurry was prepared and evaluated in the same manner as in Example 6, except that the stirring time was changed to 10 minutes.

Comparative Example 4 A scrap fiber slurry was prepared and evaluated in the same manner as in Example 5, except that the concentration of the scrap fiber was adjusted to 5%.

Comparative Example 5 The density of the shavings fiber was adjusted to 5%, and the peripheral speed of the stirrer was set to 500 m.
A slurry fiber slurry was produced and evaluated in the same manner as in Example 5 except that the rate was changed to / min.

Comparative Example 6 A scrap fiber slurry was produced and evaluated in the same manner as in Example 5, except that the peripheral speed of the stirrer was changed to 40 m / min.

Comparative Example 7 A scrap fiber slurry was produced and evaluated in the same manner as in Example 5, except that the peripheral speed of the stirrer was changed to 550 m / min.

Comparative Example 8 A swarf fiber slurry was produced and evaluated in the same manner as in Example 5, except that the stirring time was changed to 3 minutes.

Comparative Example 9 A swarf fiber slurry was prepared and evaluated in the same manner as in Example 5, except that the stirring time was changed to 120 minutes.

(Measurement method) Examples 5 to 7 and Comparative Example 4
The measurement of the freeness of the swarf fiber slurry obtained in Nos. 9 to 9 and the check of the fiber dispersion state and the fiber twist state were performed in the following manner.

The freeness of the shaving fiber was measured by a freeness tester (Canadian Standard Freeness Tester, manufactured by Tozai Seiki Co., Ltd.) based on TAPPI Standard T227.

The state of fiber dispersion and the generation of twists of the shaving fiber slurry was visually observed by dispersing the slurry in water diluted to a concentration of about 0.1% by weight.

Table 4 shows the results.

[0091]

[Table 4]

(Evaluation) As is evident from Table 4, in Examples 5 to 7, the freeness is 200 Cml or more, and a slurry with good dispersion and no twist is obtained.

On the other hand, in Comparative Examples 4 and 5, stirring was not possible due to the high concentration of the shaving fiber slurry (Comparative Example 4), or the freeness was reduced and the curling was caused (Comparative Example 5). Also, in Comparative Example 6, stirring was not possible because the peripheral speed of the stirrer was low.

In Comparative Example 7, the peripheral speed of the stirrer at the time of shaving the slurry fiber was high, the fiber was rapidly damaged, the freeness was reduced, and the drainage was deteriorated.

In Comparative Example 8, since the stirring time was short, the running length of the stirring blade was insufficient and the stirring was insufficient.

In Comparative Example 9, the drainage was deteriorated by excessive stirring.

(Preparation of Recycled Leather Paper Base Paper) Example 8 Softwood bleached kraft pulp (NBKP) containing pine and spruce as a main raw material was disintegrated, and then beaten to a freeness of 600 ml with a laboratory beater to prepare a pulp raw material. And N
BKP was 20% by weight based on the total weight of the recycled leather paper base paper, and the tannin tanned swarf fiber prepared in Example 1 was 60% by weight based on the total weight of the recycled leather paper base paper.
2. A fiber raw material was blended so that a fiber diameter of 3 denier × fiber length of 3 mm (manufactured by Chisso Corporation) was 20% by weight based on the total amount. Polystron 191 (manufactured by Arakawa Chemical Industry Co., Ltd.) as a dry paper strength enhancer is added to such a fiber material at 0.2% based on the total weight of the base paper, and Euramine P-560 is used as a wet paper strength enhancer.
0 (manufactured by Mitsui Toatsu Chemicals) per 0.3% of the total weight of the base paper
%, And F-30D (manufactured by Matsumoto Yushi Co., Ltd.) as a foaming agent was adjusted so as to be 5% based on the total weight of the base paper to adjust the stock. / Minute of stirring for 10 minutes to make the freeness of the stock 370 ml.
/ M ² of recycled leather paper base paper was prepared. 120 ° C
For 1 minute and subjected to a foaming treatment. (The foaming treatment was performed in the same manner.) The density of the base paper after the foaming treatment was 0.2 g.
/ Cm ³ .

