KR101552161B1 - Rubber sheet composition for bonding sole of shoes, and method for preparing sole of shoes - Google Patents

Rubber sheet composition for bonding sole of shoes, and method for preparing sole of shoes Download PDF

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Publication number
KR101552161B1
KR101552161B1 KR1020150068987A KR20150068987A KR101552161B1 KR 101552161 B1 KR101552161 B1 KR 101552161B1 KR 1020150068987 A KR1020150068987 A KR 1020150068987A KR 20150068987 A KR20150068987 A KR 20150068987A KR 101552161 B1 KR101552161 B1 KR 101552161B1
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South Korea
Prior art keywords
rubber
outsole
sheet
bonding
midsole
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KR1020150068987A
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Korean (ko)
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이성율
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화인케미칼 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/122—Soles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2410/00—Soles

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Mechanical Engineering (AREA)

Abstract

A composition for integrating an outsole and a midsole, the polymer base comprising an ethylene copolymer and a rubber having a melting point of 35 to 90 占 폚; A rubber composition for sole bonding comprising a mixture of a vulcanizing agent and a vulcanizing agent; And a polymer base including an ethylene copolymer and a rubber having a melting point of 35 to 90 DEG C, And a vulcanizing agent, on an outsole sheet; And a step of fabricating the outsole sheet and the foamed midsole preform in which the bonding sheet is laminated by using a shoe sole mold as a sole with an outsole and a midsole integrated with each other.

Description

TECHNICAL FIELD [0001] The present invention relates to a rubber composition for shoe sole bonding and a method for manufacturing the shoe sole,

The technique disclosed in this specification relates to a rubber composition for sole bonding and a method for manufacturing a sole using such a rubber composition.

A shoe is made of a natural rubber and synthetic rubber rubber outsole (hereinafter referred to as "outsole") on the floor contacting the ground to lighten the weight, and a midsole between the rubber window and the upper It is common to use an ethylene copolymer foamed foam such as EVA foam having a good cushioning property.

The outsole is prepared by mixing and vulcanizing silica (SiO 2 ) and a vulcanizing agent as a reinforcing material in natural rubber and synthetic rubber to realize abrasion resistance and slip resistance, and the ethylene copolymer foamed foam midsole is made of an ethylene copolymer such as EVA , A cross-linking agent and a blowing agent are mixed and then usually produced by the following four methods:

First, the formulation is foamed at an appropriate ratio, then skiving-cutting-buffing, and then molded into a midsole.

This method is simple and inexpensive, but has a disadvantage in that the surface shape of the midsole is simple and the appearance of the foamed foam is not visible due to the cell exposure, which is applied to some low-priced products.

Second, the blend is pelletized by an extruder, cross-linked foaming is carried out by injection and hot pressing in a mold provided in the starting furnace, and then the product is taken out from the mold to produce a product with a midsole having a predetermined expansion ratio of about 150 to 170% .

Although this method is relatively simple and inexpensive in cost, it may be difficult to obtain a clean product because the product may be foamed in the mold and thus the dimensional stability may be poor or the surface condition of the product may be poor.

Third, according to the Phylon process, a midsole molded product (hereinafter referred to as a 'midsole preform') was first prepared through the first method. Then, a midsole preform having a mold inner volume of 1.52 times the inner volume of the mold was placed in the final product mold, (Hereinafter referred to as "heating and pressing"), followed by heating to 15 to 30 ° C., followed by pressing for 10 to 20 minutes (hereinafter referred to as "cooling and pressing")

This method has the same size of the product and the mold, so it is possible to obtain a high-quality product with a beautiful appearance, but the manufacturing process is cumbersome, and the factory area and cost are disadvantageous.

Fourthly, according to the CMP-Phylon process, which is a modification of the third method, the compounding is placed on a mold and crosslinked and foamed under heating to form a compression molded preform (CMP: Then, a midsole preform (CMP) 1.5 to 2 times the internal volume of the mold is placed in the final product mold, and the resultant is heated and pressurized for 10 to 20 minutes, then heated to 15 to 30 ° C. and pressurized for 1020 minutes. system.

