JPH07164576A - Slush molded shoes composed of multiple layers and its manufacture - Google Patents

Abstract

PURPOSE:To provide slush molded shoes with various functions improved and upgraded to a large extent and also provide a manufacturing method thereof. CONSTITUTION:In slush molded shoes, the whole of a part 2 of a sole is constituted of a heat gelled product of a plastisol composed of a crosslinking polyvinyl chloride resin and a thermosetting plasticizer mixed together, and other sections 3 of the sole are constituted of a heat gelled product of a plastisol mixed with polyvinyl chloride. Shoes are manufactured by a publicly known slush molding method in which slushing is carried out two times.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slush molded shoe having a multi-layer structure and a method of manufacturing the slush molded shoe. In particular, the material of all or a part of the sole of the shoe body is different from the material of the other portion of the shoe body. TECHNICAL FIELD The present invention relates to a slush molded shoe having multiple layers and a method for manufacturing the same.

[0002]

2. Description of the Related Art As is well known, slush molded shoes made of polyvinyl chloride resin are first made into actual shoes using materials such as leather and synthetic leather, and then made into an original model. A shoe-shaped tubular mold for slush molding has been manufactured by electroplating with metal plating, and polyvinyl chloride resin is poured into the slush molding mold thus manufactured, and the surrounding area is heated for a short time. By forming a polyvinyl chloride resin on the inner surface of the slush molding mold in a semi-gelled state with a certain thickness, then discharge the extra polyvinyl chloride resin in the non-gelled state outside the slush molding mold, and By heating the whole and completely solidifying the semi-gelled film in the slush molding mold, the shoe body consisting of the sole and other parts After cooling and demolding, the back cloth (inner boots) sewn from the shoe back cloth material and parts such as the insole and fasteners are assembled by sewing and adhering and then painted. The finished product is finished. The discharged excess polyvinyl chloride resin is collected and sent to the circulation step, and is used for the next and subsequent injections.

This slush molding shoe uses a slush molding mold produced by applying metal plating to the outer surface of the original model. Therefore, the inner surface of the slush molding mold is made of the material, stitches and even cuts used for the original model. Etc. are faithfully reproduced and excellent design expression is obtained, and there is no joint or seam between the sole and other parts of the shoe body, so it is a perfect tubular shape, so it is highly waterproof and moistureproof To obtain
Up to now, it has been mass-produced as cold boots such as boots.

In recent years, slush-molded shoes are not limited to conventional cold-wear shoes due to their excellent mass productivity, and are considered to be expanded and applied to short shoes of various designs such as rain shoes, cutter shoes, and pumps. It started to come.

However, since slush-molded boots completely compete with other leather shoes such as leather and synthetic leather, a shoe body other than the sole of the slush-molded shoe has an appropriate hardness, strength and texture. The function of the shoe sole is further improved, while ensuring the strength of the shoe sole, such as strength of the shoe sole, cigarette resistance (heat resistance), abrasion resistance, and oil resistance and chemical resistance in consideration of use at gas stations and various food factories. Furthermore, in addition to these, it is necessary to comprehensively improve various functions of the sole such as anti-slip properties in consideration of use in snowy areas.

In order to improve the above-mentioned various functions of the shoe sole without changing the function of the shoe body, it is the surest means to use both of them as different materials. Therefore, the conventionally proposed slush molding technology in which the shoe sole and the other portion excluding the shoe sole of the shoe main body of the slush molded shoe are made of different materials are listed below.

(1) Japanese Examined Patent Publication No. 40-13590 A slush molding mold is heated in advance, and vinyl resin plastisol (polyvinyl chloride paste resin: 100 parts by weight, plasticizer dioctyl phthalate: 30 parts by weight) is provided on the bottom of the inner surface of the mold. Part, plasticizer dioctyl adipate: 20 parts by weight, stabilizer: 3 parts by weight, colorant: 1 part by weight) to cause gelation, and further vinyl resin plastisol (vinyl chloride vinyl acetate copolymer paste resin: 100 parts by weight, plasticizer dioctyl phthalate: 45 parts by weight, plasticizer dioctyl adipate: 30 parts by weight, stabilizer: 3 parts by weight, colorant: 1 part by weight) are injected to a required height to a required thickness. The layered gel is formed on the inner surface of the mold, and the excess ungelled plastisol is completely discharged to completely melt the layered gelled layer. It is a basic technique for manufacturing a two-layer slush molded shoe by performing two injections of two kinds of plastisol.

