JPH05115304A - Manufacture of injection molded fabric shoes - Google Patents

Abstract

PURPOSE:To provide a manufacturing method of injection-molded fabric shoes which assures better integral bonding of an upper cover on shoes soles by an injection molding method of a shoes sole material mainly composed of a thermoplastic resin with the texture of a surface fabric of an upper cover material produced by laminating fabrics kept as intrinsic as possible. CONSTITUTION:A shoes sole material with a melting viscosity in an injection molding of 10<2>-10<4>g/cm.sec under a load of 10kg at 190 deg.C on a hardening type flow tester basis with 1mm split dies containing 5-50 pts.wt. of a thermoplastic polyurethane elastomer and 80-120 pts.wt. of a plasticizer per 100 pts.wt of ethylene-vinyl chloride copolymer undergoes an injection molding and is bonded integral on an upper cover produced by laminating fabrics. The surface fabric of the upper cover herein used is such as those with a pore capacity rate of 50-90% prescribed by JISL-1096 and yet to be subjected to a adhesive treatment. The thermoplastic polyurethane elastomer herein used is a hot melt type polyurethane elastmer with a molecular weight of 10<4>-10<5> based on polyester.

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 an injection-molded cloth shoe, in which a shoe sole material containing a thermoplastic resin as a main component is bonded and integrated with a cloth covering material obtained by laminating cloth by an injection molding method. With regard to the above, particularly, an injection-molded cloth capable of ensuring a strong joint state between the covering material and the sole material while maintaining the texture of the outer cloth used for the covering material in the original cloth texture. The present invention relates to a method for manufacturing shoes.

[0002]

[Technical Background] Generally, in order to manufacture cloth shoes by an injection molding method, a mold cover formed by laminating cloth is hung on a last mold, and a bottom mold and a side mold are fitted to the last mold. A method has been adopted in which a shoe sole material mainly composed of a thermoplastic resin is injected into the cavity to mold the shoe sole, and at the same time, the shoe sole and the above-mentioned cover are bonded and integrated. However, since the outer fabric of the armor cover and the shoe sole material originally lack adhesiveness, the following techniques have been conventionally adopted as a method for firmly bonding the two. There was such a problem.

(1) A solvent-based polyurethane adhesive, polyester adhesive, or the like is applied to the surface cloth of the cover of the portion where the cover and the shoe sole to be injection-molded are bonded by a method such as brush coating. After drying (so-called partial coating of an adhesive), the shoe sole material is injected, and the shoe sole and the cover are bonded and integrated by the adhesive.

However, in this technique, the adhesive is extruded from a predetermined bonded portion to deteriorate the appearance quality, and since the manual work is mainly performed, the workability and the productivity are deteriorated, which causes a cost increase. , Furthermore, it lacks adhesion stability.

(2) As can be seen in Japanese Patent Publication No. 58-29081 and Japanese Patent Publication No. 3-20241, hot-melt type polyurethane-based treatment agent, polyester The surface treatment agent is entirely treated with a 30-50 mesh gravure roll, or the whole surface is coated with a knife coater or the like, cut and sewn to form a cover, and at the same time the shoe sole is formed by injection molding. The sole and the cover are adhered and integrated by the treatment agent of.

[0006] In this technique, since the outer fabric of the cover is entirely treated at the stage of the original fabric, the productivity is good and the adhesiveness is stabilized, but the weaving structure and the knitting structure of the fabric are dependent on the resin content of the treating agent. Is hardened, the texture of the cloth becomes hard, and the original feel of the material is lost. Furthermore, there is a problem that the original color cannot be utilized as a product, such as the color of the material being shifted to the dark side or being out of focus when the cloth fiber is wet with the resin component. In addition, when a raised material or a material with a raised feeling is used as the cloth for covering the hair, the hair falls asleep during the treatment, and is fixed by the resin component of the treatment agent, so that the raised or raised feeling is completely eliminated. Not applicable. In addition, since the covering is hardened by the treatment agent, it becomes difficult to suspend the covering in the last mold.
Fitting is impossible or extremely difficult to hang.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to manufacture a new injection-molded cloth shoe capable of solving various problems in the above-mentioned conventional technique of adhering and integrating the injection-molded shoe sole and the covering layer formed by laminating cloth. The purpose is to provide a method.

[0008]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention is an injection molding of a shoe sole material containing a thermoplastic resin as a main component,
In a method for producing an injection-molded cloth shoe, which is formed by laminating cloth and adhesively integrated with a cover, the sole material is 5 to 50 parts by weight of a thermoplastic polyurethane elastomer with respect to 100 parts by weight of an ethylene-vinyl chloride copolymer. And plasticizer 80-120
Including the parts by weight, the melt viscosity at the time of injection molding is 190 ° C, 10kg by a 1 mm split die high-performance flow tester.
The load is 10 ² to 10 ⁴ g / cm · sec.

Further, according to the present invention, the cover fabric formed by laminating the above-mentioned fabrics has a pore volume ratio of 50 to 90% specified in JIS L-1096 and is not treated with an adhesive. Also features.

Further, the present invention is characterized in that the thermoplastic polyurethane elastomer is a hot melt type polyurethane elastomer having a polyester skeleton and a molecular weight of 10 ⁴ to 10 ⁵ .

