JP3020844B2 - Method of manufacturing multi-layer slush molded shoes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a slush-molded shoe comprising a plurality of layers, in which a sole portion of a shoe body and another portion of the shoe body are slush-molded with a plastisol mixed with different polyvinyl chloride resins. In addition, it can be formed along the sole of the shoe without discharging the non-gelled plastisol for the shoe sole.

[0002]

2. Description of the Related Art To manufacture shoes by slush molding made of polyvinyl chloride resin, a slash molding mold having the same recess as the outer shape of the shoe is manufactured by electroforming, and polyvinyl chloride resin is poured into this mold. After forming a semi-gelled film of a certain thickness on the inner surface by heating for a short time, the extra polyvinyl chloride resin that has not been gelled is discharged out of the slush molding mold and heated as a whole,
The semi-gelled film is completely solidified to obtain a skin to be a shoe body, which is cooled and demolded.

[0003] Parts such as a backing cloth (inner boots), an insole, and a fastener are sewn and adhered to the inside of the skin thus formed by slush molding, and further painted to finish a slush molded shoe as a final product.

[0004] In the shoe thus formed by slush molding, the design of the inner surface of the slush molding mold and the like are reproduced as it is, and the sole of the shoe main body (hereinafter simply referred to as the sole) and the sole of the shoe main body. Other parts (hereinafter,
In the slash molding process, the slash molding process also includes a part that is molded on the sole of the shoe), and can provide a complete waterproof / moisture-proof function without seams. It was used for manufacturing, but recently a large number of shoe types (boots) have been developed due to diversification of designs.

[0005] The slash-molded shoes diversified in this way are not only required to have a waterproof and moisture-proof function by integrally molding the sole and the shoe body, but are required to have various functions. The functions required as the shoe body are different,
A certain degree of hardness and abrasion resistance are required for the sole portion of the shoe, and flexibility and the like are required for the shoe body.

[0006] For this reason, conventionally, the shoe sole and the shoe body have been formed into a multilayer structure such as two layers of different materials to provide hardness, abrasion resistance, oil resistance, chemical resistance and the like. ing.

[0007] As a conventional method for forming the sole portion and the shoe body of a slash-formed shoe into two layers, for example,
: There is a method of molding footwear using a plastisol disclosed in Japanese Patent Publication No. 40-13590. As shown in FIG. 3, a cross-sectional structure applied to overshoes is used to heat an outer mold (mold) 11 having the same recess as the outer shape of the footwear. Then, a vinyl resin plastisol is injected into the bottom of the mold 11 so that the bottom 1
After gelling 2, the plastic resin plastisol is further injected by a normal slush molding method to a required height to form a layered gel on the inner surface of the mold 11 to a required thickness, and excess ungelled plastisol is completely discharged. Gelled layer 13
Is completely melted to produce a two-layer slush molded shoe.

Further, in the method for manufacturing oil-resistant shoes disclosed in Japanese Patent Publication No. 59-37963, although not shown, a large amount (50-100 parts) of an oil-resistant polymerizable polyester plasticizer is used in a shoe mold for shoe soles. A certain amount of plastisol A blended in is injected and semi-gelled under heating, and the tread portion is 3 mm to 6 mm.
After forming an oil-resistant bottom having a thickness of 2 mm, the outer layer of plastisol B is filled and filled from above, and heated until the desired thickness is adhered. It is completed and then cooled and taken out.

In the method of manufacturing a multi-layer slush-molded shoe disclosed in Japanese Patent Laid-Open Publication No. Sho 56-70702, a predetermined position inside the slush-molding mold 11 is shown in FIG. Polyvinyl chloride plastisol is injected until heating, an appropriate thickness of the semi-gelled layer 12 is adhered to the inner surface by heating, and the ungelled plastisol is discharged by vacuum suction. The plastisol is injected into the mold 11 slightly above the upper end of the mouth forming portion of the mold 11 by a normal slush molding method using a vinyl plastisol, and a semi-gelled layer 13 having an appropriate thickness is formed by heating. After discharging by the method, the semi-gelled layers 12, 13 attached to the inner surface by heating are completely gelled and molded.

Further, in the method for manufacturing a multi-layer slash-molded shoe disclosed in Japanese Patent Publication No. 58-35683, as shown in a sectional view of FIG. 11a and 11b are provided, polyvinyl chloride plastisol is injected to a predetermined position so as not to stain the inner wall surface, and a semi-gelled layer 12 having an appropriate thickness is adhered to the inner surface by heating, and After discharging from the holes 11a and 11b of the mold 11, the plastisol is slightly raised to the upper end of the mouth forming portion of the mold 11 by a normal slash molding method using polyvinyl chloride plastisol having a different color and physical properties from the bottom portion 12. Inject, heat to form a semi-gelled layer of appropriate thickness, discharge the gelled plastisol by an appropriate method, and then heat the inner surface. Adhere to that two half gelling layer 1
2 and the like are completely gelled.

[0011]

According to the conventional method of manufacturing a two-layer slash-molded shoe, different materials are used for the sole 12 and the other shoe body 13 (the sole 12 is made of a material different from the sole). Two layers with the shoe body).

However, the first production method:
No. 13590) and the second production method:
In Japanese Patent No. 37963), an amount of plastisol necessary for film formation on the sole of a shoe is injected and heated to be semi-gelled. The shape of the bottom is not flat,
For example, as shown in FIG. 3B, since the toe portion 16 and the non-step portion 17 are higher than the ground portion such as the heel 14 and the tread portion 15, the mold 11 for forming the shoe sole portion 12 is formed.
The surface of the liquid plastisol to be injected into the inside is horizontal, and the thickness of the ground contact portion such as the low heel 14 and the tread portion 15 is thick,
There is a problem that the thickness of the high toe portion 16 or the non-step portion 17 becomes thin, and it is difficult to form a film with a uniform desired thickness.

Therefore, a third production method:
No. 70702) and the fourth production method:
No. 35683), a slightly larger amount of plastisol is injected than the plastisol necessary for molding the shoe sole, and the semi-gelled layer is attached by heating, and then the excess plastisol is discharged by vacuum suction. The plug that closes the hole at the bottom must be removed so that excess ungelled plastisol is discharged, and a uniform semi-gelled layer can be formed on the inner surface of the mold. There is a problem that the efficiency is extremely low.

The present invention has been made in view of the above-mentioned problems of the prior art. When a multi-layer slash-molded shoe is manufactured using different materials for a shoe sole and a shoe body, a plastisol for a shoe sole is injected and gold is injected. An object of the present invention is to provide a method for producing a slush-molded shoe having a multilayer structure capable of forming a semi-gelled layer in a mold and discharging the non-gelled plastisol into a shape along the shoe sole without discharging the degreased plastisol.

The present invention also provides a method of manufacturing a multi-layer slush-molded shoe which can gradually change the function of the shoe sole and the shoe body and can clearly distinguish the function of the shoe sole and the shoe body. It is something to offer.

Further, the present invention is intended to provide a method for producing a slash-molded shoe comprising a plurality of layers capable of imparting strength, hardness, abrasion resistance, oil resistance, chemical resistance and the like to the sole of the shoe.

[0017]

According to a first aspect of the present invention, there is provided a method of manufacturing a multi-layer slush-molded shoe, comprising: After injecting the plastisol for the amount required for molding the sole of the shoe, the slush molding mold is heated to leave the ungelled plastisol and to form a semi-gelled layer along the shoe sole shape, The plastisol for the shoe body mixed with the polyvinyl chloride resin different from the plastisol for the shoe sole is injected and further heated, through the mixed semi-gelled layer of the non-gelled plastisol for the sole and the mixed plastisol for the shoe body. After the shoe body semi-gelled layer is formed, the non-gelled plastisol is discharged and gelled by heating.

According to a second aspect of the present invention, there is provided a method of manufacturing a multi-layer slash-molded shoe according to the first aspect of the present invention, wherein the injection amount of the plastisol for the shoe sole and the residual non-gel of the plastisol for the shoe sole are added. And at least one of the amount of the plastisol is changed to change the film forming range and the mixing ratio of the mixed semi-gelled layer of the plastisol for the shoe sole and the plastisol for the shoe body. is there.

Further, according to a third aspect of the present invention, there is provided a method of manufacturing a multi-layer slash-molded shoe according to the first or second aspect, wherein a polyvinyl chloride resin is injected into a shoe sole of the slush-molded mold. Plastisol mixed with a crosslinkable polyvinyl chloride resin, thermosetting plasticizer,
It is characterized by comprising any one of the three oil-resistant plasticizers or a combination of two or more thereof.

According to a fourth aspect of the present invention, there is provided a method for manufacturing a multi-layer slush-molded shoe, wherein a polyvinyl chloride resin injected into a shoe sole of the slush-molding mold is mixed. The plastisol thus obtained is characterized by further mixing an anti-slip material.

Here, the sole portion is a portion that can be projected on a horizontal surface when the shoe is placed on a horizontal surface in a normal use state, and includes a heel portion, a tread portion, a ground contact portion, and the like. It is composed of a toe part and a non-step part, but it does not necessarily include all of these constituent parts, and a part such as a step part is also a shoe sole here.