(2) Japanese Unexamined Patent Publication (Kokai) No. 48-6834, Plastisol (polyvinyl chloride paste resin: 100 parts by weight, mixed with a thermosetting plasticizer in a shoe mold, plasticizer di-
2-Ethylhexyl phthalate: 65 to 85 parts by weight, thermosetting plasticizer trimethylolpropane trimethacrylate: 5 to 25 parts by weight, catalyst di-t-butyl peroxide: 0.1 to 0.5 parts by weight, stabilizer Ba- Cd-Zn organic composite: 2 parts by weight, stabilizer organotin maleate compound:
1 part by weight) to the upper end of the shoe mold, and the bottom of the shoe mold is heated from the outside to attach a semi-gelling layer to the bottom of the inner wall of the mold and the peripheral edge of the undercover, The ungelled plastisol was discharged, and then the usual plastisol (polyvinyl chloride paste resin: 100 parts by weight, plasticizer di-2 ethylhexyl phthalate: 70 to 90 parts by weight, stabilizer Ba
-Cd-Zn organic complex: 2 parts by weight, stabilizer: organotin malate compound: 1 part by weight), injection, heating and discharge are repeated, and a heel core is incorporated and finally heated. According to this method, not only the shoe sole of the shoe main body but also other portions except the shoe sole have a two-layer structure.

(3) Japanese Unexamined Patent Publication No. 56-70702 Japanese Unexamined Patent Publication (Kokai) No. 56-70702 Polyvinyl chloride plastisol (resin for polyvinyl chloride plastisol: 100 parts by weight, plasticizer di- 2-Ethylhexyl phthalate: 85 parts by weight, stabilizer di-butyltin dilaurate: 1.5 parts by weight, stabilizer epoxy soybean oil: 1 part by weight, white pigment: 2 parts by weight) are poured and heated to be suitable for the inner surface. A non-gelled polyvinyl chloride plastisol is vacuum-sucked and discharged, and a polyvinyl chloride plastisol different from and / or foreign to the above polyvinyl chloride plastisol (polyvinyl chloride plastisol Resin for plastisol: 100 parts by weight, plasticizer di-2-ethylhexyl phthalate: 90 parts by weight, stabilizer di-butyl Chin dilaurate: 1.5 parts by weight, stabilizer epoxy soybean oil: 1 part by weight, yellow pigment: 2
(Part by weight) is injected to slightly above the upper end of the mouth opening forming part of the slush molding mold, a semi-gelled layer of an appropriate thickness is attached by heating, and the ungelled polyvinyl chloride plastisol is vacuum sucked or by an appropriate means. This is a discharging method, and prevents the slush molding shoe of high commercial value from being produced by preventing the polyvinyl chloride plastisol injected first time from adhering to the upper portion of the inner surface of the slush molding mold at the time of discharging.

(4) Japanese Examined Patent Publication No. 58-35683 Japanese Unexamined Patent Publication (Kokai) No. 58-35683 A hole for opening and closing is provided on the bottom surface of a mold for slush molding, and polyvinyl chloride plastisol (vinyl chloride emulsion polymerization resin is used so as not to stain the inner wall surface to a predetermined position. : 1
00 parts by weight, plasticizer di-2-ethylhexyl phthalate: 85 parts by weight, stabilizer di-butyltin dilaurate: 2.5 parts by weight, stabilizer epoxy soybean oil: 3 parts by weight,
(White pigment: 2 parts by weight) is injected, and a semi-gelled layer having an appropriate thickness is adhered to the inner surface by heating, and the ungelled polyvinyl chloride plastisol is discharged from the hole portion to obtain the polyvinyl chloride plastisol. Is a discolored and / or foreign substance of polyvinyl chloride plastisol (vinyl chloride emulsion polymerization resin: 100 parts by weight, plasticizer di-2-ethylhexyl phthalate: 90 parts by weight, stabilizer di-butyltin dilaurate: 2.5 parts by weight, stable (Epoxy soybean oil: 3 parts by weight, yellow pigment: 2 parts by weight) is poured into the slush molding mold slightly above the upper part of the mouth opening forming part, and a semi-gelled layer of an appropriate thickness is formed by heating. Is a method of completely gelating the semi-gelled layer adhered to the inner surface by heating after discharging the modified polyvinyl chloride plastisol by an appropriate method, Is performed by the hole portion provided with the discharge of polyvinyl chloride plastisol injected in time th to the bottom of slush molding mold.