Unlike the vinyl chloride homopolymer used for injection-molded shoe soles, the ethylene-vinyl chloride copolymer in the present invention is a copolymer of ethylene, and the ethylene copolymerization rate is 0. It can be used in the range of 0.5 to 10%, preferably 0.8 to 5%. By the copolymerization of ethylene, the viscosity of polyvinyl chloride during melting is lowered, the flow characteristics during injection are significantly improved, and it penetrates into the pores of the cover fabric of the fabric covered by laminating the cloth, It facilitates adhesive integration with the laminated cover, but when the ethylene copolymerization rate is less than 0.5%, the flow characteristics during injection deteriorate, and when it exceeds 10%, vinyl chloride resin originally The characteristics are significantly deteriorated, making it unsuitable as a shoe sole material.

The ethylene-vinyl chloride copolymer according to the present invention may have any degree of polymerization as long as it is within the range generally used as a shoe sole material, but the average degree of polymerization is preferably 800 to 4000, More preferably, the average degree of polymerization of 1000 to 2500 is suitable. When the average degree of polymerization of the ethylene-vinyl chloride copolymer changes, the viscosity at the time of melting also changes, but if the average degree of polymerization is less than 800, the melt viscosity will decrease and the flow characteristics at the time of injection will be good, and the cloth It is easy to penetrate into the pores of the cover fabric of the laminated cover and facilitates the adhesion and integration with the cover, but the physical properties of the shoe sole material deteriorate and it is practically used as a shoe sole. You will not get it. On the other hand, if the average degree of polymerization exceeds 4000, the physical properties as a shoe sole material will be good, but the melt viscosity will be high, the flow characteristics during injection will be deteriorated, and it will be difficult to bond and integrate with the cover.

The thermoplastic polyurethane elastomer blended with the above ethylene-vinyl chloride copolymer is 1,4
-Polyalkylene diadipates represented by butanediol adipate, 1,6-hexanediol adipate, etc., and representative polyesters such as polycaprolactone obtained by ring-opening polymerization of ε-caprolactone, ethylene glycol, propylene glycol, neopentyl glycol ，
1,3-butanediol, 1,4-butanediol,
Low-molecular-weight aliphatic glycols such as 1,5-pentanediol, low-molecular-weight alicyclic glycols represented by water-added bisphenol A, organic compounds such as ethylenediamine, propylenediamine, piperazine, isophoronediamine, 4,4'-diaminodicyclohexylmethane A chain extender such as a diamine is used if necessary, and a compound obtained by reacting with an aliphatic, alicyclic or aromatic diisocyanate is used. As the diisocyanate, a non-yellowing aliphatic or alicyclic group or a yellowing type aromatic can be used depending on the required properties of the shoe sole, color and the like.

The above-mentioned thermoplastic polyurethane elastomer is a main component of ethylene-vinyl chloride copolymer 100.
5 to 50 parts by weight, preferably 8 to 30 parts by weight are used with respect to parts by weight. When the amount is less than 5 parts by weight, the sole of the present invention is molded by injection of the sole material, and at the same time, the sole and the cover layer formed by laminating the cloth are bonded and integrated, that is, the sole and the sole. The effect of adhering to the cloth disappears, and when it exceeds 50 parts by weight, the sole material injected during injection molding becomes extremely sticky and sticks or adheres to the bottom mold and side molds, making the molding operation difficult.

In the present invention, the thermoplastic polyurethane elastomer is preferably a hot melt having a polyester skeleton and a molecular weight of 10 ⁴ to 10 ⁵ , more preferably 2 × 10 ^{4 to} 5 × 10 ^4. Type polyurethane elastomers are used. In this case, the molecular weight is less than 10 ^4, although the flow properties during injection molding is good, adhesion to the injection molding soles and胛被fabric is lowered, no longer meet the object of the present invention, more than 10 ⁵ As a result, the flow characteristics during injection deteriorate, and the adhesive characteristics between the injection-molded shoe sole and the covering cloth also deteriorate.

In the present invention, the following method can be adopted as a method for adding and blending the above-mentioned thermoplastic polyurethane elastomer to the injection molding sole material.
It is not limited to these. (1) A thermoplastic polyurethane elastomer is blended with other compounding ingredients and pelletized as a full compound. (2) The thermoplastic polyurethane elastomer is ethylene-
A vinyl chloride copolymer, a plasticizer, etc. are mixed in a high concentration in advance (that is, made into a masterbatch), and a necessary amount is added to the shoe sole compound. (3) The thermoplastic polyurethane elastomer is pulverized and powdered, added to the shoe sole material compound, and used in the powder state without being pelletized.

As the plasticizer blended with the ethylene-vinyl chloride copolymer and the thermoplastic polyurethane elastomer, any plasticizer used for blending ordinary polyvinyl chloride resins can be used. For example, phthalic acid derivatives typified by dibutyl phthalate and dioctyl phthalate, adipic acid derivatives typified by dioctyl adipate, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, azelaic acid derivatives, sebacic acid derivatives, maleic acid derivatives, fumaric acid. Derivatives, trimellitic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, linoleic acid derivatives, stearic acid derivatives,
Phosphoric acid derivative, glycol derivative, glycerin derivative,
Examples include paraffin derivatives, but the invention is not limited thereto.