This method has the same size of product and mold, so it is possible to obtain high-quality products with beautiful appearance and the manufacturing process is shortened not only by the third Phylon process but also by the skyling-cutting- And 20-30%, respectively.

As a result, the resulting midsole can not be used as a shoe sole, and can be used as a finished window by adhering it on an outsole using an adhesive or the like. In the midsole according to the first process, the room temperature buffing is a final step, Is released from the mold when it is demolded, so that it is not possible to replace the adhesive process.

On the other hand, in the third and fourth processes, since the size of the product and the mold are the same when the product is demolded, the outsole vulcanized at the bottom of the compression mold for the midsole is inserted and the midsole preforms 1.5 to 2.0 times larger than the mold contents are sequentially stacked According to Korean Patent Registration No. 1214673, for example, an outsole is placed on a mold, and then an adhesive film such as an epoxy-based adhesive and an EVA foam are stacked And then cooling and pressurizing by heating, pressing, cooling and demolding. However, this method requires two or more adhesive films and also has the disadvantage of a long process of cooling and pressing after heating and energy consumption.

Accordingly, the present inventors have focused on a novel rubber composition for sole-shoe bonding as a substitution technique for a bonding process using an adhesive between an outsole and a midsole, or a bonding process using two or more adhesive films in place of an adhesive, I have come to completion.

That is, one object of the presently disclosed subject matter is to provide an ethylene copolymer having a specific melting range to form a bridge structure between an outsole and a midsole without additional heating using the compression molding die take-out temperature of the midsole And to provide a rubber composition for shoe sole bonding.

Another object of the present invention is to provide a method of manufacturing a sole with improved adhesion strength and heat resistance by performing the bonding process between the outsole and the midsole by using the rubber composition for sole bonding without further heating of the final sole of the product mold I have to.

According to one aspect of the techniques disclosed herein,

A composition for integrating an outsole and a midsole, the polymer base comprising an ethylene copolymer and a rubber having a melting point of 35 to 90 占 폚; And a mixture of a vulcanizing agent.

According to another aspect of the techniques disclosed herein,

A polymer substrate comprising an ethylene copolymer and a rubber having a melting point of 35 to 90 캜; And a vulcanizing agent, on an outsole sheet; And a step of manufacturing the outsole sheet and the foamed midsole preform (CMP) in which the bonding sheet is laminated, using a shoe sole mold, as a sole with an outsole and a midsole integrated with each other.

According to another aspect of the techniques disclosed herein,

The ethylene copolymer in the bonding sheet, which is manufactured by the above-described manufacturing method and which is melted by hot mold-taking-out of the foamed midsole preform (CMP), forms a bridge structure between the outsole sheet and the foamed midsole to provide an integrated sole .

According to the technique disclosed in this specification, by using a rubber composition for sole-joint bonding comprising an ethylene copolymer having a specific melting point range so as to form a bridge structure between the outsole and the midsole, And a method of manufacturing a sole with improved bonding strength and heat resistance by omitting the step of heating the final product mold.

Hereinafter, the techniques disclosed in this specification will be described in more detail.

Conventional shoe sole manufacturing processes include a bonding process using an adhesive between an outsole and a midsole, and a heating process in a final product mold. By omitting these processes, an enormous energy saving and shortening of the process time are required.

Therefore, according to the technology disclosed in this specification, in order to omit the bonding process using the adhesive between the outsole and the midsole, and to produce a sole having improved bonding strength and heat resistance omitting the heating process of the final product mold, Provided is a novel rubber composition for sole-shoe bonding which can be melted by the temperature of taking out a press-formed mold and form a bridge structure between the outsole and the midsole.