(5) Japanese Patent Publication No. 59-37963 Japanese Patent Publication No. 59-37963 Plastisol (polyvinyl chloride paste resin: 100 parts by weight) containing a large amount of oil-resistant polymerizable polyester plasticizer for shoe soles in a slush molding mold, primary plasticizer: 20 to 70 parts by weight, polymerizable polyester plasticizer: 5
0-100 parts by weight, stabilizer: 2-4 parts by weight, pigment: 1-
(5 parts by weight) is injected and semi-gelled under heating to form an oil-resistant bottom with a stepped portion having a wall thickness of 3 to 6 mm, and then from above, an outer plastisol (polyvinyl chloride). Paste resin: 100 parts by weight, primary plasticizer: 70-1
(00 parts by weight, stabilizer: 2 to 4 parts by weight, pigment: 1 to 5 parts by weight), and the mixture is heated to a desired wall thickness, and then ungelled plastisol is discharged for gelation. This method is completed and taken out after cooling, and is intended to improve the oil resistance of the soles of slush-molded shoes used in oily environments such as various food factories and gas stations.

(6) Japanese Examined Patent Publication No. 2-3572 A vinyl chloride resin paste resin (100 parts by weight), an acrylic resin (10 to 50 parts by weight), a liquid nitrile rubber (5 to 45 parts by weight), and a crosslinking agent (2 parts by weight) to the liquid nitrile rubber are added. An outer sole molding composition for slush molded shoes, which comprises plastisol as a main component, and uses nitrile rubber for the purpose of improving cold resistance, flexibility and flexibility of the soles of slush molded shoes.

(7) Japanese Patent Publication No. 4-50802 Japanese Patent Publication No. 4-50802 Plastisol (polyvinyl chloride paste resin: 100 parts by weight) for molding insert pieces surrounded by a protruding wall having good thermal conductivity at the heel bottom of a slush molding mold. , Acrylic resin: 20 parts by weight, liquid nitrile rubber: 1
0 parts by weight, plasticizer: 40 parts by weight, stabilizer: 4 parts by weight, crosslinking agent: 2 parts by weight, crosslinking accelerator: 1 part by weight, red pigment: 2
(Parts by weight), and this is semi-gelled by heating to form an insert piece, and then a plastisol (polyvinyl chloride paste resin: 100 parts by weight) for molding a shoe body different from the above plastisol, a plasticizer: 70 parts by weight, stabilizer: 8 parts by weight, dark blue pigment: 2 parts by weight) are injected, and after heating, excess plastisol is discharged and heated, and the material injected into the surrounding compartment is replaced with other parts. It is possible to use another material.

[0014]

However, in these conventional techniques, a shoe sole having desired strength, abrasion resistance, oil and chemical resistance, cigarette (heat resistance), slip resistance, etc. It is not possible to provide a slush-molded shoe having a multilayer having excellent hardness, strength and texture and other portions other than the shoe sole, and having excellent overall characteristics as a shoe.

In the method for manufacturing a slush molded shoe proposed in Japanese Patent Publication No. 40-13590, hardness can be imparted because the amount of the plasticizer compounded in the shoe sole, which is the first layer, is relatively small. The functions required as a sole such as abrasion resistance, oil resistance, chemical resistance, cigarette resistance (heat distortion resistance), and slip resistance cannot be particularly improved.

The technique proposed in Japanese Patent Laid-Open No. 48-6834 is extremely difficult to implement on a production line. That is, a part (5 to 25 parts by weight) of the plasticizer is replaced with trimethylolpropane trimethacrylate, which is an acrylic acid ester thermosetting plasticizer. This acrylic acid ester thermosetting plasticizer serves as a polymerization catalyst. Since a peroxide such as di-t-butyl peroxide is added, the peroxide is decomposed and generates heat by heating, the molecules of the thermosetting plasticizer are cut off, and radical polymerization reactions occur in a chain. Therefore, when polyvinyl chloride plastisol containing a thermosetting plasticizer is injected into a slush molding mold and heated, gelation proceeds beyond a desired wall thickness due to a radical polymerization reaction that occurs in a chain, and the entire Even if it solidifies, or even if solidification does not proceed to the whole, the radical polymerization reaction gradually progresses in the discharged polyvinyl chloride plastisol, and the viscosity increases in the circulation process described above or solidification progresses due to self-heating and circulates. I can not do it.