Further, in the present invention, in addition to the above ethylene-vinyl chloride copolymer, thermoplastic polyurethane elastomer and plasticizer, a stabilizer, a thermal decomposition type foaming agent, a filler, a pigment and other appropriate additives are blended. can do. Of these, a barium / zinc-based stabilizer can be preferably used as the stabilizer, and any barium / zinc-based stabilizer can be used as long as it is used in a polyvinyl chloride resin, and there is no particular limitation. Absent. The barium / zinc stabilizer is a stabilizer that has little effect on the durability of the thermoplastic polyurethane elastomer, that is, physical properties such as hydrolysis resistance, and also functions as a decomposition catalyst for the thermal decomposition type foaming agent described later. It is a thing. Along with this barium / zinc stabilizer, epoxy resin, epoxidized soybean oil, phosphate, phosphite, antioxidant, UV absorber,
Stabilizers such as calcium hydroxide, magnesium oxide, and calcium oxide can be used in combination, but those that affect the durability (hydrolysis resistance) of the thermoplastic polyurethane elastomer, such as organotin and organolead, are used. It is not preferable to do so.

The shoe sole material containing the above components has a melt viscosity of 10 ² to 10 ⁴ g / cm ² during injection molding.
・ Sec (Koka type flow tester, 190 ℃, 10kg
It is important that the load is within the range of 1 mm split die. The melt viscosity at the time of injection molding is the most important element for molding the shoe sole by injection molding of the shoe sole material and at the same time, for adhering and integrating the shoe sole and a cover formed by laminating cloth. More specifically, a shoe sole material having a melt viscosity within the above range is most suitable for intruding into the texture and the fiber gap of the cover fabric during injection molding to bond and integrate the sole and the cover fabric. Achieves an important anchoring effect, promotes wetting with the fiber surface, and realizes even stronger adhesion through a synergistic effect with the adhesive effect of the thermoplastic polyurethane elastomer that is a compounding component of the shoe sole material. ..

The above melt viscosity is 10 ² g / cm · sec.
If it is less than the range, the shoe sole material composition melted during injection molding easily leaks as burrs from the mold fitting part and the mold rubbing part, making the injection molding operation difficult and stable foam injection molding difficult. Also, 10 ⁴ g / cm
When it exceeds sec, it becomes difficult for the injected shoe sole material mixture to efficiently penetrate into the grain and the fiber gap of the cover fabric, which is an important anchor for anchoring and integrating the shoe sole and cover. ) The effect cannot be realized, the fiber surface is not sufficiently wetted, and the effect of the thermoplastic polyurethane elastomer, which is a compounding component of the shoe sole, cannot be sufficiently exerted.

[0021] In the present invention, a cover fabric of a cover which is a laminate of fabrics to which the above-mentioned shoe sole material composition is preferably applied (means a fabric on the surface of the cover; (When it is laminated, it means at least the uppermost cloth)
Has a pore volume ratio of 50 specified by JIS L-1096.
It is in the range of 90% to 90%, and is a so-called untreated cloth that is not treated with an adhesive. This outer cloth is made of cotton, suf, acrylic fiber, which is commonly used for shoes.
Polyester fiber, nylon fiber and each fiber blend,
Mixed woven, knit, and non-woven fabrics can be used. In order to enhance the anchoring effect, the synthetic fiber is preferably a woven fabric, a knitted fabric or a non-woven fabric made of short fibers or staple fibers, rather than filament fibers. JI
The pore volume ratio defined in SL-1096 can be expressed by the following formula.

[0022]

[Equation 1]

The pore volume ratio of the cover cloth is 50 to 90%.
In this range, the melt of the shoe sole material at the time of injection described above efficiently penetrates into the texture and the fiber gap of the cover fabric and is important for anchoring the sole and the cover together. Achieves (anchor) effect, facilitates wetting with the fiber surface, facilitates exerting the adhesive effect of the thermoplastic polyurethane elastomer that is a compounding component of the sole material, and facilitates strong adhesive integration. ..

If the pore volume ratio is less than 50%, the melt of the shoe sole material at the time of injection cannot efficiently penetrate into the grain and the fiber gap of the garment cover cloth, and the shoe sole material and the garment cover are bonded and integrated. Becomes difficult. On the other hand, when the porosity volume ratio exceeds 90%, the physical properties of the cover fabric of the armor cover are not suitable for shoes, and it becomes substantially impossible to make shoes.

[0025]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 (1) Fabrication of a veiled cover A plain weave woven fabric with a texture of (20/2 × 16/3) / (70 × 24) and a pore volume ratio of 68% was used as a front fabric, and a suture twill woven fabric was used. As a backing cloth, a solvent-based natural rubber laminated original fabric was manufactured. After cutting and sewing this raw material, the insole material was attached to obtain a bag-shaped cover, which is generally called California instep.

(2) Injection-molded shoe sole material compound As a thermoplastic polyurethane elastomer, pellets of polyurethane elastomer having an average molecular weight of 4 × 10 ^{4 and made} of polyhexane adipate, 1,4-butanediol, and hexamethylene diisocyanate are used as a bulk weight. Obtained legally. An injection-molded shoe sole material was prepared by compounding an injection-molded shoe sole material mixture using this elastomer by the dry blending method with the formulation shown in Table 1, followed by kneading with Banbury and pelletizing by the hot cut method with a single screw extruder. I got a compound. The melt viscosity of this compound at 190 ° C. is 9 × 10 ² g / cm · sec (Koka type flow tester, 10 kg load, 1 mm split die),
It was in accordance with the object of the present invention.