Example 9 NBKP was used in an amount of 30% by weight based on the total weight of recycled leather paper base paper.
Recycled leather paper base paper was obtained in the same manner as in Example 8, except that the fiber raw material was blended so that the tannin tanned swarf fiber was 70% by weight.

The freeness of the furnish was 310 ml.

Comparative Example 10 30% by weight of NBKP, 45% by weight of tannin tanned shaving fiber, and 25% by weight of heat-fusible fiber (EA842, manufactured by Chisso Corporation, fiber diameter 3 denier × fiber length 3 mm) per weight
A recycled leather paper base paper was obtained in the same manner as in Example 8, except that the fiber raw material was blended so as to obtain the following.

The freeness of the fiber raw material was 350 ml.

Comparative Example 11 55% by weight of NBKP and 45% of tannin-tanned shavings fiber
Example 8 except that the fiber raw material was blended so as to be in a weight%.
In the same manner as described above, a recycled leather paper base paper was obtained. The freeness of the fiber raw material was 300 ml.

(Evaluation) Examples 8 and 9, Comparative Examples 10 and 11
Was evaluated for breakability. The obtained four types of samples were folded in two, and when opened again, the inside cracks (folding property) were visually evaluated. Table 5 shows the results.

In general, no cracks occur in the real leather, but cracks occur in the paper.

[0105]

[Table 5]

(Preparation of Chitosan-Supported Recycled Leather Paper Base Paper) Example 10 The stock was adjusted in the same manner as in Example 8, and the chitosan (SK
-10, manufactured by Koyo Chemical Co., Ltd.) was added in an amount of 0.9% by weight based on the tannin tanned shaving fiber. The freeness of the furnish was 350 ml. Using the stock, a recycled leather paper base paper was prepared in the same manner as in Example 8.

The antibacterial property of the recycled leather paper base paper was measured and determined by the following method.

(Preparation of antibacterial evaluation sample) 1) A recycled leather paper base paper was prepared and measured immediately.

2) After preparing the recycled leather paper base paper, the sample was immersed in water by an etching processor and dried by blowing air at 40 ° C. This process was performed once, and the base paper, which was repeated 10 times, was measured as an evaluation sample.

(Antibacterial property) According to JIS L-1902,
Evaluation was performed using Staphylococcus aureus. When no bacterial colonies were found, the sample was indicated as (-) and judged to be acceptable. When colonies were found, the sample was indicated as (+) and judged as failed.

Example 11 Example 1 was repeated except that chitosan (SK-10) was added in an amount of 3.5% by weight based on the tannin tanned skin fiber.
In the same manner as in Example No. 0, a recycled leather paper base paper was obtained. The antibacterial property of the recycled leather base paper was measured and determined in the same manner as in Example 10.

Comparative Example 12 Example 1 was repeated except that chitosan (SK-10) was added in an amount of 0.7% by weight based on the tannin tanned skin fiber.
In the same manner as in Example No. 0, a recycled leather paper base paper was obtained. The antibacterial property of the recycled leather base paper was measured and determined in the same manner as in Example 10.

Comparative Example 13 Without adding chitosan (SK-10), impregnated with an etching processor such that Amorden HS (manufactured by Daiwa Chemical Industry Co., Ltd.) as an antibacterial agent was 0.9% by weight with respect to the tannin tanned skin fiber. A recycled leather paper base paper was obtained in the same manner as in Example 10 except for the above. Example 1 Antibacterial Property of Recycled Leather Paper Base Paper
It was measured and judged in the same manner as in the case of 0.

Table 6 shows the measurement results of the examples and the comparative examples.

[0115]

[Table 6]

(Evaluation) As is clear from Table 6, the antibacterial function can be imparted by adding chitosan to the recycled leather paper base paper at a specific value or more (Examples 10 to 11). On the other hand, when the added amount of chitosan is small, the antibacterial function cannot be imparted, and it becomes practically unsuitable (Comparative Example 12). When a general antibacterial agent was impregnated into recycled leather paper base paper, the antibacterial property immediately after the preparation was passed, but after 10 times of water immersion and drying treatment, the antibacterial property was rejected and became unsuitable for practical use. Example 13).