The technique proposed by Japanese Patent Laid-Open No. 56-70702 is a technique for discharging the ungelled sol of the shoe sole, which is the first layer, by vacuum suction. The first layer is the bottom and the second layer is the second layer. Since the composition of each body part uses general polyvinyl chloride plastisol, the functions such as abrasion resistance, oil and chemical resistance, cigarette resistance (heat distortion resistance) and slip resistance must be improved significantly. I can't.

The technique proposed in Japanese Patent Publication No. 58-35683 is a technique for discharging the ungelled sol at the bottom which is the first layer from the holes at the bottom of the mold. The composition of the body, which is a layer, also uses a general polyvinyl chloride plastisol, so that the function cannot be specially improved. It should be noted that this technique requires a great number of man-hours for discharging from the bottom surface of the slush molding mold, and is difficult to apply to a production line.

According to the technique proposed in Japanese Patent Publication No. 59-37963, the oil resistance of the shoe sole can be secured, but the functions such as strength, abrasion resistance, cigarette resistance, and slip resistance are improved. Is something that cannot be done.

In the composition for the sole of the slush molded shoe proposed by Japanese Patent Publication No. 2-3572, the plasticizer is transferred to the nitrile rubber and the nitrile rubber is swollen and deformed. Is difficult

Further, in the method proposed by Japanese Patent Publication No. 4-50802, plastisol is introduced into a molding chamber surrounded by a protruding wall having good heat conductivity at the bottom of the heel and heated and semi-gelled. It is a technology for molding the first layer and does not improve functions such as abrasion resistance, oil resistance and chemical resistance, cigarette resistance, anti-slip properties, etc.In the actual production line, it is possible to eliminate the bounce at the time of injection. Therefore, it is not possible to eliminate the overflow or spillage from the surrounding area.

As described above, since the conventionally proposed techniques have not been able to comprehensively improve various functions required for slush-molded shoes, for example, the wall thickness of the shoe sole is increased or the shoe sole is increased. Although it has been dealt with by adhering as a separate component, the flexibility of the design is reduced and the manufacturing cost is increased, and the advantages of the slush molding technique cannot be enjoyed.

The present invention has been made in view of the problems of the prior art, and the shoe main body other than the sole has an appropriate hardness,
Slash molding that enhances the sole strength, abrasion resistance, cigarette resistance (heat distortion resistance), oil resistance and chemical resistance, as well as the slip resistance while ensuring strength and texture. The present invention seeks to provide a shoe and a manufacturing method thereof.

[0024]

In order to solve the above problems, a slush molded shoe having a multilayer structure according to the present invention is
All or part of the sole of the shoe body is a plastisol mixed with a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer, preferably a slip-resistant material, and / or has coloring transparency. The heat-gelated plastisol is further provided, and the other part of the shoe body is made of a heat-gelled plastisol mixed with a polyvinyl chloride resin.

Further, in the present invention, a plastisol in which a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer are mixed so as to cover the whole or a part of the inner surface of the bottom of the slush molding mold, preferably, a slip resistant material is mixed. And / or a first step of forming a first layer in a semi-gelled state on all or part of the inner surface of the bottom by injecting and heating plastisol further having coloring transparency, and A second semi-gelled state on the surface of the first layer and the inner surface of the slush molding mold by injecting and heating plastisol mixed with polyvinyl chloride resin to the upper end opening of the slush molding mold or in the vicinity thereof. By mixing the second step of forming a layer and the ungelled polyvinyl chloride resin remaining on the inner surface of the slush molding mold. A third step of discharging the plastisol, injecting the plastisol for the heel into the heel portion as necessary, and then heating the material to crosslink the first layer and gelate the second layer. Is a method of manufacturing a slush molded shoe having multiple layers.

[0026]

The present invention will be described in detail below along with its effects. The crosslinkable polyvinyl chloride resin used in the sole of the slush-molded shoe according to the present invention (hereinafter referred to as "the slush-molded shoe of the present invention") has a hydroxyl group, a carboxyl group, an epoxy group, an alkoxy group, and the like in the molecule. It has one kind or two or more kinds, and is crosslinked and cured by mixing a crosslinking agent such as isocyanate and heating.

As the crosslinking agent, tolylene diisocyanate, tolylene isocyanate dimer, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylolpropane-tolylene diisocyanate adduct, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, succinic acid, glutar Acids, adipic acid, pimelic acid, azelaic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid and their anhydrides, epoxies up to n = 10, triglycidyl isocyanate, 4,4'-diaminodiphenylmethaneglycidylamine, triazine, etc. It is illustrated.