[0027]

[Table 1]

(3) Shoe Making The garment cover obtained in (1) above was suspended in a last mold, and a side mold and a bottom mold were fitted to the last mold to form a shoe sole molding cavity. The injection molding sole material compound obtained in (2) above was injected into this cavity with an injection molding machine at an injection temperature of 190 ° C.
At the same time, the shoe sole was molded by injecting with 1. to put the sole on the cover (that is, the cover and the sole were bonded and integrated), and after cooling, a shoe product was obtained.

Since the shoe products produced in this manner have not been subjected to the conventional surface treatment of the cover fabric, not only the texture of the cover fabric but also the color development is good. Not only that, the coat covered the last mold well, and the finish as a shoe was good and beautiful.
Further, the adhesive strength between the hood and the shoe sole was 3.5 kg / cm, and there was no problem as a shoe.

Example 2 (1) Preparation of cover layer A cotton plain weave knitted fabric having a structure of (10/2 × 10/2) / (45 × 34) and a pore volume ratio of 73% was used as a top fabric, and a urethane foam (thick Taste 3 mm) and nylon tricot half laminated on one side as a backing, using a solvent-based natural rubber laminating paste (basis weight of 400 g / m ² ) for laminating, drying, vulcanizing, and laminating for laminating. Got the counter. After cutting and sewing this raw material, the insole material was attached to obtain a bag-shaped cover, which is generally called California instep.

(2) Injection molding shoe sole compounding As a thermoplastic polyurethane elastomer, a polyurethane elastomer having an average molecular weight of 6 × 10 ⁴ consisting of polycaprolactone, 1,4-butanediol and isophorone diisocyanate was produced by a melt polymerization method. , After desolvation,
A flaky elastomer was obtained. An injection-molded shoe sole material was prepared by compounding an injection-molded shoe sole compound composition using this elastomer with the formulation shown in Table 2 by dry blending, kneading with Banbury, and pelletizing by a hot cut method with a single-screw extruder. I got a compound. The melt viscosity of this compound at 190 ° C. is 3 × 10 ³ g /
cm ・ sec (Koka type flow tester, 10kg load,
It was a 1 mm split die.

[0032]

[Table 2]

(3) Shoe Making A shoe product was obtained by making shoes in the same manner as in Example 1 by using the coat obtained in (1) above and the mixture of the sole material for injection molding according to (2).

Since the shoe products produced in this manner are not subjected to the conventional surface treatment of the cover fabric, not only the texture of the cover and the color development are good, but also The scabbard fits the last mold well, and the finish as a shoe was also beautiful. Further, the adhesion strength between the hood and the injection-molded shoe sole was 3.3 kg / cm, which was a good strength as a shoe, which was consistent with the object of the present invention.

Comparative Example 1 (1) Preparation of cover layer The same cover layer as in Example 1 was prepared.

(2) Injection molding shoe sole material composition Table 3 shows a typical composition which has been generally used in the past.
Using the formulation shown in, a shoe sole material compound pellet was prepared in the same manner as in Example 1.

[0037]

[Table 3]

(3) Shoe Making Shoes were made in the same manner as in Example 1 by using the above-mentioned covering of (1) and the sole material compound of (2) to obtain a shoe product.

In the shoe product manufactured in this manner, the finish of the cover was similar to that of Example 1, but the adhesive strength between the cover and the injection-molded sole, which is the most important for the shoe, was 0.8 kg /
Since it was only cm, it was completely unusable.

COMPARATIVE EXAMPLE 2 (1) Preparation of cover fabric To the same cotton plain weave fabric as in Example 1, 5 parts by weight of an isocyanate curing agent was added, and an aromatic polyester adhesive was applied as an undercoat layer. A surface-treated finished base cloth coated with an aromatic polyester resin containing no isocyanate-based curing agent is used as a front cloth, and a suture twill woven cloth is used as a back cloth, and a solvent-based natural rubber laminating paste (weight per unit area 500 g / m ² ), followed by drying, followed by vulcanization to obtain a laminated original fabric for covering. After cutting and sewing this raw material, a midsole material was attached to prepare a bag-shaped cover, which is generally called California instep.

(2) Shoe sole compound for injection molding The same sole compound pellet as in Comparative Example 1 was prepared.

[0042]

[Table 3]

(3) Shoe Making A shoe product was obtained by making shoes in the same manner as in Example 1 by using the above-mentioned covering of (1) and the sole material compound of (2).

The shoe product manufactured in this manner has an adhesive strength of 3.5 kg / cm between the cover and the injection-molded sole,
Although the strength of the shoe was not a problem, the surface of the garment cover was treated with an adhesive, so the texture of the garment cover was extremely hard, and the color was out of focus. The texture and appearance that he had had completely disappeared. In addition, since the texture of the undercoat is hard, the shoe toe part is not easy to insert, and the shape of the last cannot be reproduced when it is hung on the last (foot type), and the overall finish of the shoe is beautiful. It was something I couldn't say.

[0045]

As described in detail above, the method of the present invention is
The one that enables adhesive integration between the cover and the injection-molded shoe sole, which is the most important in the manufacturing technology of injection-molded fabric shoes, without applying an adhesive to the cover cloth or treating the surface with the adhesive. By utilizing the natural texture, touch, texture and color of the cloth, and by improving the texture of the cloth, the sewing and loosing properties of the cloth are significantly improved and the last (foot type) ) It is possible to manufacture a product that reproduces the shape as it is. Further, since it is not necessary to apply an adhesive agent to the cover and to treat the surface with the adhesive agent, these steps are eliminated, and the steps can be shortened and rationalized, leading to a large cost reduction.