Example 12 (Preparation of recycled leather paper) The recycled leather paper base paper prepared in Example 8 was etched with an etching processor and had a glass transition temperature of -35.
C. (P-5Z68, manufactured by Sumitomo A & L Co., Ltd.) was impregnated with 5% by weight of a base paper to obtain a recycled leather paper.

The punching property, embossing property and branding property of the recycled leather paper were measured by the following methods and judged.

(Punching property) Recycled leather paper was punched by a 10-ton press using a 10 cm square mold. If the punched surface was frayed or partially connected and punching was defective, it was rejected and punched out without connection. In that case, it was judged to be acceptable.

(Embossing property) Recycled leather paper was embossed using a test embossing machine with a linear pressure of 100 kg / cm, an embossing roll temperature of 30 ° C, an embossing speed of 5 m / min, and a herringbone embossing pattern. When the emboss was able to be cut without breaking, it was judged as pass, and when the emboss pattern was broken, it was judged as fail.

(Branding property) A donut-shaped branding having an inner diameter of 4 cm and an outer diameter of 5 cm was heated by a direct heat of a gas burner, pressed on recycled leather paper for 3 seconds, and pressed. A pass was determined if the branding entered without burning or fading, and a reject was determined if burning or fading occurred.

Example 13 Example 12 was repeated except that the recycled leather paper base paper prepared in Example 8 was impregnated with a synthetic resin having a glass transition temperature of -35 ° C. by an etching processor so as to be 38% by weight of the base paper.
Recycled leather paper was obtained in the same manner as described above. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Example 14 A synthetic resin (S-301, glass transition temperature 7 ° C.) having a glass transition temperature of 7 ° C. was applied to the recycled leather paper base paper prepared in Example 8 using an etching processor.
Recycled leather paper was obtained in the same manner as in Example 12 except that 5% by weight of the base paper was impregnated with Sumitomo Chemical Co., Ltd.). The punching property, embossing property and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Example 15 The same procedure as in Example 12 was carried out except that the recycled leather paper base paper prepared in Example 8 was impregnated with a synthetic resin having a glass transition temperature of 7 ° C. by an etching processor so as to be 38% by weight based on the base paper. Recycled leather paper was obtained in the same manner.

The punching property, embossing property and branding property of the recycled leather paper were measured and judged in the same manner as in Example 12.

Example 16 Example 12 was repeated except that the recycled leather base paper of Example 9 was used.
Recycled leather paper was obtained in the same manner as described above. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Example 17 Example 16 was repeated except that the recycled leather paper base paper prepared in Example 9 was impregnated with a synthetic resin having a glass transition temperature of -35 ° C. by an etching processor so as to be 38% by weight of the base paper.
Recycled leather paper was obtained in the same manner as described above. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Example 18 A synthetic resin (S-301, glass transition temperature 7 ° C.) having a glass transition temperature of 7 ° C. was applied to the recycled leather paper base paper prepared in Example 9 using an etching processor.
Recycled leather paper was obtained in the same manner as in Example 16 except that the base paper was impregnated with 5% by weight of the base paper. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Example 19 The same procedure as in Example 16 was carried out except that the recycled leather paper base paper prepared in Example 9 was impregnated with a synthetic resin having a glass transition temperature of 7 ° C. by an etching processor so as to be 38% by weight based on the base paper. Recycled leather paper was obtained in the same manner. The punching property, embossing property and branding property of the recycled leather paper were measured in the same manner as in Example 12,
Judged.