Therefore, the amount required for forming the sole portion is defined as the heel portion, the tread portion,
In the case of the toe part and the non-step part, it means the injection amount that can be formed by covering these parts.For example, the heel part, which is the ground contact part to the ground, is put on separately, In the case where only the attachment portion is to be formed as a shoe sole portion, it means the injection amount that can be formed by covering only the tread portion.

Further, the shoe body refers to a part other than the sole part of the shoe. In the slash molding process, the shoe body includes the part formed so as to overlap with the sole part.

The term "leaving the non-gelled plastisol" means that the non-gelled plastisol remains in a state in which a semi-gelled layer is formed on the sole of the shoe, and the amount of the plastisol required for molding is reduced. The amount varies depending on the amount of excess plastisol and the molding thickness of the semi-gelled layer.

Further, the mixed semi-gelled layer refers to a semi-gelled layer formed by mixing a non-gelled plastisol for a shoe sole and a plastisol for a shoe body injected later, and the remaining ungelled layer. Depending on the amount of gelled plastisol, the range of the mixed semi-gelled layer and the mixing ratio will change.If the amount of the remaining ungelled plastisol is extremely small, the mixed semi-gelled layer is hardly formed and the sole of the shoe is not formed. The functions of the shoe sole and the shoe body are clearly distinguished, and if the amount is large, the mixed semi-gelled layer is formed over a wide area, and the functions of the shoe sole and the shoe body gradually change.

[0026]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a method for manufacturing a multi-layer slash-formed shoe according to the present invention will be described in detail with reference to the drawings.

FIG. 1 is a process diagram in the case where the method for producing a multi-layer slush molded shoe of the present invention is applied to the production of a two-layer slush molded shoe.

(1) In the method of manufacturing a slush-molded shoe, as a first step, as shown in FIG. 1A, the shoe sole 2 of a slush-molding mold 1 (hereinafter simply referred to as a mold 1). A plastisol mixed with a polyvinyl chloride resin as the plastisol 3 for the shoe sole is injected in an amount more than necessary to form the shoe sole 2.

The shoe sole 2 to be formed here is a toe 2
a, the stepped portion 2b, the non-stepped portion 2c, and the heel portion 2d, and the injection amount of the plastisol 3 for the sole is the thickness of the sole 2 at the highest part of the non-stepped portion 2c. Is the amount that the plastisol 3 for shoe soles is injected beyond the height of the plastisol.

The shoe sole 2 to be formed has a function required as a shoe sole, for example, when abrasion resistance is required, the tread portion 2b and the heel portion 2 which are in contact with the ground.
Since mold d should have the minimum function, mold 1
It is sufficient that the amount of the plastisol 3 for soles exceeds the height obtained by adding the film thickness to the tread portion 2b and the heel portion 2d, which are the lower portions, and the floor or the like which is wet with oil can be used. In the case of oil resistance required for walking, the toe 2a, the tread 2b,
The function is required for the shoe sole 2 including both the non-stepped portion 2c and the heel 2d. Also, in the case of high heels,
It is also possible to make the heel part separate and adhere after completion of the molding. In this case, it is sufficient to form only the tread portion 2 b as the sole 2.

As the plastisol 3 mixed with polyvinyl chloride resin for the sole of the shoe, a general plastisol blended with polyvinyl chloride resin used in the manufacture of slush-molded shoes is used. However, in addition to the functions required for the sole portion 2 of the slash-formed shoe, for example, abrasion resistance, oil resistance, hardness, etc., it is appropriately determined in consideration of cost and the like.

For example, as a preferred compounding example, a plastisol containing 100 parts by weight of a polyvinyl chloride paste resin, 80 to 100 parts by weight of a plasticizer, and 3 to 5 parts by weight of a stabilizer can be used.

As the plasticizer, phthalate plasticizers such as DOP and other plasticizers such as adipic ester, polyester and epoxy can be used.

Examples of the stabilizer include tin laurate stabilizers such as diphthyltin dilaurate, tin malate stabilizers such as dibutyltin dimaleate, tin mercapto stabilizer, Ba
System, Zn system, Ca system, and their composites, etc. can be used.

(2) Thereafter, the sole 2 of the mold 1 is heated so that the injected plastisol 3 for the sole of the shoe is semi-gelled on the sole 2 of the mold 1 and adhered as the semi-gelled layer 4.

The mold 1 of the plastisol 3 for shoe soles
When the injection amount into the shoe sole 2 to be molded is very slightly larger than the shoe sole 2 to be molded, the mold 1 is inclined at least once at one side or both sides of the toe 2a or the heel 2d. Thus, the semi-gelled layer 4 can be formed by adhesion.

(3) By heating the mold 1 in this manner, the plastisol 3 for a sole in a liquid state, which has been injected into the sole 2 of the shoe, has an increased viscosity and is semi-gelled to form a film around the mold 1. In the semi-gelling step of the plastisol 3 for a shoe sole, the plastisol 3
Since the injection amount of the mold 1 is large, the amount is small, the viscosity does not increase, and the fluidity does not deteriorate.
By adjusting the heating, a semi-gelled layer 4 having a desired thickness to be formed on the shoe sole 2 can be formed.

Then, in a state where the semi-gelled layer 4 having a desired thickness is formed, an ungelled plastisol 5 remains due to the presence of extra plastisol for shoe soles.

Therefore, in the semi-gelling step of the sole 2, the heating temperature of the sole 2 of the mold 1 is
It is necessary to increase the viscosity of the plastisol 3 for shoe sole injected into the mold so that the plastisol 3 can be semi-gelled or gelled. When the heating temperature of the sole 2 of the mold 1 is 100 ° C. or lower, film formation is sufficiently performed. On the other hand, if heated to 200 ° C. or higher, the injected plastisol 3 gels in a short time and loses fluidity, making it impossible to obtain a smooth surface. The heating temperature of 2 should just be in the range of 120-200 degreeC, Preferably it is about 140-180 degreeC. If the heating temperature is set within the above range and the heating amount is changed, the mold 1
The thickness of the semi-gelled layer 4 to be formed can be adjusted.

When the mold 1 is inclined,
The plastisol 3 for soles flows to the part lowered by the inclination, and the semi-gelled layer 4 conforming to the shape of the sole part 2 can be further deposited and deposited.

Further, a plastisol mold 1 for shoe soles
For example, the injection into the mold 1 may be the same as the conventional injection means in which the injection nozzle is inserted into the mold 1 and sprayed with appropriate pressure toward the shoe sole 2 so as not to adhere to anything other than the shoe sole 2. I do.

According to such a semi-gelling step for the sole 2, the plastisol 3 for the sole is injected and heated in an amount required for molding the sole 2, and the plastisol flows by heating. As shown in FIG. 1B, the semi-gelled layer 4 having a desired thickness is formed along the inner surface of the mold 1 with a large amount of the plastisol 3 for the sole as shown in FIG. Can be formed.

By changing the amount of heating, the thickness of the semi-gelled layer 4 to be formed can be changed, and by partially changing the amount of heating, the semi-gelled layer 4 can be partially changed. The film thickness of No. 4 can also be changed.

(4) Thereafter, in the normal slush molding method, the excess ungelled plastisol 5 that has become excessive due to the formation of the semi-gelled layer 4 on the shoe sole 2 is discharged, and then the plastisol 6 for the shoe body is injected. According to the present invention, the plastisol 6 for the shoe body is injected while leaving the ungelled plastisol 5 for the sole of the shoe as it is.

As the plastisol 6 for the shoe body injected onto the ungelled plastisol 5 for the sole, a plastisol mixed with a polyvinyl chloride resin different from the plastisol 3 for the sole is used. 1 to the opening at the upper end of the mold 1 or in the vicinity thereof, depending on the height required for the product shoe.

As the plastisol 6 for the shoe body, a plastisol obtained by mixing a conventionally used ordinary polyvinyl chloride resin is used. For example, a composition example of such a plastisol is a polyvinyl chloride paste resin: 100
Parts by weight, plasticizer: 80-100 parts by weight, stabilizer: 2-3
Parts by weight, pigment: 1 to 2 parts by weight.

When the plastisol 6 for the shoe body is injected into the ungelled plastisol 5 for the shoe sole in this way, FIG.
As shown in FIG. 2A, a mixing portion 7 of two plastisols is formed in the mold 1, and a mixing ratio (concentration) of the plastisol 3 for a shoe sole is high in a portion of the mold 1 near the shoe sole 2. The mixing ratio (concentration) of the plastisol 3 for shoe soles becomes lower toward the upper part of the mold 1, and if it exceeds a certain height, there is only the plastisol 6 for shoe soles where the plastisol 3 for soles hardly mixes.

The range in which the mixed portion 7 of the two plastisols is formed can be changed by the amount of the residual ungelled plastisol 5, the amount of the plastisol 6 for the shoe body to be injected, and the injection method. By injecting the plastisol 6 for the shoe body in small portions, the portion where the mixing ratio (concentration) of the mixing portion 7 is high and the range thereof can be changed.

Thereafter, the shoe body 8 and the heel portion (heel portion) 9 are slush-molded in the same manner as in the usual slush molding method. These steps will be briefly described.