The rubber composition for sole-shoe bonding according to one embodiment of the present invention is a composition for integrating an outsole and a midsole, and includes an ethylene copolymer having a melting point of 35 to 90 DEG C and a rubber- materials; And mixtures of vulcanizing agents. The ethylene copolymer is low in price, low in hardness and excellent in compatibility with a rubber base material as compared with a general ethylene polymer, melts when taken out from a midsole preform press-molding mold, forms a bonding bridge between the outsole and the midsole, The rubber base material has high abrasion resistance, high elasticity, and maintains the physical properties of the final shoe sole.

In particular, the melting point of the ethylene copolymer may be within a range that can be melted at the take-off surface temperature to suit the role of the adhesive bridge between the outsole and the midsole, and may be, for example, 35 to 90 캜 or 38 to 88 캜. It is possible to prevent deformation and shrinkage of the sole according to the change of the external environment (particularly temperature) within the above range, and also to dissolve at a surface temperature of 120 to 150 캜 of the foamed midsole preform taken out from the midsole- Can be provided.

When the melting point of the ethylene copolymer is less than 35 占 폚, the ethylene polymer contained in the rubber composition for bonding is melted, and when the melting point of the ethylene copolymer is lower than 35 占 폚, Adhesion may drop during wearing. When the melting point of the ethylene copolymer exceeds 90 캜, the foamed preform having a surface temperature of 120 to 150 캜, which is taken out from the compression molding die, melts the ethylene copolymer contained in the upper surface of the outsole The adhesive strength is low and it may be difficult to put it into practical use.

The melting point refers to the melting point peak temperature measured by differential scanning calorimetry (DSC) thermal analysis unless otherwise specified.

The weight ratio of the ethylene copolymer to the rubber may be from 2: 8 to 8: 2, from 3: 7 to 7: 3, or from 4: 6 to 6: 4, The bonding strength between the bonding sheet and the outsole sheet obtained from the rubber composition for sole bonding the shoe sole, the bonding strength between the bonding sheet and the foamed preform, and the heat resistance can be remarkably improved.

For reference, if the content of the rubber is insufficient, the adhesive strength between the outsole sheet and the bonding sheet obtained from the rubber composition for bonding may be poor, and if the content of the ethylene copolymer is insufficient, the adhesive force between the bonding sheet and the midsole may be poor.

Such ethylene copolymers are, for example, i) ethylene and ii) C 3 -C 10 alpha olefins, C 1 -C 12 alkyl esters of C 3 -C 20 monocarboxylic acids, unsaturated C 3 -C 20 mono or dicarboxylic acids, An anhydride of an unsaturated C 4 -C 8 dicarboxylic acid, and a vinyl ester of a saturated C 2 -C 18 carboxylic acid, or an ionomer of the copolymer.

Specific examples of the ethylene copolymer include ethylene vinyl acetate, ethylene vinyl acetate (EVA), ethylene butyl acrylate (EBA), ethylene methylacrylate (EMA), ethylene ethyl acrylate (EEA) ), Ethylene methyl methacrylate (EMMA), ethylene butene copolymer (EB-Co), and ethylene octene copolymer (EO-CO).

In the ethylene copolymer, ethylene preferably accounts for a major mole fraction of the whole polymer, and ethylene generally accounts for at least about 50 mole% of the total polymer. More preferably, ethylene accounts for at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent.

In terms of high elasticity, the ethylene copolymer may be a copolymer of ethylene and an alpha olefin. The alpha olefin is an olefin having 2 or more carbon atoms and having a double bond at the terminal. The substantial remainder, excluding ethylene, in the total ethylene alpha olefin copolymer preferably comprises one or more other comonomers which are alpha olefins having three or more carbon atoms. In particular, the alpha olefin is preferably butene, hexene or octene in view of commercialization and availability. For example, in the case of ethylene octene copolymers, preferred compositions comprise an ethylene content of at least about 80 mole percent of the total polymer, and an octene content of from about 10 to about 15 mole percent, preferably from about 15 to about 20 mole percent, of the total polymer .