Comparative Example 14 A synthetic resin (AE-9) having a glass transition temperature of -47 ° C. was applied to the recycled leather paper base paper prepared in Example 9 using an etching processor.
Recycled leather paper was obtained in the same manner as in Example 12 except that the base paper was impregnated with 5% by weight of the base paper. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 15 Example 12 was repeated except that the recycled leather paper base paper prepared in Example 9 was impregnated with a synthetic resin having a glass transition temperature of -47 ° C. by an etching processor so as to be 38% by weight based on the base paper.
Recycled leather paper was obtained in the same manner as described above. The punching property, embossing property and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 16 A synthetic resin (S-75) having a glass transition temperature of 15 ° C. was applied to the recycled leather paper base paper prepared in Example 9 using an etching processor.
(2, manufactured by Sumitomo Chemical Co., Ltd.) to obtain a recycled leather paper in the same manner as in Example 12 except that it was impregnated so as to be 5% by weight with respect to the base paper. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 17 Example 12 was repeated except that the recycled leather paper base paper prepared in Example 9 was impregnated with a synthetic resin having a glass transition temperature of −35 ° C. by an etching processor so as to be 38% by weight based on the base paper.
Recycled leather paper was obtained in the same manner as described above. The punching property, embossing property and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 18 Example 12 was repeated except that the recycled leather paper base paper prepared in Example 9 was impregnated with a synthetic resin having a glass transition temperature of -35 ° C. by an etching processor so as to be 3% by weight based on the base paper. Recycled leather paper was obtained in the same manner as described above. Punching properties of recycled leather paper,
The embossing property and the branding property were measured and determined in the same manner as in Example 12.

Comparative Example 19 The recycled leather paper base paper prepared in Example 9 was impregnated with a synthetic resin having a glass transition temperature of -35 ° C. by an etching processor so as to be 42% by weight based on the base paper.
Recycled leather paper was obtained in the same manner as described above. The punching property, embossing property and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 20 Example 1 was repeated except that the recycled leather base paper of Comparative Example 10 was used.
In the same manner as in Example 2, recycled leather paper was obtained. The punching property, embossing property and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 21 Example 13 was repeated except that the recycled leather paper base paper of Comparative Example 9 was used.
Recycled leather paper was obtained in the same manner as described above. The punching property, embossing property and branding property of the recycled leather paper were the same as in Example 12,
Measured and judged.

Comparative Example 22 Example 16 was repeated except that a synthetic resin (AE-942, manufactured by Nippon Synthetic Rubber Co., Ltd.) having a glass transition temperature of -47 ° C. was impregnated with an etching processor so as to be 5% by weight with respect to the base paper. Recycled leather paper was obtained in the same manner. Punching properties of recycled leather paper,
Embossability and branding were measured and determined in the same manner as in Example 12.

Comparative Example 23 Recycled leather paper was obtained in the same manner as in Example 16 except that a synthetic resin having a glass transition temperature of -47 ° C. was impregnated with an etching processor so as to be 38% by weight based on the base paper. Example 12: Punching property, embossing property and branding property of recycled leather paper
The measurement was carried out in the same manner as in the above, and the judgment was made.

Comparative Example 24 The same procedure as in Example 16 was carried out except that a synthetic resin (S-752, manufactured by Sumitomo Chemical Co., Ltd.) having a glass transition temperature of 15 ° C. was impregnated with an etching processor so as to be 5% by weight with respect to the base paper. To obtain recycled leather paper. The punching property, embossing property and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 25 Recycled leather paper was obtained in the same manner as in Example 16 except that a synthetic resin having a glass transition temperature of -35 ° C. was impregnated with an etching processor so as to be 38% by weight based on the base paper. Example 12: Punching property, embossing property and branding property of recycled leather paper
The measurement was carried out in the same manner as in the above, and the judgment was made.

Comparative Example 26 Recycled leather paper was obtained in the same manner as in Example 16 except that a synthetic resin having a glass transition temperature of -35 ° C. was impregnated with an etching processor so as to be 3% by weight based on the base paper. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 27 Recycled leather paper was obtained in the same manner as in Example 16 except that a synthetic resin having a glass transition temperature of -35 ° C. was impregnated with an etching processor so as to be 42% by weight based on the base paper. Example 12: Punching property, embossing property and branding property of recycled leather paper
The measurement was carried out in the same manner as in the above, and the judgment was made.