(5) After injecting the plastisol 6 containing the polyvinyl chloride resin for the shoe body into the mold 1 in this manner, by heating the entire mold 1, the first layer of the plastisol 3 for the sole of the shoe sole is semi-gelled. Mold 1 on layer 4
Mixed semi-gelled layer 10 of mixed plastisol of a predetermined thickness and semi-gelled layer 1 of plastisol 6 for shoe body over the entire inner surface of
1 is formed as a second layer.

The thickness of the second layers 10 and 11 is adjusted by adjusting the heating time and the heating temperature of the entire mold 1.

(6) The second layers 10, 11 thus formed in the mold 1 are composed of the mixed semi-gelled layer 10 and the shoe body semi-gelled layer 11, and the mixed semi-gelled layer 10 is The semi-gelling layer 11 having a function between the plastisols 3 and 6 constituting the shoe sole 2 and the shoe body 8 in the lower portion closer to the bottom 2 and having the function of the plastisol 6 of the shoe body 8 becomes closer to the upper portion. It is formed on the inner surface of the mold 1.

Therefore, by increasing the injection amount of the plastisol 3 for the sole and increasing the residual amount of the non-gelled plastisol 5 after the formation of the semi-gelled layer 4, the plastisol 3 for the sole can be relatively high. Now you can get more features
If the amount of the non-gelled plastisol 5 of the plastisol 3 for the sole is made small, the amount of the mixing part 7 of the two plastisols 3 and 6 is made small, so that the functions of the sole 2 and the shoe body 8 can be clearly distinguished. become able to.

Therefore, for example, if the shoe sole 2 is molded using a shoe sole plastisol 3 mixed with an oil-resistant plasticizer so that the mixed semi-gelled layer 10 is formed under the shoe body 8, At the same time as the sole has oil resistance, it also gives body oil to the part of the shoe body that comes into contact with the oil at the bottom, and gradually has the function of the shoe body as it goes to the upper part of the shoe body. Necessary functions can be provided to parts that require sex.

In this way, not only oil resistance but also strength,
Hardness, abrasion resistance, chemical resistance, and the like can be imparted to the required parts of the shoe sole and the lower part of the shoe body.

(7) Next, the plastisol 6 containing the polyvinyl chloride resin for the shoe body in the ungelled state remaining on the inner surface of the mold 1 is discharged.

(8) Thereafter, in this embodiment, as shown in FIG. 1D, a heel plastisol 12 is injected into the heel portion 4 of the mold 1 so that the heel portion 4 becomes flat. .

(9) After the injection of the plastisols 3, 6, and 12 into the shoe sole 2, the shoe body 8, and the heel 9 necessary as the skin 13 of the slush-molded shoe is completed, the entire mold 1 is sufficiently heated. Thereby, the first layer 4, which is the sole part 2, which is semi-gelled, the second layers 10, 11, which are the shoe body 8, and the third layer, which is the heel part 9, are completely solidified.

(10) After this, the mold 1 is cooled.
As shown in FIG. 2B, a skin 13 of a slush-molded shoe is obtained.

Parts such as a backing cloth (inner boots) and an insole are assembled to the thus formed skin 13 of the slash-formed shoes by sewing, bonding, etc., and further painted to finish the final product.

According to the method for manufacturing a multi-layered slash-formed shoe, when the multi-layered slash-formed shoe is manufactured using different materials for the shoe sole 2 and the shoe body 8, the shoe sole 2 and the shoe body 8 are formed. Functions such as oil resistance and abrasion resistance can be changed, and these functions can be continuously changed or relatively clearly distinguished.

Further, when the sole 2 is formed into a film, the plastisol 3 for the sole is injected in an amount larger than that required for the molding and the material is heated to be semi-gelled. It becomes easy to form a film.

Furthermore, there is no need to discharge the ungelled plastisol 5 in the shoe sole 2, so that the manufacturing process is simplified and the production efficiency is improved.

Accordingly, it is not necessary to discharge the ungelled plastisol 5 from the shoe sole 2 and a film having a required thickness is realized, and at the same time, the material is continuously formed according to the functions required for the shoe sole 2 and the shoe body 8. Multi-layer slush-molded shoes can be manufactured to vary or be distinguished.

Further, by changing one or both of the injection amount of the plastisol for the sole and the amount of the remaining ungelled plastisol of the plastisol for the sole, the plastisol for the sole and the plastisol for the sole body are changed. The mixing range and mixing ratio of the mixed semi-gelled layer can be changed, and a multilayer slash-molded shoe can be manufactured according to the functions required for the sole portion and the lower portion of the shoe body.

Next, a specific example of a plastisol mixed with a polyvinyl chloride resin as a plastisol 3 for a shoe sole used for manufacturing a multi-layer slush-molded shoe of the present invention will be described.

Particularly effective resins for improving the performance of the sole portion 2 and the lower portion of the shoe body 8 are any one of three of cross-linkable polyvinyl chloride resin, thermosetting plasticizer, and oil-resistant plasticizer, or any of these. Are combined with two or more, and specifically, there are the following seven types A to G.

A: Crosslinkable polyvinyl chloride resin B: Thermosetting plasticizer C: Oil resistant plasticizer D: Crosslinkable polyvinyl chloride resin and thermosetting plasticizer E: Thermosetting plasticizer and oil resistant plasticizer F: Cross-linkable polyvinyl chloride resin and oil-resistant plasticizer G: Cross-linkable polyvinyl chloride resin, thermosetting plasticizer, and oil-resistant plasticizer Further, for each of A to G, mixing of an anti-slip material is combined. And eventually,
A, A +, B, B +, ..., G, G + total 1
There are four types.

(1) A: cross-linkable polyvinyl chloride resin,
A + Anti-slip material The crosslinkable polyvinyl chloride resin used as the plastisol 3 for shoe soles in the present invention has one or more kinds of hydroxyl group, carboxyl group, epoxy group and alkoxy group in the molecule, and crosslinks with isocyanate etc. Crosslinking and curing are performed by mixing and heating the agents.

Examples of the crosslinking agent include tolylene diisocyanate, tolylene isocyanate dimer, diphenylmethane diisocyanate, hexamethylene diisocyanate, adduct of trimethylolpropane-tolylene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, succinic acid, glutaric acid. Acid, adipic acid, pimelic acid, azelaic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid and their anhydrides, epoxy up to n = 10, triglycidyl isocyanate, 4,4'-diaminodiphenylmethaneglycidylamine, in the molecule Mercapto (-S-
H) Group-containing azole, thiazole and triazine compounds or metal salts thereof (such as 2-R-4.6-dimercapto-S-triazine), and an azo group (-N = N-
Group), a -S-S- group, a -N-S- group, a compound containing a -O-O- group, and the like.

An example of the composition of a plastisol mixed with a crosslinkable polyvinyl chloride resin is a polyvinyl chloride paste resin:
50 to 90 parts by weight, crosslinkable polyvinyl chloride resin: 10 to 10 parts by weight
50 parts by weight, plasticizer: 80 to 120 parts by weight, stabilizer: 2
-3 parts by weight, crosslinking agent: 0.5-3 parts by weight, pigment: 0-2
Parts by weight.

In the present invention, the sole 2 of the shoe body 8
All or a part of the plastisol is formed by heating and gelling a plastisol mixed with a cross-linkable polyvinyl chloride resin. The mixing portion 7 can be formed so as to be continuous from the shoe sole 2 to a part of the shoe main body 8, and the cross-linking improves the heat resistance of the shoe sole 2, makes it difficult to melt even under heating conditions, and has a cigarette resistance. (Heat resistance) is improved, and the lower part of the shoe body 8 also has characteristics and functions similar to those of the shoe sole 2.

Further, the shoe sole 2 and the shoe body 8 are formed by bridging.
The strength, oil resistance, chemical resistance and abrasion resistance of the lower part are also improved.

If the plastisol mixed with the cross-linkable polyvinyl chloride resin is injected to the upper end of the slush molding mold 1 and cross-linking is performed, the cross-linking makes it difficult to peel off the slush molding mold 1 and the mold release property. However, in this invention, the sole plastisol 3 mixed with a cross-linkable polyvinyl chloride resin is used for all or only a part of the sole 2, and the lower part of the shoe body 8 is used in the present invention. Since the concentration is lowered by mixing, the releasability does not decrease much, and the amount of plastisol mixed with expensive cross-linkable polyvinyl chloride resin can be suppressed to the minimum necessary, so that the production cost is reduced. The rise can be suppressed.

The shoe body 8 is made of a heated gel of a plastisol mixed with an ordinary polyvinyl chloride resin which has been conventionally used. Does not change,
A composition example of such a plastisol is 100 parts by weight of polyvinyl chloride paste resin, 80 to 100 parts by weight of a plasticizer, 2 to 3 parts by weight of a stabilizer, and 1 to 2 parts by weight of a pigment.

According to the present invention, a plastisol 3 containing a crosslinkable polyvinyl chloride resin as a raw material
In addition, if necessary, by further mixing an anti-slip material, it is possible to further improve the anti-slip property of the shoe sole in addition to the strength, oil and chemical resistance and wear resistance of the shoe sole.