In the plastisol mixed with the crosslinkable polyvinyl chloride resin, since the crosslinkable polyvinyl chloride resin is a powder and tends to have a relatively high viscosity, the workability of work such as injection into a slush molding mold is deteriorated. May occur. Therefore, a thermosetting plasticizer is mixed with the plastisol described above in order to prevent a decrease in workability.

Since the thermosetting plasticizer is a liquid before curing, when mixed with a plastisol mixed with a crosslinkable polyvinyl chloride resin, the viscosity of this plastisol can be adjusted, and after heating, it crosslinks to become a resin. Also, as will be described later, there are a wide variety of thermosetting plasticizers, and since the hardness after curing can be selected from many types, from relatively soft to hard, the hardness of the sole can be freely set to some extent. You can

The types of thermosetting plasticizers are listed below. Allyl ester-based thermosetting plasticizers diallyl phthalate, allyl acrylate, triallyl theateryl, diallyl maleate, dichloroallyl maleate, diallyl itaconic acid, diallyl sebacate, diallyl adipate, diallyl malonate, diallyl glycolate, Triallyl aconitate, triallyl phosphate, etc.

Acrylic ester type 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 etc.

Unsaturated Polyester Thermosetting Plasticizer Radical polymerization is carried out by heating with a linear polyester having some 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 cycloaliphatic epoxy resin to cure it.

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

Examples of the composition of the plastisol in which the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer are mixed are: polyvinyl chloride paste resin: 50 to 90 parts by weight, crosslinkable polyvinyl chloride resin: 10 to 50 parts by weight, plastic Agent: 80-12
0 parts by weight, thermosetting plasticizer: 10 to 40 parts by weight, catalyst:
0.3-1 parts by weight, stabilizer: 2-3 parts by weight, cross-linking agent:
0.5 to 3 parts by weight, pigment: 0 to 2 parts by weight.

In the slush-molded shoe of the present invention, the whole or a part of the sole of the shoe body is made of a heat-gelated plastisol in which a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer are mixed. Crosslinking improves the heat resistance of the shoe sole, makes it difficult to melt even under heating conditions, and improves cigarette resistance (heat distortion resistance). Further, the cross-linking also improves the strength, oil resistance, chemical resistance, and wear resistance of the sole.
In addition, if plastisol mixed with crosslinkable polyvinyl chloride resin and thermosetting plasticizer is injected to the upper end of the slush molding mold to perform crosslinking, peeling from the slush molding mold becomes difficult due to crosslinking, and demolding occurs. However, in the slush molded shoe according to the present invention, the plastisol mixed with the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer is used for all or part of the sole of the shoe. Therefore, the mold release property does not decrease so much, and the use amount of the plastisol mixed with the expensive crosslinkable polyvinyl chloride resin and the thermosetting plasticizer can be suppressed to the necessary minimum, which increases the manufacturing cost. Can be suppressed as much as possible.

In the slush-molded shoe according to the present invention, the other part of the shoe body except the sole is made of a heat-gelled plastisol mixed with a conventional polyvinyl chloride resin. Therefore, the hardness, strength, and feel of conventional slush molded shoes do not change.

A composition example of a plastisol mixed with such a polyvinyl chloride resin is polyvinyl chloride paste resin: 100 parts by weight, plasticizer: 80 to 120 parts by weight, stabilizer: 2 to 3 parts by weight, pigment: 1 ~ 2 parts by weight.

In the slush-molded shoe of the present invention, a plastisol in which a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer, which are raw materials for the sole of the shoe, are mixed with a slip-preventing material if necessary. In addition to the strength, oil resistance, chemical resistance and abrasion resistance of the sole, the slip resistance of the sole can be further improved. Since the anti-slip material is generally colored and insoluble, if it mixes into a part other than the sole of the shoe body, it will be recognized as a foreign substance and the appearance quality will be significantly deteriorated.However, in the present invention, it is mixed only in the sole. Therefore, it is possible to impart the anti-slip action to the shoe sole without deteriorating the appearance quality. Rather, by mixing the anti-slip material, the anti-slip property that can be surely imparted to the shoe sole can be visually appealed, so that the commercial property of the slush-molded shoes to be sold in a snowy place or the like can be improved.