Comparative Example 28 Example 1 was repeated except that the recycled leather base paper of Comparative Example 15 was used.
In the same manner as in Example 2, recycled leather paper was obtained. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Comparative Example 29 Example 1 was repeated except that the recycled leather paper base paper of Comparative Example 11 was used.
In the same manner as in Example 3, a recycled leather paper was obtained. The punching property, embossing property, and branding property of the recycled leather paper were measured and determined in the same manner as in Example 12.

Table 7 shows the measurement results of the examples and comparative examples.

[0147]

[Table 7]

(Evaluation) As is evident from Table 7, the punching property, embossing property and branding property were improved by supporting a specific range of the synthetic resin having a glass transition temperature in a specific numerical range with respect to the weight of the base paper. Can be applied (Examples 12 to 19). On the other hand, if the glass transition temperature of the synthetic resin is smaller than a specific value, the punching property becomes unacceptable and becomes unsuitable for practical use (Comparative Examples 14 to 15 and Comparative Examples 22 to 23). Further, when the glass transition temperature of the synthetic resin is higher than a specific value, the embossability is rejected, and the resin becomes unsuitable for practical use (Comparative Examples 16 to 17, and Comparative Examples 24 to 25). Further, even if the glass transition temperature of the synthetic resin is in a specific numerical range, the punching property is rejected if the content of the synthetic resin is less than 5% (Comparative Examples 18 and 26), and if the content exceeds 40%. On the contrary, the embossability is rejected (Comparative Examples 19 and 27), so that each is not practically suitable. Further, when a recycled leather paper base paper made with an addition ratio of the scrap fiber of less than 50% by weight is used, the branding property is rejected, and it is not practically suitable (Comparative Examples 20 to 21, Comparative Examples 28 to 29). .

(Recycled Leather Paper Pressed and Compressed by Calendar) Examples 20 to 23 The furnish prepared in Example 8 was used.
A recycled leather paper base paper of 500 g / m ² of rice tsubo was prepared.

The obtained base paper was impregnated with an SBR latex (T5-20 ° C, P5Z66, manufactured by Sumitomo Dow) at a resin impregnation ratio of 30% by weight per base paper, and dried to prepare a recycled leather paper.

Next, the recycled leather paper was subjected to a linear pressure of 100 kg / c.
m, processing speed 10 m / min, processing temperature 20 ° C. (Example 2
0), 50 ° C. (Example 21), 130 ° C. (Example 22)
And the effect of calendering temperature was examined. In Example 23, the linear pressure was 200 kg / cm, and the temperature was 130.
It calendered similarly at ° C. The density, stiffness, and smoothness of the obtained recycled leather paper were measured, and the texture was observed.

The rigidity is TAPPI standard T543
It was measured with a Gurley-type stiffness tester based on the paper stiffness measurement method described in pm-84. Smoothness is JIS-P-8
The paper and paperboard described in 119 were measured with a Beck smoothness tester. The texture of the recycled leather paper was evaluated by sensory evaluation of the flexibility, flexibility and elasticity of the leather-like leather, and further, bone formation was observed when the leather was folded at 180 °. Table 8 shows the results.

[0153]

[Table 8]

(Evaluation) The heated calender treatment of the recycled leather paper improved the density and smoothness and lowered the rigidity. Along with this, the flexibility of recycled leather paper has been improved, and even when folded,
Cracks no longer crack. The density also approached that of natural leather, and as a whole, approached the texture of natural leather.

[0155]

As described above, according to the present invention, since the core material for shoes is mainly made of recycled leather paper using swarf fibers, the texture and flexibility of natural leather are excellent. Has strength, moldability, dyeability, and printability. Further, it is lighter than conventional natural leather, has good workability, has less variation in products, has uniform quality, and can provide effects such as price reduction. Further, when the recycled leather paper is subjected to a pressure compression treatment, the density and the surface properties thereof are close to those of natural leather, and the texture of the leather as a whole approaches the texture of natural leather.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a core material according to the present invention.