The ethylene and alpha-olefin copolymers may be random copolymers or block copolymers. Examples of commercially available products include Engage and Infuse from Dow Chemical, Tafmer from Mitsui, Exact Mobile from Exxon Mobile, and LG-POE from LG Chemical. In particular, the low-cost process disclosed in this specification includes a random copolymer of ethylene and an alpha olefin Coalescence is preferred. In the case of the ethylene random copolymer, the ethylene content may be from about 60 mol% to about 99.5 mol%, in some embodiments from about 80 mol% to about 99 mol%, and in some embodiments from about 85 mol% to about 98 mol% have. Likewise, the alpha-olefin content may range from about 0.5 mole percent to about 40 mole percent, in some embodiments from about 1 mole percent to about 20 mole percent, and in some embodiments from about 2 mole percent to about 15 mole percent. The distribution of alpha-olefin comonomers is typically random and uniform over different molecular weight fractions forming ethylene copolymers.

The rubber may be at least one selected from natural rubber, isoprene rubber, butadiene rubber, and styrene-butadiene rubber. The natural rubber may be a general natural rubber or a modified natural rubber. The above-mentioned general natural rubber may be used as long as it is known as natural rubber, and the country of origin and the like are not limited. The natural rubber is polyisoprene, which contains cis-1,4-polyisoprene as a main component, but may also contain trans-1,4-polyisoprene in accordance with required properties. Therefore, in addition to natural rubber containing cis-1,4-polyisoprene as a main component, natural rubber including trans-1,4-isoprene as a main component, such as balata, Rubber may also be included. The modified natural rubber means that the general natural rubber is modified or purified. Examples of the modified natural rubber include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber and the like. The natural rubber is not limited to any form such as crepe rubber, sheet rubber, skim rubber and the like.

The rubber is, for example, a high-sheath rubber which is selected from at least one of i) styrene-butadiene rubber, and ii) high cis 1,4-isoprene rubber, and high cis 1,4- (high cis) rubber.

As a specific example, the weight ratio of the i) styrene-butadiene rubber and ii) the high sheath rubber may be from 4: 6 to 6: 4, or from 4.5: 5.5 to 5.5: Can be selected according to the kinds of the raw materials used in the condition of giving high elasticity while maintaining the physical properties of the final shoe sole . The term "high cis" means that the cis-1,4 content in the rubber is 95% or more, or 97% or more, unless otherwise specified, and the processability and abrasion resistance can be excellent within this range.

As another example, the styrene-butadiene rubber may have a Mooney viscosity (ML 1 + 4 100) of 45 to 55, and the hyacinth 1,4-isoprene rubber may have a Mooney viscosity (ML 1 + 4 100) 90, and the high sheath 1.4-butadiene rubber may have a Mooney viscosity (ML 1 +4 100) of 40 to 50. The Mooney viscosity refers to the viscosity of the unvulcanized rubber measured by a Mooney viscometer. The value is usually measured at 1 minute after preheating at 100 ° C. for 4 minutes after starting the rotor and is expressed as ML 1 +4 (100) .

The rubber composition for bonding according to one embodiment of the technology disclosed herein contains a vulcanizing agent, which is an additive for vulcanizing the rubber in the presence of the ethylene copolymer. Through the vulcanization process, the rubber base material is crosslinked and dispersed as micro-gel fine particles in the ethylene copolymer resin matrix.

The vulcanizing agent may be a sulfur or a sulfur compound. Examples of the sulfur compound include sulfur dichloride, morpholine disulfide, polysulfide, tetramethylthiuram disulfide, dimethyldithiocarbamic acid selenium (selenium dimethyl dithiocarbamate), 2- (4'-morpholinodithio) benzothiazole, and the like. The vulcanizing agent may be contained in an amount of 0.1 to 5.0 parts by weight, 0.1 to 3.0 parts by weight, or 0.3 to 1.7 parts by weight based on 100 parts by weight of the polymeric base material.