Since the anti-slip material is generally a colored and insoluble material, if it is mixed in a portion other than the sole portion 2 of the shoe body 8, it is recognized as a foreign substance and the appearance quality is remarkably deteriorated. Since it mixes only with the sole 2, the shoe sole can be provided with an anti-slip action without deteriorating the appearance quality. Rather, by mixing the anti-slip material, the anti-slip property that can be surely imparted to the sole of the shoe can be visually appealed, so that the slash-molded shoes sold in snowy areas and the like can be improved in merchantability.

When the shoe sole plastisol 3 mixed with the anti-slip material is used, it is not necessary to provide the function and characteristics to the lower part of the shoe body 8. What is necessary is just to form a film,
The injection amount may be set to an amount corresponding to this.

Specific examples of the anti-slip material include fibers such as cotton, staple (staple fiber), rayon, acrylic, vinylon, nylon, polyester, polyurethane and glass fiber, having a thickness of 50 denier or less and a length of 50 denier or less. Relatively thin and short fibers of 3.0 mm or less, leather powder, natural plant powder such as rice husk powder, walnut hull powder, metal powder such as metal whisker, inorganic whisker, iron, aluminum, alumina powder, ceramic It is an insoluble powder such as powder or synthetic rubber such as NBR, crosslinked resin, acrylic resin, urethane resin and the like. The anti-slip material of the powder has a size of 3
It is 0 mesh or less, desirably 50 mesh or less.

[0080]

【Example】

 (Example 1)

[0081]

[Table 1]

First, as a plastisol for a sole, for a sole having a composition shown in Table 1 (hereinafter, simply referred to as a first layer).
Plastisol is injected into the mold about 20 mm including the bottom design of the shoe sole, and the mold is heated at 150 ° C. for 1 to 2 minutes to form a semi-gelled layer on the entire shoe sole, leaving an ungelled plastisol. It was in a state.

Next, with the plastisol for the first layer remaining, the plastisol for the shoe body (hereinafter simply referred to as the second layer) is filled up to the upper end of the mold according to the composition shown in Table 1 above. Inject into the lower part of the shoe body for the first layer and the second
With the plastisol mixed for the layer formed, the mold was heated at 180 ° C. for 1-2 minutes to adhere the mixed semi-gelled layer and the semi-gelled layer of the desired thickness to the entire inner surface of the mold. Thereafter, the ungelled plastisol was discharged.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was injected into the heel portion according to the composition shown in Table 1 above, and filled at 200 ° C.
For 5 to 7 minutes to sufficiently crosslink the first layer and sufficiently gel the second layer and the heel.

Then, after cooling, the slush-molded shoe was taken out of the slush-molded mold to obtain a slush-molded shoe in which both the shoe sole and the shoe body were black.

On the other hand, the step of discharging the ungelled plastisol of the plastisol for shoe soles without adding the crosslinkable polyvinyl chloride plastisol to the first layer was added, and the slush molding of the comparative example was carried out under exactly the same conditions. Manufactured shoes.

The strength, abrasion resistance, cigarette resistance (heat resistance), and oil resistance and chemical resistance of these two slush-molded shoes were evaluated in the following manner. (Strength) Tensile strength, elongation, and tear strength were measured using a Shopper type tensile tester based on JIS K-6301. (Wear resistance) Wear wheel CS-1 by Taber abrasion tester
The wear loss at 1000 revolutions was measured according to 0. (Cigarette resistance) A test piece of JIS K-6301 No. 1 was cut out from the shoe sole, hung in an oven at 180 ° C. for 5 minutes, and the presence or absence of a melt-down was measured, and the elongation percentage in the case of not falling was measured.

Also, the tobacco was actually trampled with the two manufactured slash-molded shoes to extinguish the fire, and the shoe sole was melted and melted.
The deformation state was confirmed. (Oil resistance and chemical resistance) Using JIS No. 3 oil and vegetable oil (soy oil), a change in weight when immersed at 40 ° C for 96 hours was measured.

Table 2 summarizes the results of these measurements.
The slush-molded shoe formed according to the present invention has the same strength, hardness and feeling of the upper part of the shoe body as the conventional slush-molded shoe, and the shoe sole and the lower part of the shoe body are particularly heat-resistant ( Cigarette resistance), tensile strength, abrasion resistance, oil resistance and chemical resistance were also improved, and various properties of the shoe sole and the shoe body lower were improved.

[0090]

[Table 2]

Example 2 In order to confirm the improvement of the slip resistance,
As shown in Table 1, a whisker (manufactured by Shikoku Chemical Industry Co., Ltd.) was mixed as a non-slip material with the crosslinkable polyvinyl chloride plastisol, which is a raw material for the sole of the shoe used in Example 1 above. Slush molded shoes were produced in exactly the same manner by the production method of the present invention.

The resulting slash-molded shoes were evaluated for slip resistance as follows. (Anti-slip property) Shoes were placed on each of a P tile, a vinyl floor material, and ice, and were pulled under a load of 10 kgf, and the stress at the time of starting was measured.

Table 2 shows the results. Together with the results of Example 1, it can be seen that the slush-molded shoes of the manufacturing method of the present invention have excellent anti-slip properties in addition to the effects of Example 1.

(2) B: thermosetting plasticizer, B + anti-slip material The thermosetting plasticizer to be mixed with the polyvinyl chloride resin used as the plastisol 3 for shoe soles in the present invention is a liquid before curing, so that the plastisol When mixed, the viscosity of the plastisol can be adjusted.

There are many types of thermosetting plasticizers,
Since the hardness after hardening can be selected from a number of relatively soft to hard ones, the hardness of the shoe sole and the lower part of the shoe body can be set to some extent freely.

The types of thermosetting plasticizers that can be used here are listed below. Allyl ester-based thermosetting plasticizer diallyl phthalate, allyl acrylate, triallyl cyanate, diallyl maleate, dichloroallyl maleate, diallyl itaconate, diallyl sebacate, diallyl adipate, diallyl malonate, diallyl glycolate, Triallyl aconitate, triallyl phosphate and the like.

Acrylate-based thermosetting plasticizer Allyl methacrylate, diallyl fumarate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, cyclohexyl methacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butane 1,4 diol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane propylene oxide adduct triacrylate, dimethylaminoethyl methacrylate, 1,
3-butylene glycol dimethacrylate and the like.

Unsaturated polyester-based thermosetting plasticizer Radical polymerization is carried out by heating a linear polyester having several double bonds in the molecule.

Epoxy Thermosetting Plasticizer A curing agent such as an aliphatic amine or an acid anhydride is added to a long-chain or cyclic aliphatic epoxy resin to cure the resin.

In particular, an allyl ester-based thermosetting plasticizer,
Acrylic ester-based thermosetting plasticizers include benzoyl peroxide (BPO), t-butyl perbenzoate (TBPB), and dicumyl peroxide (DC) as polymerization catalysts.
PO), cumene hydroperoxide (CHPO) and the like are added and heated to undergo radical polymerization and cure.

An example of the composition of a plastisol mixed with the above thermosetting plasticizer is a polyvinyl chloride paste resin: 10
0 parts by weight, plasticizer: 80 to 120 parts by weight, thermosetting plasticizer: 10 to 40 parts by weight, catalyst: 0.3 to 1 part by weight, stabilizer: 2 to 3 parts by weight, crosslinking agent: 0.5 ~ 3 parts by weight, pigment:
0 to 2 parts by weight.

In the slush-molded shoe according to the present invention manufactured by using such a plastisol for a shoe sole (for the first layer), all or a part of the lower part of the shoe body and the sole of the shoe are mixed with a thermosetting plasticizer. Since it is composed of the gelled product of plastisol, the heat resistance of the shoe sole and the lower part of the shoe body is improved, so that it is difficult to melt even under heating conditions, and the cigarette resistance (heat deformation resistance) is improved.

Further, the strength, oil resistance, chemical resistance and wear resistance of the sole portion and the lower portion of the shoe body are also improved.

If a plastisol mixed with a thermosetting plasticizer is injected to the upper end of the slush molding mold, it is difficult to peel off from the slush molding mold, the releasability is significantly reduced, and mass production becomes difficult. However, since the plastisol mixed with the thermosetting plasticizer is used only in the sole or the lower part of the shoe body where the ungelled plastisol is mixed with all or a part of the sole of the shoe, the demoldability is not significantly reduced, Further, since the amount of use can be suppressed to the minimum necessary, an increase in manufacturing cost can be suppressed. (Example 3)

[0105]

[Table 3]

First, as a plastisol for soles, a plastisol for the first layer having a composition shown in Table 3 was added to a plastisol for about 20 hours including a sole design of a sole part in a slush molding mold.
mm, and heated at 150 ° C. for 1 to 2 minutes to form a semi-gelled layer on the entire shoe sole, leaving an ungelled plastisol.

Next, with the plastisol for the first layer remaining, the polyvinyl chloride paste resin for the second layer was poured completely up to the upper end of the slush molding mold according to the composition shown in Table 3 above. In a state where the two plastisols were mixed at the lower part of the main body, the mixture was heated at 180 ° C. for 1 to 2 minutes to attach the mixed semi-gelled layer and the semi-gelled layer having a desired thickness to the inner surface of the slush molding mold. Thereafter, the ungelled plastisol was discharged.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was poured into the heel portion of the mold according to the composition shown in Table 3 above, and filled at 200 ° C. for 5 to 7 hours. After heating for 1 minute, the first layer was sufficiently crosslinked and the second layer and the heel were sufficiently gelled.