Specific examples of the anti-slip material include cotton, suf (staple fiber), rayon, acrylic, vinylon, nylon, polyester, polyurethane, and glass fiber, which have 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, metal whiskers, inorganic whiskers, metal powder such as iron and aluminum, alumina powder, ceramic powder, crosslinked resin, acrylic resin, urethane resin Is an insoluble powder. The powder anti-slip material has a size of 3
It is 0 mesh or less, preferably 100 mesh or less.

If the plastisol mixed with the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer and the plastisol mixed with the polyvinyl chloride resin have the same color, for example, black, the joint between the shoe sole and the shoe body becomes inconspicuous. Although the appearance quality is improved, if the plastisol mixed with the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer, which are the raw materials for the sole, is colored and has transparency, the slush molding mold is formed by slush molding. Even if there is sticking to the inner surface of the mold due to bounce and vibration to the inner surface of the mold when it is first injected into the mold, the resin is transparent when it becomes a thin film by itself until the subsequent heat gelation, and the resin becomes transparent. Therefore, it becomes inconspicuous, and the bounce trace due to the first injection can be made inconspicuous in the product stage. Therefore, the reworking process associated with the bounce can be omitted, which is desirable as a slush-molded shoe that requires mass productivity. Since a plastisol mixed with a transparent cross-linkable polyvinyl chloride resin and a thermosetting plasticizer is used for the sole of the shoe, high-quality shoes similar to rubber can be obtained by approximating the hue of rubber crepe or smoke. It can also be used as the bottom, and the marketability can be further improved.

In order to impart colored transparency to a plastisol in which a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer are mixed, in a usual case, 1 to 2 per 100 parts by weight of resin is added.
About 0 to 0.2 parts by weight of a pigment (in the case of a pasty pigment or a masterbatch, the amount of a resin or a plasticizer mixed with the pigment is not included) is used, and more preferably 0.
It is reduced to 02 to 0.1 parts by weight.

In the slush-molded shoe of the present invention, when the uneven design is present in a part of the sole such as the heel portion or the stepping portion, the thickness of the convex design portion of the shoe sole is further increased. If the height (thickness) of the convex design part of the shoe sole, which is the ground contact part, is large, the design part will wear and wear when worn,
Since it takes a long time to reach the thick base portion of the shoe sole, the duration of the effects such as anti-slip properties becomes longer by the longer time, which is more desirable.

There is an injection molding method other than the slush molding method for manufacturing shoes using plastisol mixed with a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer as a raw material. In the injection molding method, molding is performed after heating. For this reason, it is conceivable that molding is carried out after crosslinking, but in the slush molding method, since crosslinking is carried out by heating after molding, there is a large degree of freedom in processing, which is also desirable from this point of view.

Next, a method of manufacturing the slush molded shoe of the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a vertical sectional view of a slush molding shoe of the present invention formed inside a slush molding mold. In the production method of the present invention, as the first step, as shown in the figure, a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer are mixed so as to cover all or part of the inner surface of the bottom of the slush molding mold 1. Mixing plastisol or anti-slip material,
And / or a plastisol further having a colored transparency is injected and heated to form the first layer 2 in a semi-gelled state on all or part of the inner surface of the bottom.

In the embodiment shown in FIG. 1, the material is injected into the front and rear ends of the shoe sole and not into the center of the shoe sole, but it may be injected into the entire surface of the shoe sole. It is appropriately determined according to the function required for the shoe sole and the manufacturing cost.

Injection may be similar to conventional means, for example:
The injection nozzle is arranged toward the inner bottom portion of the slush molding mold 1, and injection is performed by applying appropriate pressure. The injection pressure is adjusted while paying attention so that the inner surface of the slush molding mold 1 does not bounce when injecting, but it is transparent even if the plastisol mixed with the crosslinkable polyvinyl chloride resin to be injected is colored. When the second layer 3 has a dark color, it is relatively inconspicuous and naturally finished even if it is adhered to the inner surface of the slush molding mold 1 without any rework. Also, the heating time after injection may be the same as the conventional one,
It is appropriately adjusted according to the thickness of the shoe sole to be formed.

In the present invention, after the first layer 2 in a semi-gelled state is formed by heating, as a second step, a plastisol in which a polyvinyl chloride resin is mixed up to or near the upper end opening of the slush molding mold 1 is used. By injecting and heating, the semi-gelled second layer 3 is formed on the surface of the first layer 2 and the inner surface of the slush molding mold 1.

The height at which the plastisol mixed with the polyvinyl chloride resin is injected is appropriately determined according to the height required as a product. Further, the heating time after injection may be the same as the conventional one, and is appropriately adjusted according to the thickness of the shoe body to be formed.