In the rubber composition for bonding according to one embodiment of the technology disclosed herein, a vulcanizing accelerator, a softening agent such as stearic acid or ethylene bisstearamide, or a crosslinking auxiliary such as zinc oxide may be added to the rubber composition within a range not adversely affecting the reaction . For example, the vulcanization accelerator may be contained in an amount of 0.1 to 3.0 parts by weight, or 0.2 to 0.8 parts by weight, based on 100 parts by weight of the polymer base material, 0.1 to 3 parts by weight, or 0.1 to 2.5 parts by weight, and the crosslinking aid may further be contained in the range of 0.5 to 8 parts by weight, or 0.6 to 4.4 parts by weight.

A method of manufacturing a sole using a rubber composition for bonding according to an embodiment of the technique disclosed in this specification can be manufactured in the following manner. Firstly, as a composition for bonding, a polymer substrate containing an ethylene copolymer and a rubber having a melting point of 35 to 90 캜; And a vulcanizing agent are laminated on an outsole sheet. Next, the outsole sheet and the foamed midsole preform in which the bonding sheet is laminated can be provided as a sole in which the outsole and the midsole are integrated by using the sole mold.

The thickness of the outsole sheet and the bonding sheet may be, for example, 70:30 to 95: 5, or 75:25 to 90:10.

For example, the step of laminating the bonding sheet on the outsole sheet can be performed at a temperature of 150 to 160 캜 for 10 to 20 minutes, and effective lamination and further integrated structure can be provided within this range.

The foaming magnification (coefficient of linear expansion) of the foamed preform may be 170 to 190%. When the foamed midsole preform is taken out from a midsole molding die (compression molding die), the surface temperature is preferably in the range of 120 to 150 占 폚 or 120 to 145 占 폚, It is possible to effectively melt the copolymer.

The outsole sheet in which the bonding sheet is laminated may be preheated to 50 to 150 DEG C to maximize the melting of the ethylene copolymer in the bonding sheet, thereby achieving an efficient bridge structure.

Then, the outsole sheet having the bonding sheet laminated thereon and the foamed midsole preform are sequentially laminated on the sole mold, pressed at room temperature for a short time, and then demolded to provide the sole with the outsole and the midsole integrated.

Specifically, the step of fabricating the outsole and the midsole with the integrated shoe sole is performed by placing the outsole sheet having the bonding sheet laminated on the lower end of the shoe sole mold, 150 ° C, and then pressurized at room temperature for 3 to 10 minutes, followed by demolding. Particularly, according to the technology embodied in the present specification, in order to bond between the outsole and the midsole in the conventional shoe sole mold, the pressurization after pressurization by warming is performed only at a pressurizing process at room temperature for a short time such as 3 to 10 minutes or 5 to 6 minutes at room temperature And can additionally provide advantages that can be manufactured.

The composition for the outsole sheet and the foamed midsole preform may be appropriately selected if they are well known in the art. For example, the composition for the outsole sheet may contain a vulcanizing agent such as an emulsifying or emulsifying compound in 100 parts by weight of the rubber base material 0.1 to 5.0 parts by weight, and the composition for the outsole sheet is mixed with an open mill or the like and vulcanized in a mold under ordinary vulcanizing conditions, for example, at 150 to 160 캜 for 5 to 10 minutes, Can be manufactured.

The rubber base can be selected from, for example, natural rubber and synthetic rubber. Specific examples thereof include natural rubber and synthetic rubber in a weight ratio of 10:90 to 90:10, or 20:80 to 80:20 Weight ratio. Particularly, the synthetic rubber may be a high cis 1,4-butadiene rubber, and may be a high cis 1,4-butadiene rubber having a Mooney Viscosity (ML 1 + 4 100) Rubber can be used.

If necessary, the composition for the outsole sheet may contain a reinforcing agent such as silica and carbon black; A softening agent such as stearic acid and ethylenebisstearamide; Rubber auxiliary agents such as polyethylene glycol; Vulcanization accelerators; An activator; Pigments and the like within a range not adversely affecting the reaction. For example, the composition for the outsole sheet may contain the reinforcing agent in the range of 5 to 80 parts by weight, the softening agent in the range of 0.5 to 10 parts by weight, the rubber auxiliary agent in the range of 0.5 to 10 parts by weight, The accelerator may be included in the range of 0.5 to 3 parts by weight.