After cooling, the molded product was taken out of the mold to obtain a slash-molded shoe in which both the sole and the shoe body were black.

On the other hand, a plastisol containing no thermosetting plasticizer was used for the first layer, and a step of discharging the non-gelled plastisol of the plastisol for shoe soles was added. Slush molded shoes were manufactured.

The strength, abrasion resistance, cigarette resistance (heat resistance), and oil resistance and chemical resistance of these two slush-molded shoes at the shoe sole and the lower part of the shoe body were evaluated by the methods described above.

Table 4 summarizes the results of these measurements.
The slush-molded shoe according to the manufacturing method of the present invention has the same strength, hardness and feeling of the upper part of the shoe body as that of the conventional slush-molded shoe, and furthermore, the sole part and the lower part of the shoe body are particularly abrasion resistant. It was found that the properties of the shoe sole and the lower part of the shoe body were improved, as well as the tensile strength, heat deformation resistance (cigarette resistance), and oil and chemical resistance.

[0113]

[Table 4]

Example 4 In order to confirm the improvement of the slip resistance,
As shown in Table 3, a whisker (Shikoku Chemical Industry Co., Ltd.) was used as a non-slip material in a plastisol mixed with a thermosetting plasticizer, which is a raw material for the shoe sole used in Example 3 above.
Was further mixed, and slush-molded shoes were produced by the production method of the present invention in exactly the same manner as in Example 3.

The obtained slush-molded shoes were evaluated for slip resistance in the same manner as described above by the measurement method described above.
Table 4 shows the results.

In addition to the results of Example 3, it can be seen that the slush-molded shoes of the manufacturing method of the present invention have excellent anti-slip properties in addition to the effects of Example 3.

(3) C: oil-resistant plasticizer, C + non-slip material In the present invention, a plastisol mixed with an oil-resistant plasticizer (for example, a high-molecular-weight plasticizer) is used as the plastisol 3 for shoe soles. Gives oil resistance to the lower part of the shoe body and reduces the extraction into gasoline and oils,
Improve the adaptability for use in gas stations and various food factories.

The oil-resistant plasticizer is a polymerizable polyester plasticizer such as adipic acid-based polyester and phthalic acid-based polyester, and has a molecular weight of 800 or more and 4000 or less, preferably 1,000 or more and 3000 or less.

When the degree of polymerization is less than 800, the plasticizer is extracted into vegetable oil, animal oil, gasoline and the like in food factories and becomes hard, and the effect of improving oil resistance is reduced.
When it is not less than 00 and not more than 4000, the effect of improving oil resistance is large, but when the degree of polymerization exceeds 4,000, the viscosity of the plastisol is increased and the fluidity is remarkably reduced, resulting in insufficient workability.

An example of the composition of a plastisol mixed with an oil-resistant plasticizer is: polyvinyl chloride paste resin: 100 parts by weight, primary plasticizer: 10 to 60 parts by weight, oil-resistant plasticizer: 1
00 to 40 parts by weight, stabilizer: 2 to 3 parts by weight, pigment: 0 to 0 parts by weight
2 parts by weight.

In the slush-molded shoe according to the manufacturing method of the present invention, since the whole or a part of the lower part of the shoe body and the sole of the shoe are made of a heated gel of plastisol mixed with an oil-resistant plasticizer, the lower part of the shoe and the lower part of the shoe body are formed. Oil resistance and chemical resistance are improved.

When the plastisol mixed with the oil-resistant plasticizer is to be injected to the upper end of the slush molding mold, the injection is difficult or time-consuming due to the extremely high viscosity, and the efficiency is reduced. In addition, when the mold is inclined due to the time required for discharging, a problem such as accumulation of plastisol in the lower portion and an increase in the thickness occurs, but in this case, the plastisol mixed with the oil-resistant plasticizer is used. Such a problem does not occur because only the lower part of the sole of the shoe where the whole or part of the sole of the shoe and its ungelled plastisol are mixed is small and the discharge is in the city. In addition, since the amount of plastisol mixed with expensive oil-resistant plasticizer can be suppressed to the minimum necessary,
An increase in manufacturing cost can be suppressed. (Example 5)

[0123]

[Table 5]

First, as a plastisol for shoe soles, a plastisol mixed with an oil-resistant plasticizer for the first layer having a composition shown in Table 5 was injected about 20 mm inclusive of the sole design of the soles in the mold. While heating the mold for 1-2 minutes, a semi-gelled layer was formed on the entire sole of the shoe, leaving an ungelled plastisol.

Next, with the plastisol for the first layer remaining, the plastisol for the second layer was fully injected to the upper end of the slush molding mold according to the composition shown in Table 5 above, and the plastisol was applied to the lower part of the shoe body. In the state where the mixed plastisol for the first layer and the plastisol for the second layer is formed, the mold is heated at 180 ° C. for 1 to 2 minutes to form a mixed semi-gelled layer having a desired thickness on the inner surface of the slush molding mold. After that, the non-gelled plastisol was discharged.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was injected into the heel portion according to the composition shown in Table 5 above, and the heel portion was filled.
For 5 to 7 minutes to sufficiently crosslink the first layer and sufficiently gel the second layer and the heel.

After cooling, the molded product was taken out of the slush molding mold to obtain a slush molded shoe according to the method of the present invention in which both the shoe sole and the shoe body were black.

On the other hand, a plastisol containing no oil-resistant plasticizer was used for the first layer, and a step of discharging the non-gelled plastisol of the plastisol for shoe soles was added. Molded shoes were manufactured.

In addition to the oil and chemical resistance of the sole and lower part of the shoe body of these two slush molded shoes, the strength,
Abrasion resistance and cigarette resistance (heat resistance) were evaluated in the same manner as described above by the measurement method described above.

Table 6 summarizes the results of these measurements.
The slush-molded shoe formed by the present invention has the same strength, hardness and hand of the upper part of the shoe body as the conventional slush-molded shoe, and the shoe sole and the lower part of the shoe body are particularly oil-resistant. Also, it is understood that the chemical resistance is excellent, and various properties of the shoe sole and the lower part of the shoe body are improved as compared with the conventional two-layer slash-molded shoe.

[0131]

[Table 6]

Example 6 In order to confirm the improvement of the slip resistance,
As shown in Table 5, a whisker (manufactured by Shikoku Chemical Industry Co., Ltd.) was further mixed as an anti-slip material into a plastisol obtained by mixing an oil-resistant plasticizer with the raw material of the shoe sole used in Example 5. A slush-molded shoe was manufactured by the method of the present invention in exactly the same manner as described above.

The obtained slash-molded shoes were similarly evaluated for the slip resistance by the measurement method described above.

Table 6 shows the results. Together with the results of Example 5, it can be seen that the slush-molded shoes of the manufacturing method of the present invention have excellent anti-slip properties in addition to the effects of Example 5.

(4) D: Crosslinkable polyvinyl chloride resin and thermosetting plasticizer, D + anti-slip material In the present invention, a plastisol obtained by mixing a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer is used. The description of the conductive polyvinyl chloride resin is omitted because it has been described in (1) A above.

A plastisol mixed with a crosslinkable polyvinyl chloride resin tends to have a relatively high viscosity when the crosslinkable polyvinyl chloride resin is a powder and has a small amount of a plasticizer. There is a possibility that the workability of the work such as injection into the fuel cell may be reduced.

Therefore, a thermosetting plasticizer is preferably mixed with the above-mentioned plastisol in order to prevent a decrease in workability.

Since the thermosetting plasticizer is a liquid before curing, if it is mixed with a plastisol mixed with a crosslinkable polyvinyl chloride resin, the viscosity of the plastisol can be adjusted. In addition, since there are many types of thermosetting plasticizers, and the hardness after curing can be selected from relatively soft to hard, a certain degree of freedom can be set for the hardness of the shoe sole and the lower part of the shoe body. Will be able to

The types of thermosetting plasticizers that can be used here have been described in (2) B above, and will not be described.

A composition example of a plastisol obtained by mixing such a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer is as follows.
Polyvinyl chloride paste resin: 50 to 90 parts by weight, crosslinkable polyvinyl chloride resin: 10 to 50 parts by weight, plasticizer:
80 to 120 parts by weight, thermosetting plasticizer: 10 to 40 parts by weight, catalyst: 0.3 to 1 part by weight, stabilizer: 2 to 3 parts by weight,
Crosslinking agent: 0.5 to 3 parts by weight, pigment: 0 to 2 parts by weight.

The slush-molded shoe according to the present invention manufactured by using such a plastisol for a shoe sole (for the first layer) has a lower part of the shoe body and a part or all of the sole of the shoe, which are formed of a crosslinkable polyvinyl chloride resin and a thermosetting resin. Because it is composed of a heated gel of a plastisol mixed with a curable plasticizer, the cross-linking improves the heat resistance of the shoe sole and the lower part of the shoe body, making it harder to melt even under heating conditions, and resistant to cigarettes (heat-resistant deformation). ) Is improved.