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[Procedure amendment]

[Submission date] December 6, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an injection-molded cloth shoe, in which a shoe sole material containing a thermoplastic resin as a main component is bonded and integrated with a cloth covering material obtained by laminating cloth by an injection molding method. With regard to the above, particularly, an injection-molded cloth capable of ensuring a strong joint state between the covering material and the sole material while maintaining the texture of the outer cloth used for the covering material in the original cloth texture. The present invention relates to a method for manufacturing shoes.

[0002]

[Technical Background] Generally, in order to manufacture cloth shoes by an injection molding method, a mold cover formed by laminating cloth is hung on a last mold, and a bottom mold and a side mold are fitted to the last mold. A method has been adopted in which a shoe sole material mainly composed of a thermoplastic resin is injected into the cavity to mold the shoe sole, and at the same time, the shoe sole and the above-mentioned cover are bonded and integrated. However, since the outer fabric of the armor cover and the shoe sole material originally lack adhesiveness, the following techniques have been conventionally adopted as a method for firmly bonding the two. There was such a problem.

(1) A solvent-based polyurethane adhesive, polyester adhesive, or the like is applied to the surface cloth of the cover of the portion where the cover and the shoe sole to be injection-molded are bonded by a method such as brush coating. After drying (so-called partial coating of an adhesive), the shoe sole material is injected, and the shoe sole and the cover are bonded and integrated by the adhesive.

However, in this technique, the adhesive is extruded from a predetermined bonded portion to deteriorate the appearance quality, and since the manual work is mainly performed, the workability and the productivity are deteriorated, which causes a cost increase. , Furthermore, it lacks adhesion stability.

(2) As can be seen in Japanese Patent Publication No. 58-29081 and Japanese Patent Publication No. 3-20241, hot-melt type polyurethane-based treatment agent, polyester The surface treatment agent is entirely treated with a 30-50 mesh gravure roll, or the whole surface is coated with a knife coater or the like, cut and sewn to form a cover, and at the same time the shoe sole is formed by injection molding. The sole and the cover are adhered and integrated by the treatment agent of.

[0006] In this technique, since the outer fabric of the cover is entirely treated at the stage of the original fabric, the productivity is good and the adhesiveness is stabilized, but the weaving structure and the knitting structure of the fabric are dependent on the resin content of the treating agent. Is hardened, the texture of the cloth becomes hard, and the original feel of the material is lost. Furthermore, there is a problem that the original color cannot be utilized as a product, such as the color of the material being shifted to the dark side or being out of focus when the cloth fiber is wet with the resin component. In addition, when a raised material or a material with a raised feeling is used as the cloth for covering the hair, the hair falls asleep during the treatment, and is fixed by the resin component of the treatment agent, so that the raised or raised feeling is completely eliminated. Not applicable. In addition, since the covering is hardened by the treatment agent, it becomes difficult to suspend the covering in the last mold.
Fitting is impossible or extremely difficult to hang.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to manufacture a new injection-molded cloth shoe capable of solving various problems in the above-mentioned conventional technique of adhering and integrating the injection-molded shoe sole and the covering layer formed by laminating cloth. The purpose is to provide a method.

[0008]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention is an injection molding of a shoe sole material containing a thermoplastic resin as a main component,
In a method for producing an injection-molded cloth shoe, which is formed by laminating cloth and adhesively integrated with a cover, the sole material is 5 to 50 parts by weight of a thermoplastic polyurethane elastomer with respect to 100 parts by weight of an ethylene-vinyl chloride copolymer. And plasticizer 80-120
Including the parts by weight, the melt viscosity at the time of injection molding is 190 ° C, 10kg by a 1 mm split die high-performance flow tester.
The load is 10 ² to 10 ⁴ g / cm · sec.

Further, according to the present invention, the cover fabric formed by laminating the above-mentioned fabrics has a pore volume ratio of 50 to 90% specified in JIS L-1096 and is not treated with an adhesive. Also features.

Further, the present invention is characterized in that the thermoplastic polyurethane elastomer is a hot melt type polyurethane elastomer having a polyester skeleton and a molecular weight of 10 ⁴ to 10 ⁵ .

Unlike the vinyl chloride homopolymer used for injection-molded shoe soles, the ethylene-vinyl chloride copolymer in the present invention is a copolymer of ethylene, and the ethylene copolymerization rate is 0. It can be used in the range of 0.5 to 10%, preferably 0.8 to 5%. By the copolymerization of ethylene, the viscosity of polyvinyl chloride during melting is lowered, the flow characteristics during injection are significantly improved, and it penetrates into the pores of the cover fabric of the fabric covered by laminating the cloth, It facilitates adhesive integration with the laminated cover, but when the ethylene copolymerization rate is less than 0.5%, the flow characteristics during injection deteriorate, and when it exceeds 10%, vinyl chloride resin originally The characteristics are significantly deteriorated, making it unsuitable as a shoe sole material.

The ethylene-vinyl chloride copolymer according to the present invention may have any degree of polymerization as long as it is within the range generally used as a shoe sole material, but the average degree of polymerization is preferably 800 to 4000, More preferably, the average degree of polymerization of 1000 to 2500 is suitable. When the average degree of polymerization of the ethylene-vinyl chloride copolymer changes, the viscosity at the time of melting also changes, but if the average degree of polymerization is less than 800, the melt viscosity will decrease and the flow characteristics at the time of injection will be good, and the cloth It is easy to penetrate into the pores of the cover fabric of the laminated cover and facilitates the adhesion and integration with the cover, but the physical properties of the shoe sole material deteriorate and it is practically used as a shoe sole. You will not get it. On the other hand, if the average degree of polymerization exceeds 4000, the physical properties as a shoe sole material will be good, but the melt viscosity will be high, the flow characteristics during injection will be deteriorated, and it will be difficult to bond and integrate with the cover.