The composition for a foamed midsole preform may be a foamed composition comprising an ethylene copolymer and 1 to 15 parts by weight, or 1 to 10 parts by weight of a blowing agent such as azodicarbonamide based on 100 parts by weight of the ethylene copolymer, The composition for a foamed midsole preform is mixed with an open mill or the like, placed on a compression molding die (CMP mold), and foamed under heating and pressing to produce a foamed midsole preform by a compression molding method.

Such ethylene copolymers are, for example, i) ethylene and ii) C 3 -C 10 alpha olefins, C 1 -C 12 alkyl esters of C 3 -C 20 monocarboxylic acids, unsaturated C 3 -C 20 mono or dicarboxylic acids, An anhydride of an unsaturated C 4 -C 8 dicarboxylic acid, and a vinyl ester of a saturated C 2 -C 18 carboxylic acid, or an ionomer of the copolymer.

Specific examples of the ethylene copolymer include ethylene vinyl acetate (EVA), ethylene butylacrylate (EBA), ethylene methylacrylate (EMA), ethylene ethyl acrylate, EEA), ethylene methyl methacrylate (EMMA), ethylene butene copolymer (EB-Co), and ethylene octene copolymer (EO-Co).

As another example of the ethylene copolymer, ethylene and vinyl acetate may be ethylene vinyl acetate having a weight ratio of 50:50 to 85:15 or a weight ratio of 60:40 to 80:20.

The composition for a foamed midsole preform may further comprise a crosslinking agent such as dicumyl peroxide in an amount of 0.1 to 5 parts by weight or 0.5 to 3 parts by weight based on 100 parts by weight of the ethylene copolymer.

The shoe sole according to one embodiment of the technology disclosed in the present specification is manufactured by the above-described manufacturing method, wherein the ethylene copolymer in the bonding sheet melted by the mold take-out at the surface high temperature of the foamed midsole preform is formed between the outsole sheet and the foamed midsole And may have a bridge structure and an integrated structure.

The shoe sole according to one embodiment of the technology disclosed herein provides an improved adhesive force even when the heating process is omitted and a separate adhesive film or adhesive process is not applied. For example, the outsole sheet and the bonding sheet an in-between adhesive strength 5.0~6.0 kg / cm 2 range, and at the same time the bonding sheet and the foamed midsole between the adhesive strength is 4.0~5.0 kg / cm 2 range can be tomorrow.

Hereinafter, the techniques disclosed in this specification will be described with reference to various embodiments, but the technical idea of the technology disclosed in this specification is not limited by the following embodiments.

[ Example ]

<Materials Used>

Natural rubber-1: SMR-L (Standard Malaysian Rubber).

SBR1502 : a styrene-butadiene rubber containing 22.5 to 24.5% by weight of a styrene monomer and 4.5 to 6.75% by weight of an organic acid and having a Mooney viscosity (ML 1 + 4 100) of 45 to 55.

IR2200 : High cis 1,4-isoprene rubber having a Mooney viscosity (ML 1 + 4 100) of 82.

BR1208 : High cis 1,4-butadiene rubber having a Mooney viscosity (ML 1 + 4 100) of 40 to 45.

Polymer- 1: Engage 7467 (DOW, Ethylene Butene Copolymer, DSC melting point: 34 占 폚).

Polymer- 2: Engage 8842 (manufactured by DOW, Ethylene Octene Copolymer, DSC melting point: 38 占 폚)

Polymer- 3: ELVAX 460 (manufactured by Dupont, Ethylene Vinyl Acetate Copolymer, DSC melting point: 88 占 폚)

Polymer- 4: LDPE 5321 (Hanfase, LDPE, DSC melting point: 109 캜)

Polymer- 5: LLDPE 3120 (Hanwha, LLDPE, DSC melting point: 122 캜)

Polymer- 6: HDPE 3392 (Hanwha, HDPE, DSC melting point: 134 캜).