Further, the strength, oil resistance, chemical resistance and abrasion resistance of the sole portion and the lower portion of the shoe body are improved by the crosslinking.

When a plastisol in which a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer are mixed is injected to the upper end of a slush molding mold and crosslinked,
Cross-linking makes it difficult to separate from the slush molding mold and significantly reduces the removability, making mass production difficult.However, in this case, a plastisol containing a cross-linkable polyvinyl chloride resin and a thermosetting plasticizer is used in the shoe sole. This is only the lower part of the shoe body where all or part of the ungelled plastisol is mixed, so that the removability does not decrease so much, and the amount of use can be suppressed to the minimum necessary. The rise can be suppressed. (Example 7)

[0144]

[Table 7]

First, as a plastisol for soles, a plastisol for the first layer having a composition shown in Table 7 was added to a plastisol for about 20 hours including a sole design of a sole part in a slush molding mold.
mm, and heated at 150 ° C. for 1 to 2 minutes to form a semi-gelled layer on the entire sole of the shoe, leaving an ungelled plastisol.

Next, with the plastisol for the first layer remaining, the plastisol for the second layer was poured completely to the upper end of the slush molding mold according to the composition shown in Table 7 above, and the plastisol was added to the lower part of the shoe body. After the two plastisols are mixed, the mixture is heated at 180 ° C. for 1 to 2 minutes to attach the mixed semi-gelled layer and the semi-gelled layer having a desired thickness to the inner surface of the slush molding mold, and then ungelled. Plastisol was discharged.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was poured into the heel portion of the mold according to the composition shown in Table 7 above, and filled at 200 ° C. to 5 to 7 ° C. After heating for 1 minute, the first layer was sufficiently crosslinked and the second layer and the heel were sufficiently gelled.

After cooling, the molded product was taken out of the mold to obtain a slush-molded shoe in which both the sole and the shoe body were black.

On the other hand, a plastisol not containing a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer was used for the first layer.
In addition, a step of discharging the non-gelled plastisol of the plastisol for shoe soles was added, and the slush-molded shoes of the comparative example were manufactured under exactly the same conditions except for the above.

The strength, abrasion resistance, cigarette resistance (heat resistance), and oil resistance and chemical resistance of these two slush-molded shoes at the shoe sole and the lower part of the shoe body were evaluated by the methods described above.

Table 8 summarizes the results of these measurements.
In the slush-molded shoe according to the manufacturing method of the present invention, the shoe sole and the shoe body lower part are particularly excellent in heat deformation resistance (cigarette resistance), and have tensile strength, wear resistance,
It was found that the oil resistance and chemical resistance were also improved, and various properties of the shoe sole and the lower part of the shoe body were improved.

[0152]

[Table 8]

Example 8 In order to confirm the improvement of the slip resistance,
As shown in Table 7, a whisker (manufactured by Shikoku Chemical Industry Co., Ltd.) was used as a non-slip material in a plastisol obtained by mixing a cross-linkable polyvinyl chloride resin and a thermosetting plasticizer, which are raw materials for the shoe sole used in Example 7 above. ) Was further mixed, and slush-molded shoes were produced by the production method of the present invention in exactly the same manner as in Example 7.

The obtained slush-molded shoes were evaluated for slip resistance in the same manner as described above by the measurement method described above.
Table 8 shows the results.

In addition to the results of Example 7, it can be seen that the slush-molded shoes of the manufacturing method of the present invention have excellent anti-slip properties in addition to the effects of Example 7.

(5) E: Thermosetting plasticizer and oil-resistant plasticizer, E + anti-slip material In the present invention, a plastisol obtained by mixing a thermosetting plasticizer and an oil-resistant plasticizer is used. Is described in (2) B above, and the oil-resistant plasticizer is described in (3) C above, and therefore will not be described.

Here, a plastisol mixed with a thermosetting plasticizer is further mixed with an oil-resistant plasticizer (for example, a plasticizer having a high molecular weight). And improve the adaptability for use in gas stations and various food factories by reducing extraction into gasoline and oils.

The oil-resistant plasticizer has a high viscosity, whereas the thermosetting plasticizer is in a liquid state in a sol, which lowers the viscosity and improves workability.

A composition example of a plastisol in which a thermosetting plasticizer and an oil-resistant plasticizer are mixed is as follows: 100 parts by weight of a polyvinyl chloride paste resin, 10 to 50 parts by weight of a primary plasticizer, 80 to 80 parts by weight of an oil-resistant polyester plasticizer. 40 parts by weight, thermosetting plasticizer: 10 to 40 parts by weight, catalyst: 0.3 to 1 part by weight, stabilizer: 2 to 3 parts by weight, pigment: 0 to 2 parts by weight.

In the slush-molded shoe according to the manufacturing method of the present invention, the whole or a part of the lower part of the shoe body and the sole of the shoe are made of a heated gel of a plastisol mixed with a thermosetting plasticizer and an oil-resistant plasticizer. The crosslinking improves the heat resistance of the shoe sole and the lower part of the shoe body, makes it difficult to melt even under heating conditions, and improves the cigarette resistance (heat deformation resistance). Crosslinking also improves the strength and wear resistance of the sole. Furthermore, oil and chemical resistance is improved because an oil-resistant plasticizer is mixed.

When a plastisol in which a thermosetting plasticizer and an oil-resistant plasticizer are mixed is injected to the upper end of the slush molding mold and heated, a radical polymerization reaction by the thermosetting plasticizer is generated in a chain, and While the entire plastisol may thicken or solidify and become difficult to discharge, cross-linking makes it difficult to remove from the slush molding mold, significantly reduces the releasability and makes mass production difficult. The use of a plastisol mixed with a thermosetting plasticizer and an oil-resistant plasticizer is used only on all or part of the sole of the shoe sole and on the lower part of the shoe body where mixing with the ungelled plastisol occurs, so the demoldability is also significantly reduced. No, and because the amount of plastisol mixed with expensive thermosetting plasticizer and oil-resistant plasticizer can be suppressed to the minimum necessary, It is possible to suppress the rise of the concrete cost. (Example 9)

[0162]

[Table 9]

First, as a plastisol for shoe soles, a plastisol mixed with a thermosetting plasticizer and an oil-resistant plasticizer for the first layer having a composition shown in Table 9 was mixed with a plastisol including the sole design of the sole in the mold. Inject 20mm and at 150 ° C 1 ~
While heating the mold for 2 minutes, a semi-gelled layer was formed on the entire shoe sole, leaving an ungelled plastisol.

Next, with the plastisol for the first layer remaining, the plastisol for the second layer was poured completely up to the upper end of the slush molding mold according to the composition shown in Table 9 above, and the plastisol was applied to the lower part of the shoe body. In the state where the mixed plastisol for the first layer and the plastisol for the second layer is formed, the mold is heated at 180 ° C. for 1 to 2 minutes to form a mixed semi-gelled layer having a desired thickness on the inner surface of the slush molding mold. After that, the non-gelled plastisol was discharged.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was injected into the heel portion according to the composition shown in Table 9 above, and the heel portion was filled.
For 5 to 7 minutes to sufficiently crosslink the first layer and sufficiently gel the second layer and the heel.

After cooling, the slush-molded shoe was removed from the slush-molding mold to obtain a slush-molded shoe according to the method of the present invention in which both the shoe sole and the shoe body were black.

On the other hand, a step of using a plastisol containing neither a thermosetting plasticizer nor an oil-resistant plasticizer in the first layer and discharging a non-gelled plastisol of a plastisol for shoe soles was added, and the other conditions were the same. As a result, a slush molded shoe of a comparative example was manufactured.

The strength, abrasion resistance, cigarette resistance (heat resistance), and oil / chemical resistance of these two slash-formed shoes, such as the shoe sole and the lower part of the shoe body, were measured in the same manner as described above. evaluated.

Table 10 summarizes the results of these measurements. The slush-molded shoe formed by the present invention has the same strength, hardness and feeling of the upper part of the shoe body as the conventional slush-molded shoe. It has excellent resistance (cigarette resistance), improved tensile strength, abrasion resistance, oil resistance and chemical resistance, and improved characteristics of the sole and lower part of the shoe body compared to conventional two-layer slush molded shoes Understand.

[0170]

[Table 10]

Example 10 In order to confirm the improvement of the slip resistance, as shown in Table 9, a plastisol obtained by mixing a thermosetting plasticizer and an oil-resistant plasticizer as raw materials for the sole of the shoe used in Example 9 was used. Then, a whisker (manufactured by Shikoku Chemical Industry Co., Ltd.) was further mixed as an anti-slip material, and slush-molded shoes were manufactured by the method of the present invention in the same manner as in Example 9.

The resulting slash-molded shoes were evaluated for slip resistance in the same manner by the measurement method described above.

Table 10 shows the results. Together with the results of Example 9, it can be seen that the slush-molded shoes of the manufacturing method of the present invention have excellent anti-slip properties in addition to the effects of Example 9.