The thermoplastic polyurethane elastomer blended with the above ethylene-vinyl chloride copolymer is 1,4
-Polyalkylene diadipates represented by butanediol adipate, 1,6-hexanediol adipate, etc., and representative polyesters such as polycaprolactone obtained by ring-opening polymerization of ε-caprolactone, ethylene glycol, propylene glycol, neopentyl glycol ，
1,3-butanediol, 1,4-butanediol,
Low-molecular-weight aliphatic glycols such as 1,5-pentanediol, low-molecular-weight alicyclic glycols represented by water-added bisphenol A, organic compounds such as ethylenediamine, propylenediamine, piperazine, isophoronediamine, 4,4'-diaminodicyclohexylmethane A chain extender such as a diamine is used if necessary, and a compound obtained by reacting with an aliphatic, alicyclic or aromatic diisocyanate is used. As the diisocyanate, a non-yellowing aliphatic or alicyclic group or a yellowing type aromatic can be used depending on the required properties of the shoe sole, color and the like.

The above-mentioned thermoplastic polyurethane elastomer is a main component of ethylene-vinyl chloride copolymer 100.
5 to 50 parts by weight, preferably 8 to 30 parts by weight are used with respect to parts by weight. When the amount is less than 5 parts by weight, the sole of the present invention is molded by injection of the sole material, and at the same time, the sole and the cover layer formed by laminating the cloth are bonded and integrated, that is, the sole and the sole. The effect of adhering to the cloth disappears, and when it exceeds 50 parts by weight, the sole material injected during injection molding becomes extremely sticky and sticks or adheres to the bottom mold and side molds, making the molding operation difficult.

In the present invention, the thermoplastic polyurethane elastomer is preferably a hot melt having a polyester skeleton and a molecular weight of 10 ⁴ to 10 ⁵ , more preferably 2 × 10 ^{4 to} 5 × 10 ^4. Type polyurethane elastomers are used. In this case, the molecular weight is less than 10 ^4, although the flow properties during injection molding is good, adhesion to the injection molding soles and胛被fabric is lowered, no longer meet the object of the present invention, more than 10 ⁵ As a result, the flow characteristics during injection deteriorate, and the adhesive characteristics between the injection-molded shoe sole and the covering cloth also deteriorate.

In the present invention, the following method can be adopted as a method for adding and blending the above-mentioned thermoplastic polyurethane elastomer to the injection molding sole material.
It is not limited to these. (1) A thermoplastic polyurethane elastomer is blended with other compounding ingredients and pelletized as a full compound. (2) The thermoplastic polyurethane elastomer is ethylene-
A vinyl chloride copolymer, a plasticizer, etc. are mixed in a high concentration in advance (that is, made into a masterbatch), and a necessary amount is added to the shoe sole compound. (3) The thermoplastic polyurethane elastomer is pulverized and powdered, added to the shoe sole material compound, and used in the powder state without being pelletized.

As the plasticizer blended with the ethylene-vinyl chloride copolymer and the thermoplastic polyurethane elastomer, any plasticizer used for blending ordinary polyvinyl chloride resins can be used. For example, phthalic acid derivatives typified by dibutyl phthalate and dioctyl phthalate, adipic acid derivatives typified by dioctyl adipate, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, azelaic acid derivatives, sebacic acid derivatives, maleic acid derivatives, fumaric acid. Derivatives, trimellitic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, linoleic acid derivatives, stearic acid derivatives,
Phosphoric acid derivative, glycol derivative, glycerin derivative,
Examples include paraffin derivatives, but the invention is not limited thereto.

Further, in the present invention, in addition to the above ethylene-vinyl chloride copolymer, thermoplastic polyurethane elastomer and plasticizer, a stabilizer, a thermal decomposition type foaming agent, a filler, a pigment and other appropriate additives are blended. can do. Of these, a barium / zinc-based stabilizer can be preferably used as the stabilizer, and any barium / zinc-based stabilizer can be used as long as it is used in a polyvinyl chloride resin, and there is no particular limitation. Absent. The barium / zinc stabilizer is a stabilizer that has little effect on the durability of the thermoplastic polyurethane elastomer, that is, physical properties such as hydrolysis resistance, and also functions as a decomposition catalyst for the thermal decomposition type foaming agent described later. It is a thing. Along with this barium / zinc stabilizer, epoxy resin, epoxidized soybean oil, phosphate, phosphite, antioxidant, UV absorber,
Stabilizers such as calcium hydroxide, magnesium oxide, and calcium oxide can be used in combination, but those that affect the durability (hydrolysis resistance) of the thermoplastic polyurethane elastomer, such as organotin and organolead, are used. It is not preferable to do so.