< Bonding  Manufacture of sole containing sole Example  1 to 5, Comparative Example  1 to 4)

1) Bonding sheet manufacture :

30 parts by weight of natural rubber SMR-L, 70 parts by weight of synthetic rubber BR1208, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide, 40 parts by weight of silica (SiO2), 2 parts by weight of polyethylene glycol, 2 parts by weight of sulfur, M) were mixed in an open mill to prepare an outsole sheet having a thickness of 4.0 mm.

The polymer substrate of the ethylene copolymer and the rubber was blended in a Kneader having a capacity of 1 L according to the composition published in Table 1 below. The temperature of the kneader chamber was raised to the temperature above the DSC melting point of the ethylene (co) polymer, . After mixing, 1.0 part by weight of sulfur as a vulcanizing agent, 0.51.0 parts by weight of promoter M as a vulcanization accelerator, 1.0 part by weight of stearic acid as a softening agent and 2.5 parts by weight of zinc oxide as a crosslinking assistant were further added to 100 parts by weight of the polymer substrate, After further mixing, the reaction was terminated and nine types of bonding sheets having a thickness of 1.0 mm were produced.

For reference, the numbers representing the contents of each component in Table 1 are parts by weight.

division Example 1 Comparative Example 1 Example 2 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 3 Example 4 Example 5 SBR1502 50 50 50 50 50 50 20 IR2200 50 15 BR1208 50 15 Polymer-1 50 Polymer-2 50 Polymer-3 50 50 50 50 Polymer-4 50 Polymer-5 50 Polymer-6 50

2) When the bonding sheet is laminated Outsole sheet manufacture :

The outsole sheet obtained through the item 1) above was placed on the bottom of a mold having an internal volume of 100x200x5 mm, and the bonding sheet was laminated on the top. Then, the bonding sheet was laminated on the top and then heated and pressed at 160 DEG C for 10 minutes. Outsole.

3) Production of foamed midsole preform:

100 parts by weight of EVA (VA 21 wt.%), 1 part by weight of stearic acid, 2 parts by weight of zinc oxide, 0.9 parts by weight of a crosslinking agent DCP and 4.0 parts by weight of a blowing agent ADCA were mixed in an open mill, placed in a compression mold (CMP mold) 160 ° C / 100 kg / cm 2 ) to obtain a foamed preform having a foam expansion ratio (linear expansion coefficient) of 190% of 100x200x20 mm. The surface temperature of the foamed preform was measured by an infrared thermometer immediately after being taken out from the compression mold, Respectively.

4) Outsole - Midsole  Manufacture of integrated products:

(1) A foamed midsole preform having a surface temperature of 125 ° C was laminated on the upper side of the above (2) above while placing 1) out of 9 kinds of each of the vulcanized outsole sheets laminated with a bonding sheet of 100x200x5 mm on the bottom of a mold having a size of 100x200x 15mm The mold was sealed and pressurized and maintained at room temperature for 5 minutes. Then, the mold was demolded to obtain a finished shoe sole having a 100x200x15 mm outsole-midsole integrated therein.

The physical properties of the finished shoe sole were measured according to the following test items, and the results of physical properties test are shown in Table 2 below.

<Test items>

One) Outsole sheet and bonding Bonding strength between sheets : Prior to laminating the bonding sheet on the outsole sheet, the bonded portion between the outsole sheet and the bonding sheet was separated by a knife, and then the bonding strength was measured using an Instron Tester. For reference, when the adhesive strength is 3.0 kg / cm 2 or more, it is good, and when it is less than 3.0 kg / cm 2, it is judged to be defective.

2) Adhesion strength between the bonding sheet and the foamed midsole : The bonded portion between the bonding sheet and the foamed midsole on the foamed midsole preform laminated with the bonding sheet was separated by a knife, and the adhesive strength was measured using an Instron Tester. For reference, when the adhesive strength is 3.0 kg / cm 2 or more, it is good, and when it is less than 3.0 kg / cm 2, it is judged to be defective.