FIG. 2 is a plan view of the moon of FIG. 1;

FIG. 3 is a perspective view showing another example of the core material according to the present invention.

FIG. 4 is a front view showing the moon shape of FIG. 3;

FIG. 5 is a perspective view showing still another example of the core material according to the present invention.

FIG. 6 is a plan view of the moon shape of FIG. 5;

FIG. 7 is a perspective view showing still another example of the core material according to the present invention.

8 is a plan view of the moon of FIG. 7;

9 is an enlarged cross-sectional view taken along the line BB of FIGS.

FIG. 10 is an enlarged cross-sectional view taken along line AA of FIGS. 4 and 8;

FIG. 11 is a perspective view showing a conventional core material.

FIG. 12 is a plan view of the moon of FIG. 11;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Core material 2 ... Moon shape 3 ... Curved inner surface 4 ... Curved outer surface 5 ... Rawhide 6 ... Impregnated paper 7 ... Adhesive

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takuya Nomura 1-10-6 Shinonome, Koto-ku, Tokyo Inside Oji Paper Co., Ltd. Shinonome Research Center (72) Inventor Mina Yoshida 1-10-10, Shinonome, Koto-ku, Tokyo No. 6 Oji Paper Co., Ltd. Shinonome Research Center (72) Inventor Yoshiaki Kabayama 1-10-6 Shinonome, Koto-ku, Tokyo Oji Paper Co., Ltd. Shinonome Research Center (72) Inventor Hiroo Uenuma Sumida, Tokyo 6-29-3 Higashi-Mukojima Ward, Tokyo

Claims (12)

[Claims] 1. A shoe for a lug or the like, comprising a recycled leather paper obtained by impregnating a synthetic resin into a recycled leather paper base paper containing a tannin tanned leather fiber obtained by dry-grinding tannin tanned leather. Core material. 2. The recycled leather paper base paper adjusts the tannin tanning swarf to a water content of 12% by weight or less, and has a peripheral speed of 1,000 m / min or more, and a clearance between the rotary blade and the fixed blade of 0.3 mm or more.
Pulverization was performed with a dry pulverizer at a setting of 0.5 mm.
2. A shoe core material according to claim 1, wherein the core material is made of shaving fibers that are dry-selected with a round hole screen having a diameter of 5 mm to 1.5 mm. 3. The recycled leather base paper contains natural cellulose fibers and / or synthetic fibers.
Or the shoe core material according to 2. 4. The shoe core according to claim 3, wherein the synthetic fibers are heat-fusible fibers. 5. The shoe core material according to claim 1, wherein the recycled leather base paper carries 0.8% by weight or more of chitosan. 6. 0.5 to 10% by weight of recycled leather paper base paper
The shoe core material according to any one of claims 1 to 5, wherein the core material contains a foamable resin in an amount of 1% by weight. 7. The synthetic resin has a glass transition temperature of −40 ° C. to +
10 ° C. synthetic resin and the amount of synthetic resin carried is 5-4
The shoe core material according to any one of claims 1 to 6, wherein the content is 0% by weight. 8. The shoe core material according to claim 1, wherein the recycled leather paper is subjected to a pressure compression treatment. 9. The shoe core material according to claim 1, wherein a lump is attached to at least one surface of the recycled leather paper. 10. The shoe core material according to claim 1, wherein an impregnated paper is attached to at least one surface of the recycled leather paper. 11. The core material for shoes according to claim 1, wherein a lump is adhered on one side of the recycled leather paper and an impregnated paper is adhered on the other side. 12. The impregnated paper may be a base paper made of wood pulp alone, a base paper made of wood pulp mixed with shavings, or a base paper made of wood pulp mixed with shavings and synthetic fibers, made of SBR synthetic latex or acrylic. The shoe core material according to claim 10 or 11, wherein the main compounding resin material is impregnated with a resin by dipping resin processing and dried.