The shoe sole material containing the above components has a melt viscosity of 10 ² to 10 ⁴ g / cm ² during injection molding.
・ Sec (Koka type flow tester, 190 ℃, 10kg
It is important that the load is within the range of 1 mm split die. The melt viscosity at the time of injection molding is the most important element for molding the shoe sole by injection molding of the shoe sole material and at the same time, for adhering and integrating the shoe sole and a cover formed by laminating cloth. More specifically, a shoe sole material having a melt viscosity within the above range is most suitable for intruding into the texture and the fiber gap of the cover fabric during injection molding to bond and integrate the sole and the cover fabric. Achieves an important anchoring effect, promotes wetting with the fiber surface, and realizes even stronger adhesion through a synergistic effect with the adhesive effect of the thermoplastic polyurethane elastomer that is a compounding component of the shoe sole material. ..

The above melt viscosity is 10 ² g / cm · sec.
If it is less than the range, the shoe sole material composition melted during injection molding easily leaks as burrs from the mold fitting part and the mold rubbing part, making the injection molding operation difficult and stable foam injection molding difficult. Also, 10 ⁴ g / cm
When it exceeds sec, it becomes difficult for the injected shoe sole material mixture to efficiently penetrate into the grain and the fiber gap of the cover fabric, which is an important anchor for anchoring and integrating the shoe sole and cover. ) The effect cannot be realized, the fiber surface is not sufficiently wetted, and the effect of the thermoplastic polyurethane elastomer, which is a compounding component of the shoe sole, cannot be sufficiently exerted.

[0021] In the present invention, a cover fabric of a cover which is a laminate of fabrics to which the above-mentioned shoe sole material composition is preferably applied (means a fabric on the surface of the cover; (When it is laminated, it means at least the uppermost cloth)
Has a pore volume ratio of 50 specified by JIS L-1096.
It is in the range of 90% to 90%, and is a so-called untreated cloth that is not treated with an adhesive. This outer cloth is made of cotton, suf, acrylic fiber, which is commonly used for shoes.
Polyester fiber, nylon fiber and each fiber blend,
Mixed woven, knit, and non-woven fabrics can be used. In order to enhance the anchoring effect, the synthetic fiber is preferably a woven fabric, a knitted fabric or a non-woven fabric made of short fibers or staple fibers, rather than filament fibers. JI
The pore volume ratio defined in SL-1096 can be expressed by the following formula.

[0022]

[Equation 1]

The pore volume ratio of the cover cloth is 50 to 90%.
In this range, the melt of the shoe sole material at the time of injection described above efficiently penetrates into the texture and the fiber gap of the cover fabric and is important for anchoring the sole and the cover together. Achieves (anchor) effect, facilitates wetting with the fiber surface, facilitates exerting the adhesive effect of the thermoplastic polyurethane elastomer that is a compounding component of the sole material, and facilitates strong adhesive integration. ..

If the pore volume ratio is less than 50%, the melt of the shoe sole material at the time of injection cannot efficiently penetrate into the grain and the fiber gap of the garment cover cloth, and the shoe sole material and the garment cover are bonded and integrated. Becomes difficult. On the other hand, when the porosity volume ratio exceeds 90%, the physical properties of the cover fabric of the armor cover are not suitable for shoes, and it becomes substantially impossible to make shoes.

[0025]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 (1) Fabrication of a veiled cover A plain weave woven fabric with a texture of (20/2 × 16/3) / (70 × 24) and a pore volume ratio of 68% was used as a front fabric, and a suture twill woven fabric was used. As a backing cloth, a solvent-based natural rubber laminated original fabric was manufactured. After cutting and sewing this raw material, the insole material was attached to obtain a bag-shaped cover, which is generally called California instep.

(2) Injection-molded shoe sole material compound As a thermoplastic polyurethane elastomer, pellets of polyurethane elastomer having an average molecular weight of 4 × 10 ^{4 and made} of polyhexane adipate, 1,4-butanediol, and hexamethylene diisocyanate are used as a bulk weight. Obtained legally. An injection-molded shoe sole material was prepared by compounding an injection-molded shoe sole material mixture using this elastomer by the dry blending method with the formulation shown in Table 1, followed by kneading with Banbury and pelletizing by the hot cut method with a single screw extruder. I got a compound. The melt viscosity of this compound at 190 ° C. is 9 × 10 ² g / cm · sec (Koka type flow tester, 10 kg load, 1 mm split die),
It was in accordance with the object of the present invention.

[0027]

[Table 1]

(3) Shoe Making The garment cover obtained in (1) above was suspended in a last mold, and a side mold and a bottom mold were fitted to the last mold to form a shoe sole molding cavity. The injection molding sole material compound obtained in (2) above was injected into this cavity with an injection molding machine at an injection temperature of 190 ° C.
At the same time, the shoe sole was molded by injecting with 1. to put the sole on the cover (that is, the cover and the sole were bonded and integrated), and after cooling, a shoe product was obtained.

Since the shoe products produced in this manner have not been subjected to the conventional surface treatment of the cover fabric, not only the texture of the cover fabric but also the color development is good. Not only that, the coat covered the last mold well, and the finish as a shoe was good and beautiful.
Further, the adhesive strength between the hood and the shoe sole was 3.5 kg / cm, and there was no problem as a shoe.

Example 2 (1) Preparation of cover layer A cotton plain weave knitted fabric having a structure of (10/2 × 10/2) / (45 × 34) and a pore volume ratio of 73% was used as a top fabric, and a urethane foam (thick Taste 3 mm) and nylon tricot half laminated on one side as a backing, using a solvent-based natural rubber laminating paste (basis weight of 400 g / m ² ) for laminating, drying, vulcanizing, and laminating for laminating. Got the counter. After cutting and sewing this raw material, the insole material was attached to obtain a bag-shaped cover, which is generally called California instep.