After the completion of this second step, as the third step,
After discharging the plastisol mixed with the ungelled polyvinyl chloride resin remaining on the inner surface of the slush molding mold 1, injecting the plastisol for the heel into the heel portion as necessary, and then heating it sufficiently. As a result, the first layer 2 is crosslinked and the second layer 3 and the heel portion 4 are gelated.

The discharge of the plastisol mixed with the ungelled polyvinyl chloride resin and the subsequent heating are carried out by known means.

Since the skin of the slush-molded shoe is formed in this way, after cooling and demolding, the inner boot and the parts such as the insole and fastener are assembled to this skin by sewing, bonding, etc., and the final coating is performed. The product.

As described above, according to the method of the present invention, the sole of the shoe body of the shoe body is maintained while the proper hardness, strength and texture of the skin other than the sole are ensured. Strength, abrasion resistance, cigarette resistance (heat resistance)
Further, it is possible to manufacture a slush-molded shoe in which oil- and chemical resistance, and in addition to these, comprehensive improvement of various functions of the sole such as slip resistance.

[0054]

[Example 1]

[0055]

[Table 1]

A cross-linkable polyvinyl chloride paste resin for the first layer having the composition shown in Table 1 was formed to a predetermined position on the bottom of the inner surface of the slush molding mold 1 shown in FIG. Pouring to 150 ℃
Then, the mixture was heated for 1 to 2 minutes to form a semi-gelled state on the bottom surface of the slush molding mold 1.

Next, according to the above composition, the polyvinyl chloride paste resin for the second layer was fully injected to the upper end of the slush molding mold 1 and heated at 180 ° C. for 1 to 2 minutes to form the slush molding mold 1. A semi-gelled layer having a desired wall thickness was attached to the inner surface of the plaque, and the ungelled plastisol was discharged.

Further, according to the above-mentioned composition, plastisol mixed with polyvinyl chloride resin for heel is injected into the portion corresponding to the heel portion and filled therein, and heated at 200 ° C. for 5 to 7 minutes to sufficiently form the first layer. The second layer 3 and the heel portion 4 were gelated sufficiently while being crosslinked. Then, after cooling, it was taken out from the slush molding mold 1 to obtain a slush molding shoe of the present invention example in which both the shoe sole and the shoe body were black.

On the other hand, a plastisol containing no crosslinkable polyvinyl chloride resin and thermosetting plasticizer is used for the first layer,
A slush molded shoe of a comparative example was manufactured under exactly the same conditions except the above.

The strength, abrasion resistance, cigarette resistance (heat resistance) and oil resistance and chemical resistance of the soles of these two types of slush molded shoes were evaluated as follows. (Strength) Based on JIS K-6301, tensile strength, elongation and tear strength were measured by a Shopper type tensile tester. (Abrasion resistance) Wearing wheel CS-1 by Taber abrasion tester
The wear loss at 1000 revolutions was measured by 0. (Cigarette resistance) A JIS K-6301 No. 1 test piece was cut out from the shoe sole and hung in an oven at 180 ° C for 5 minutes, and the presence or absence of melt drop and the elongation rate when it did not drop were measured.

Further, the manufactured slush-molded shoe of the present invention was used to actually step on the cigarette to extinguish the fire, and the melting / deformed state of the shoe sole was confirmed. (Oil and chemical resistance) For JIS No. 3 oil and soybean oil, heat and hold at 40 ° C. for 96 hours to obtain J
The extraction status of the plasticizer with IS 3 oil and soybean oil was investigated.

The results are summarized in Table 2. The slush-molded shoe of the present invention has the same strength, hardness and texture of the shoe body as those of the conventional slush-molded shoe, and moreover, the sole has particularly excellent heat distortion resistance (cigarette resistance). In addition, the tensile strength, abrasion resistance, and oil resistance and chemical resistance are also improved, and it can be seen that the examples of the present invention have improved various properties of the sole as compared with the conventionally known two-layer slush molded shoes.

[0063]

[Table 2]

[0064]

Example 2 As shown in Table 1, in Example 1, a plastisol mixed with a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer, which are raw materials for shoe soles, was added to whiskers (Shikoku Kasei Kogyo Co., Ltd.) is further mixed,
A slush molded shoe of the present invention was manufactured in exactly the same manner as in Example 1.