(6) F: Crosslinkable polyvinyl chloride resin and oil resistant plasticizer, D + anti-slip material In the present invention, a plastisol obtained by mixing a crosslinkable polyvinyl chloride resin and an oil resistant plasticizer is used. The vinyl resin and the oil-resistant plasticizer have been described in the above (1) A and (3) C, and thus will not be described. An example of the composition of a plastisol in which a crosslinkable polyvinyl chloride resin and an oil-resistant plasticizer are mixed is 90 to 0 parts by weight of a polyvinyl chloride paste resin, 10 to 100 parts by weight of a crosslinkable polyvinyl chloride resin, and primary plastic. Agent: 10 to 50 parts by weight, oil-resistant polyester plasticizer: 80 to 40 parts by weight,
Stabilizer: 2 to 3 parts by weight, crosslinking agent: 0.5 to 3 parts by weight, pigment: 0 to 2 parts by weight.

A slash-formed shoe manufactured using a plastisol for a shoe sole having such a composition has a lower part and a part of the sole of the shoe body which are made of a plastisol in which a crosslinkable polyvinyl chloride resin and an oil-resistant plasticizer are mixed. Since it is constituted by a heated gelled product, the heat resistance of the shoe sole and the lower part of the shoe main body is improved by crosslinking, so that it is difficult to melt even under heating conditions, and the cigarette resistance (heat deformation resistance) is improved.

Further, the strength and abrasion resistance of the sole portion and the lower portion of the shoe body are improved by the crosslinking.

In addition, since the oil-resistant plasticizer is mixed, the chemical resistance of the sole of the shoe and the lower part of the shoe body is improved.

If a plastisol containing a cross-linkable polyvinyl chloride resin and an oil-resistant plasticizer is injected to the upper end of the slush molding mold to carry out crosslinking, it becomes difficult to peel off the slush molding mold due to the crosslinking. The removability is remarkably reduced and mass production becomes difficult.However, the use of a plastisol mixed with a cross-linkable polyvinyl chloride resin and an oil-resistant plasticizer in this case makes it possible to use all or part of the sole of the shoe and only this gelled plastisol. Since the mixing occurs only in the lower part of the shoe body, the removability is not significantly reduced, and the amount of plastisol mixed with expensive cross-linkable polyvinyl chloride resin and oil-resistant plasticizer is minimized. Therefore, an increase in manufacturing cost can be suppressed. (Example 11)

[0179]

[Table 11]

First, as a plastisol for shoe soles, Table 11 was used.
The plastisol for the first layer having the composition shown in the following is included in the slush molding mold including the sole design of the shoe sole for about 20 hours.
Injected to a height exceeding the thickness of 150 mm
While heating for 1-2 minutes, a semi-gelled layer was formed on the entire sole of the shoe, leaving an ungelled plastisol.

Next, with the plastisol for the first layer remaining, the plastisol for the second layer was poured completely up to the upper end of the slush molding mold according to the composition shown in Table 11 above, and the plastisol was applied to the lower part of the shoe body. Mixing the plastisol for the first layer and the second layer With the plastisol formed, the mold is heated at 180 ° C. for 1 to 2 minutes to mix and semi-gel the desired thickness on the entire inner surface of the slush molding mold. After depositing the layer and the semi-gelled layer, the ungelled plastisol was drained.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was injected into the heel portion according to the composition shown in Table 11 above, and the heel portion was filled.
C. for 5 to 7 minutes to sufficiently crosslink the first layer and sufficiently gel the second layer and the heel.

After cooling, the molded product was taken out of the slush molding mold to obtain slush molded shoes in which both the sole and the shoe body were black.

On the other hand, a step of using a plastisol not containing a crosslinkable polyvinyl chloride resin and an oil-resistant plasticizer for the first layer and adding a step of discharging the ungelled plastisol of the plastisol for shoe soles was added, and the other parts were completely the same. A slush-molded shoe of a comparative example was manufactured according to the conditions.

The strength, abrasion resistance, cigarette resistance (heat resistance), and oil resistance and chemical resistance of these two slash-formed shoes, such as the sole and the lower part of the shoe body, were measured in the same manner as described above. Was evaluated.

Table 12 summarizes the results of these measurements. The slush-molded shoe formed according to the present invention has the same strength, hardness and feeling of the upper part of the shoe body as the conventional slush-molded shoe, and the shoe sole and the lower part of the shoe body are particularly heat-resistant ( It is clear that cigarette resistance is excellent, tensile strength, abrasion resistance, oil resistance and chemical resistance are also improved, and various characteristics of the shoe sole and the lower part of the shoe body are improved as compared with conventional two-layer slash-molded shoes.

[0187]

[Table 12]

Example 12 In order to confirm the improvement of slip resistance, as shown in Table 11, a cross-linkable polyvinyl chloride resin, which is a raw material of the sole used in Example 11, and an oil-resistant plasticizer were mixed. Example 1 A whisker (manufactured by Shikoku Chemical Industry Co., Ltd.) was mixed with a plastisol as an anti-slip material.
A slush-molded shoe was manufactured by the manufacturing method of the present invention in exactly the same manner as in Example 1.

The obtained slush-molded shoes were evaluated for slip resistance by the measurement method described above.

Table 12 shows the results. In conjunction with the results of Example 11, the slush molded shoes of the production method of the present invention are:
It can be seen that in addition to the effect of Example 11, the anti-slip property is also excellent.

(7) G: Crosslinkable polyvinyl chloride resin, thermosetting plasticizer and oil-resistant plasticizer, E + anti-slip material In the present invention, crosslinkable polyvinyl chloride resin, thermosetting plasticizer and oil-resistant plasticizer Is used, but the cross-linkable polyvinyl chloride resin and the oil-resistant plasticizer are omitted because they have been described in (1) A, (2) B and (3) C above. Examples of the composition of a plastisol in which a crosslinkable polyvinyl chloride resin, a thermosetting plasticizer and an oil-resistant plasticizer are mixed are as follows: polyvinyl chloride paste resin: 50 to 90 parts by weight; crosslinkable polyvinyl chloride resin: 10 to 10 parts by weight. 50 parts by weight, primary plasticizer: 10 to 50 parts by weight, oil-resistant polyester plasticizer: 80 to 40 parts by weight,
Thermosetting plasticizer: 10 to 40 parts by weight, catalyst: 0.3 to 1
Parts by weight, stabilizer: 2-3 parts by weight, crosslinking agent: 0.5-3 parts by weight, pigment: 0-2 parts by weight.

The slash-molded shoes according to the method of the present invention are:
All or part of the sole of the shoe and the lower part of the shoe body are made of a heated gel of a plastisol mixed with a crosslinkable polyvinyl chloride resin, a thermosetting plasticizer and an oil-resistant plasticizer. The heat resistance of the lower part is improved, so that it is difficult to melt even under heating conditions, and the cigarette resistance (heat deformation resistance) is improved. Further, the strength and abrasion resistance of the sole portion and the lower portion of the shoe body are also improved by the crosslinking.

Furthermore, since the oil-resistant plasticizer is mixed, the oil-resistant chemical resistance of the shoe sole and the lower part of the shoe body is also improved.

If a plastisol containing a cross-linkable polyvinyl chloride resin, a thermosetting plasticizer and an oil-resistant plasticizer is injected into the upper end of the slush molding mold and crosslinked, the slush molding mold is crosslinked. It is difficult to peel off from the mold, and the removability is significantly reduced, making mass production difficult.However, the use of a plastisol containing a cross-linkable polyvinyl chloride resin, a thermosetting plasticizer and an oil-resistant plasticizer is used in the sole of the shoe. Because only the lower part of the shoe body where all or part and its ungelled plastisol are mixed, the releasability does not decrease much, and expensive crosslinkable polyvinyl chloride resin, thermosetting plasticizer and oil resistant Since the use amount of the plastisol mixed with the plasticizer can be suppressed to the minimum necessary, an increase in the production cost can be suppressed. (Example 13)

[0195]

[Table 13]

First, as a plastisol for shoe sole, Table 13 was used.
The plastisol for the first layer having the composition shown in the following is included in the slush molding mold including the sole design of the shoe sole for about 20 hours.
mm, and the mold was heated at 150 ° C. for 1 to 2 minutes to form a semi-gelled layer on the entire sole of the shoe, leaving an ungelled plastisol.

Next, with the plastisol for the first layer remaining, the plastisol for the second layer was poured completely up to the upper end of the slush molding mold according to the composition shown in Table 13 above, and the plastisol was poured into the lower part of the shoe body. 180 ° C. in a state where a mixed plastisol of the plastisol for the first layer and the plastisol for the second layer is formed.
After heating for 1 to 2 minutes to adhere the mixed semi-gelled layer and the semi-gelled layer of a desired thickness to the entire inner surface of the mold, the ungelled plastisol was discharged.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was injected into the heel portion according to the composition shown in Table 13 above, and the heel portion was filled.
Heating at 5 ° C. for 5 to 7 minutes sufficiently crosslinked the first layer and sufficiently gelled the second layer and the heel.

Then, after cooling, the slush-molded shoe was taken out of the slush-molded mold to obtain slush-molded shoes in which both the shoe sole and the shoe body were black.