(2) Injection molding shoe sole compounding As a thermoplastic polyurethane elastomer, a polyurethane elastomer having an average molecular weight of 6 × 10 ⁴ consisting of polycaprolactone, 1,4-butanediol and isophorone diisocyanate was produced by a melt polymerization method. , After desolvation,
A flaky elastomer was obtained. An injection-molded shoe sole material was prepared by compounding an injection-molded shoe sole compound composition using this elastomer with the formulation shown in Table 2 by dry blending, kneading with Banbury, and pelletizing by a hot cut method with a single-screw extruder. I got a compound. The melt viscosity of this compound at 190 ° C. is 3 × 10 ³ g /
cm ・ sec (Koka type flow tester, 10kg load,
It was a 1 mm split die.

[0032]

[Table 2]

(3) Shoe Making A shoe product was obtained by making shoes in the same manner as in Example 1 by using the coat obtained in (1) above and the mixture of the sole material for injection molding according to (2).

Since the shoe products produced in this manner are not subjected to the conventional surface treatment of the cover fabric, not only the texture of the cover and the color development are good, but also The scabbard fits the last mold well, and the finish as a shoe was also beautiful. Further, the adhesion strength between the hood and the injection-molded shoe sole was 3.3 kg / cm, which was a good strength as a shoe, which was consistent with the object of the present invention.

Comparative Example 1 (1) Preparation of cover layer The same cover layer as in Example 1 was prepared.

(2) Injection molding shoe sole material composition Table 3 shows a typical composition which has been generally used in the past.
Using the formulation shown in, a shoe sole material compound pellet was prepared in the same manner as in Example 1.

[0037]

[Table 3]

(3) Shoe Making Shoes were made in the same manner as in Example 1 by using the above-mentioned covering of (1) and the sole material compound of (2) to obtain a shoe product.

In the shoe product manufactured in this manner, the finish of the cover was similar to that of Example 1, but the adhesive strength between the cover and the injection-molded sole, which is the most important for the shoe, was 0.8 kg /
Since it was only cm, it was completely unusable.

COMPARATIVE EXAMPLE 2 (1) Preparation of cover fabric To the same cotton plain weave fabric as in Example 1, 5 parts by weight of an isocyanate curing agent was added, and an aromatic polyester adhesive was applied as an undercoat layer. A surface-treated finished base cloth coated with an aromatic polyester resin containing no isocyanate-based curing agent is used as a front cloth, and a suture twill woven cloth is used as a back cloth, and a solvent-based natural rubber laminating paste (weight per unit area 500 g / m ² ), followed by drying, followed by vulcanization to obtain a laminated original fabric for covering. After cutting and sewing this raw material, a midsole material was attached to prepare a bag-shaped cover, which is generally called California instep.

(2) Shoe sole compound for injection molding The same sole compound pellet as in Comparative Example 1 was prepared.

(3) Shoe Making Shoes were made in the same manner as in Example 1 by using the above-mentioned covering material of (1) and the sole material compound of (2) to obtain a shoe product.

The shoe product manufactured in this manner has an adhesive strength of 3.5 kg / cm between the cover and the injection-molded sole.
Although the strength of the shoe was not a problem, the surface of the garment cover was treated with an adhesive, so the texture of the garment cover was extremely hard, and the color was out of focus. The texture and appearance that he had had completely disappeared. In addition, since the texture of the undercoat is hard, the shoe toe part is not easy to insert, and the shape of the last cannot be reproduced when it is hung on the last (foot type), and the overall finish of the shoe is beautiful. It was something I couldn't say.

[0044]

As described in detail above, the method of the present invention is
Without adhesive coating or surface treatment with an adhesive, which enables the adhesive integration of the hood and the injection-molded sole, which is the most important in the manufacturing technology of injection-molded fabric shoes. By utilizing the natural taste, texture, texture and color of the cloth, and by improving the texture of the cloth, the sewing and loosing properties of the cloth are significantly improved and the last (foot type) ) It is possible to manufacture a product that reproduces the shape as it is. Further, since it is not necessary to apply an adhesive to the cover and to treat the surface with the adhesive, these steps are eliminated, and the steps can be shortened and rationalized, which leads to a large cost reduction.

Claims (3)

[Claims] 1. A method for manufacturing an injection-molded cloth shoe in which a shoe sole material comprising a thermoplastic resin as a main component is injection-molded and adhesively integrated with a cover layer formed by laminating cloth, wherein the sole material is ethylene. -A high-performance flow tester containing 5 to 50 parts by weight of a thermoplastic polyurethane elastomer and 80 to 120 parts by weight of a plasticizer per 100 parts by weight of a vinyl chloride copolymer, and having a melt viscosity during injection molding of a 1 mm split die. At 190 ℃, 10kg load,
A method for manufacturing an injection-molded cloth shoe, which is 10 ² to 10 ⁴ g / cm · sec. 2. A cover fabric made of a stack of fabrics according to JIS
Porosity volume ratio specified in L-1096 is 50 to 90%
The method of manufacturing an injection-molded cloth shoe according to claim 1, wherein the injection-molded cloth shoe is not treated with an adhesive. 3. A thermoplastic polyurethane elastomer comprising:
The method for producing an injection-molded cloth shoe according to claim 1 or 2, which is a hot-melt polyurethane elastomer having a polyester skeleton and a molecular weight of 10 ⁴ to 10 ⁵ .