Regarding the slush molded shoe of the present invention,
The slip resistance was evaluated as follows. (Anti-slip) P-tiles, vinyl flooring, put shoes on ice,
The load was measured by applying a load of 10 kg and starting tension.

The results are shown in Table 2. In addition to the results of Example 1, it can be seen that the slush molded shoe of the present invention is excellent in slip resistance in addition to the effects of Example 1.

[0067]

Example 3 As shown in Table 1, in Examples 1 and 2, the pigment mixed in the plastisol containing the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer, which are raw materials for the sole of the shoe, was added to the organic pigment. -Based crepe color tone pigment: Slush molded shoes were manufactured in the same manner by reducing the amount to 0.1 part by weight.

The plastisol mixed with the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer of the first layer constituting the sole for reducing the pigment becomes colored and transparent, and the plastisol of the mold for slush molding by the first injection is formed. The slush molded shoe with excellent appearance quality could be manufactured by the second injection without repairing the adhesion on the inner surface.

[0069]

As described above in detail, in the present invention, the sole of the slush molded shoe and the shoe main body excluding the sole are made of different materials, and in particular, the sole has abrasion resistance and cigarette resistance ( Heat resistance), oil- and chemical-resistant cross-linkable polyvinyl chloride resin and a thermosetting plasticizer are mixed to form a gelled product of plastisol, so the strength, hardness and texture of the shoe body are the same as before. It was possible to improve the various functions of the sole comprehensively while maintaining it.

In the present invention, slip resistance can be imparted to the sole by mixing the plastisol, which is the raw material for the sole, with the anti-slip material.

In the present invention, by reducing the amount of the pigment contained in the plastisol, which is the raw material of the shoe sole, to impart the coloring transparency, the slush molding by double injection is performed at 1
It is not necessary to repair stains on the inner surface of the slush molding mold associated with the second injection, and productivity can be improved.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a slush molding shoe of the present invention formed inside a slush molding mold.

[Explanation of symbols]

 1 Slush molding mold 2 1st layer 3 2nd layer 4 Heel part

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[Procedure amendment]

[Submission date] March 30, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

As the crosslinking agent, tolylene diisocyanate, tolylene isocyanate dimer, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylolpropane-tolylene diisocyanate adduct, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, succinic acid, glutar Acids, adipic acid, pimelic acid, azelaic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid and their anhydrides, epoxies up to n = 10, triglycidyl isocyanate, 4,4'-diaminodiphenylmethaneglycidylamine , in the molecule Mercapto (-S-
H) group containing azoles, thiazoles and triazines
Compound or its metal salt (2-R-4.6-dimercapto
-S-triazine, etc.), an azo group (-N = N-) in the molecule.
Group), a —S—S— group, a —N—S— group, and a —O—O— group.
Examples thereof include compounds .

Claims (6)

[Claims] 1. The whole or a part of the sole of the shoe body is made of a heat-gelated plastisol mixed with a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer, and the other part of the shoe body is A slush molded shoe consisting of multiple layers, which is made of a heat-gelled plastisol mixed with polyvinyl chloride resin. 2. The multi-layered slush molded shoe according to claim 1, wherein the plastisol in which the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer are mixed further comprises an anti-slip material. 3. The multilayer slush molded shoe according to claim 1 or 2, wherein the plastisol in which the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer are mixed has color transparency. 4. A plastisol mixed with a crosslinkable polyvinyl chloride resin and a thermosetting plasticizer is injected so as to cover all or a part of the inner surface of the bottom of the slush molding mold, and the whole inner surface of the bottom is heated by injecting the plastisol. Or a first step of forming a first layer in a semi-gelled state in part, and by injecting a plastisol mixed with a polyvinyl chloride resin to the upper end opening of the slush molding mold or in the vicinity thereof and heating it A second step of forming a second layer in a semi-gelled state on the surface of the first layer and the inner surface of the slush molding mold, and an ungelled polyvinyl chloride resin remaining on the inner surface of the slush molding mold. And discharging the mixed plastisol and then heating to crosslink the first layer and gelate the second layer. A method for manufacturing a slush-molded shoe having multiple layers, which is characterized in that 5. The method of manufacturing a multilayer slush molded shoe according to claim 4, wherein the plastisol in which the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer are mixed is mixed with a slip resistant material. 6. The method for producing a slush molded shoe having a multilayer structure according to claim 4 or 5, wherein the plastisol in which the crosslinkable polyvinyl chloride resin and the thermosetting plasticizer plasticizer are mixed has color transparency.