On the other hand, a step of using a plastisol that does not contain a crosslinkable polyvinyl chloride resin, a thermosetting plasticizer and an oil-resistant plasticizer in the first layer, and discharging an ungelled plastisol of a plastisol for shoe soles is added. The slash-molded shoes of the comparative example were manufactured under exactly the same conditions as above.

The strength, abrasion resistance, cigarette resistance (heat resistance), and oil resistance and chemical resistance of the sole and lower part of the shoe body of these two slash-molded shoes were measured in the same manner as described above using the measurement methods described above. evaluated.

Table 14 shows the results of these measurements. The slush-molded shoe formed by the present invention has a heat-resistant deformation (cigarette resistance), a tensile strength, an abrasion resistance, an oil resistance and a chemical resistance, which are particularly excellent in the sole portion and the lower portion of the shoe body. It can be seen that the characteristics of the sole portion and the lower portion of the shoe main body were improved as compared with the two-layer slash-molded shoe from the above.

[0203]

[Table 14]

Example 14 In order to confirm the improvement of the slip resistance, as shown in Table 13, the cross-linkable polyvinyl chloride resin, the thermosetting plasticizer and the raw material of the sole used in Example 13 were used. Whisker (manufactured by Shikoku Kasei Kogyo Co., Ltd.) was mixed as an anti-slip material with a plastisol mixed with an oil-resistant plasticizer, and slush-molded shoes were manufactured by the manufacturing method of the present invention in exactly the same manner as in Example 13.

The slush-molded shoes thus obtained were evaluated for slip resistance in the same manner as described above by the measurement method described above.

The results are shown in Table 14. Together with the results of Example 13, it can be seen that the slush-molded shoes produced by the manufacturing method of the present invention have excellent anti-slip properties in addition to the effects of Example 13.

(Example 15) In order to confirm that the oil resistance changes from the shoe sole to the upper part of the shoe body,
A mold having a capacity of about 2400 cc was used as a mold. First, as a plastisol for shoe soles, a plastisol mixed with an oil-resistant plasticizer for a first layer having a composition shown in Table 5 was used.
100 cc, so as to have a height of about 20 mm including the bottom design of the shoe sole in the mold.
While heating the mold for minutes, a semi-gelled layer was formed on the entire sole of the shoe, leaving an ungelled plastisol.

Next, with the plastisol for the first layer remaining, 2000 cc of the plastisol for the second layer was injected according to the composition shown in Table 5 to fill the upper end of the mold with the plastisol for the second layer. In the state where the mixed plastisol for the first layer and the plastisol for the second layer is formed, the mold is heated at 180 ° C. for 1 to 2 minutes to form a mixed semi-gel having a desired thickness on the inner surface of the slush molding mold. After depositing the layer and the semi-gelled layer, the ungelled plastisol was drained.

Further, in order to form a heel portion, a plastisol mixed with a polyvinyl chloride resin for a heel portion was poured into the heel portion according to the composition shown in Table 5 above, and filled at 200 ° C.
For 5 to 7 minutes to sufficiently crosslink the first layer and sufficiently gel the second layer and the heel.

After cooling, the slush-molded shoe was removed from the slush-molding mold to obtain a slush-molded shoe according to the method of the present invention in which both the shoe sole and the shoe body were black.

Then, the oil resistance of the resulting slash-formed shoe, such as the sole portion and the lower portion of the shoe body, was measured by the measurement method described above, and the four measurement points A, B, and B shown in FIG.
The height from the soles of c and d is 0mm, 50mm, 100mm,
The measurement was performed at 200 mm, and the results are shown in Table 15.

As is clear from the table, in the slush-molded shoes formed according to the present invention, the oil resistance (weight loss%) of the sole of the shoe is the highest, and the oil resistance decreases as the height increases from the sole of the shoe. It was confirmed that the oil resistance gradually changed.

[0213]

[Table 15]

[0214]

[0215]

As described above, the first aspect of the present invention is as follows.
According to the method for manufacturing a slush-molded shoe according to the multilayer described above, after injecting a plastisol mixed with a polyvinyl chloride resin into the shoe sole of the slush-molding mold in an amount required for molding the shoe sole, Since the sole of the mold was heated to leave a non-gelled plastisol to form a semi-gelled layer, injection of plastisol in an amount more than necessary for molding the sole caused irregularities in the sole of the sole. A semi-gelled layer having a thickness can be deposited.

Then, the plastisol for the shoe body was injected into the remaining ungelled plastisol to form the shoe body by slush molding, so that the two plastisols were mixed and gradually the only plastisol for the shoe body was gradually mixed from the portion where the two contacted. The concentration can be changed in parts and the semi-gelled layer of the shoe body can be formed via the mixed semi-gelled layer.

As a result, the functions of the shoe sole and the shoe body can be gradually changed or can be clearly distinguished.

According to the method for manufacturing a slush-molded shoe comprising a plurality of layers according to the second aspect of the present invention, at least one of the injection amount of the plastisol for shoe soles and the amount of the non-gelled plastisol to be left (each of them). Both) were adjusted, so that the range of the mixed semi-gelled layer and the mixing ratio would change depending on the amount of the remaining ungelled plastisol, and the amount of the remaining ungelled plastisol could be minimized. For example, the mixed semi-gelled layer is hardly formed, and the functions of the sole and the shoe body can be clearly distinguished.If the amount is large, the mixed semi-gelled layer is formed in a wide range and the sole and the sole are formed. The function with the shoe body can be changed gradually.

Further, according to the method for producing a slush-molded shoe comprising a plurality of layers according to the third aspect of the present invention, the general composition of a plastisol mixed with a polyvinyl chloride resin used for a shoe sole of a normal slush-molded shoe is obtained. Replacement, crosslinkable polyvinyl chloride resin, thermosetting plasticizer, oil-resistant plasticizer
Any one of them, or a combination of two or more of them, so that any of these, the strength of the sole and the lower part of the shoe body, wear resistance, heat deformation resistance, and oil and chemical resistance It can be improved overall.

Further, according to the method for manufacturing a slush-molded shoe comprising a plurality of layers according to the fourth aspect of the present invention, since various anti-slip materials are further mixed with the various plastisols according to the third aspect, a total of the shoe sole is obtained. In addition to performance, anti-slip properties can be further improved.

[Brief description of the drawings]

FIG. 1 is a process diagram in a case where the method for producing a slush-molded shoe of the present invention is applied to the production of a two-layer slush-molded shoe.

FIG. 2 is a cross-sectional view of a mixed plastisol production state and a cross-sectional view of a slush shoe when the method for manufacturing a slush formed shoe of the present invention is applied to the manufacture of a two-layer slush formed shoe.

FIG. 3 is a cross-sectional view of a slush molded shoe according to a conventional manufacturing method.

FIG. 4 is a cross-sectional view and an external view of a slash-formed shoe according to a conventional manufacturing method.

FIG. 5 is a cross-sectional view of a slush molded shoe according to a conventional manufacturing method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Mold for slash molding (mold) 2 Sole part (first layer) 2a Toe part of sole part 2b Tread part of sole part 2c Non-step part of sole part 2d Heel part of sole part 3 Plastisol for sole 4 Semi-gel Layer (sole bottom) 5 Ungelled plastisol 6 Plastisol for shoe body 7 Plastisol mixing section 8 Shoe body (second layer) 9 Heel part (heel part) 10 Mixed semi-gelled layer (lower part of shoe body) 11 Semi-gel Layer (upper part of shoe body) 12 Plastisol for heel 13 Skin (slush molded body) A, B, C, D Measurement points of oil resistance

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A43B 1/14 A43B 3/02 B29D 31/50

Claims (4)

(57) [Claims] 1. A plastisol for shoe sole obtained by mixing a polyvinyl chloride resin into a shoe sole of a mold for slush molding is injected in an amount of at least an amount necessary for molding the sole of the shoe. After the semi-gelled layer is layered along the shape of the sole with the plastisol remaining, the plastisol for the shoe body mixed with a polyvinyl chloride resin different from the plastisol for the sole is injected and further heated, and the sole is heated. After forming a shoe body semi-gelled layer through a mixed semi-gelled layer in which the ungelled plastisol and the shoe body plastisol are mixed, the non-gelled plastisol is discharged and gelled by heating. A method for producing a slash-molded shoe comprising a plurality of layers. 2. The mixing of the plastisol for the sole and the plastisol for the sole body of the shoe by changing at least one of an injection amount of the plastisol for the sole and an amount of residual ungelled plastisol of the plastisol for the sole. 2. The method for producing a multi-layered slash-molded shoe according to claim 1, wherein the range of film formation and the mixing ratio of the semi-gelled layer are varied. 3. A plastisol for a shoe sole mixed with a polyvinyl chloride resin to be injected into the slush molding mold, wherein at least one of a crosslinkable polyvinyl chloride resin, a thermosetting plasticizer, and an oil-resistant plasticizer, or The method for producing a multi-layered slash-molded shoe according to claim 1 or 2, wherein two or more are used in combination. 4. The multi-layer slush-molded shoe according to claim 3, wherein a slip-resistant material is further mixed with a plastisol for shoe sole mixed with polyvinyl chloride resin to be injected into the mold for slush molding. Production method.