3) Heat resistance: The shoe sole with integrated outsole and midsole was cut to 20mm width. The outsole and the midsole were attached to the outsole, and the midsole was attached to the upper clip. . If there is no change in the adhesion surface after 24 hours, it is judged as good. If the adhesion surface is further widened, it is judged as defective. Also, it was indicated that the adhesive was not adhered from the beginning and not worth the experiment.

division Example 1 Comparative Example 1 Example 2 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 3 Example 4 Example 5 Bond strength between outsole sheet and bonding sheet (kg / cm 2 ) 5.0 5.0 6.0 5.5 5.5 5.5 5.0 4.5 4.5 Bond strength between bonding sheet and foamed midsole (kg / cm 2 ) 4.0 4.0 4.5 0.7 0.6 0.5 4.5 4.5 4.5 Heat resistance Good Bad Good No bonding No bonding No bonding Good Good Good

As shown in Table 2, a polymer substrate containing an ethylene copolymer and a rubber having a melting point within a range of 35 to 90 占 폚; And the vulcanizing agent according to Examples 1 to 5 using the rubber composition for sole bonding, it was confirmed that the adhesion strength between the outsole sheet and the bonding sheet, the bonding strength between the bonding sheet and the foamed midsole, and the heat resistance All the results were confirmed.

On the other hand, according to the sole prepared according to Comparative Example 1 using the rubber composition for sole bonding including an ethylene copolymer having a melting point lower than 35 캜, the bonding strength between the outsole sheet and the bonding sheet was improved, It was confirmed that the interlaminar bond strength and heat resistance were respectively poor.

<Add Experimental Example  1 to 3>

The shoe sole was manufactured by differentiating the composition of the rubber composition for bonding to produce the bonding sheet as shown in Table 3 below, and the shoe sole was manufactured through the bonding process between the outsole and the midsole without the bonding sheet, Physical properties were measured in the same manner as in Table 2 and are summarized in Table 4. For reference, the numbers indicating the contents of each component in Table 3 are parts by weight.

division Additional Experimental Example 1 Further Experimental Example 2 Further Experimental Example 3 SBR1502 10 90 - IR2200 - BR1208 - Polymer-1 - Polymer-2 - Polymer-3 90 10 - Polymer-4 - Polymer-5 - Polymer-6 - brimstone 0.2 1.8 - Accelerator M 0.1 0.9 - Stearic acid 1.0 1.0 - Zinc oxide 0.5 4.5 -

division Additional Experimental Example 1 Further Experimental Example 2 Further Experimental Example 3 Bond strength between outsole sheet and bonding sheet (kg / cm 2 ) 1.0 8.0 - Bond strength between bonding sheet and foamed midsole (kg / cm 2 ) 5.0 0.5 - Heat resistance No bonding No bonding Good

From the results of Table 4, it can be seen that the shoe sole product of the technique disclosed in this specification can be replaced with adhesive strength and heat resistance according to the composition of the bonding sheet, and even if the adhesive process between the outsole and the midsole is omitted, There is an advantage to provide.

Claims (13)

A composition for integrating an outsole and a midsole, the polymer base comprising an ethylene copolymer and a rubber having a melting point of 35 to 90 占 폚; And a vulcanizing agent, wherein the outsole and the midsole are integrated into a bridge structure. The method according to claim 1,
Wherein the ethylene copolymer is selected from the group consisting of i) ethylene, and ii) a C 3 -C 10 alpha olefin, a C 1 -C 12 alkyl ester of a C 3 -C 20 monocarboxylic acid, an unsaturated C 3 -C 20 mono or dicarboxylic acid, an unsaturated C 4 Wherein the copolymer is a copolymer of at least one ethylenically unsaturated monomer selected from the group consisting of an anhydride of -C 8 dicarboxylic acid and a vinyl ester of a saturated C 2 -C 18 carboxylic acid, or an ionomer of the copolymer. The method according to claim 1,
Wherein the rubber is at least one selected from natural rubber, isoprene rubber, butadiene rubber and styrene-butadiene rubber. The method according to claim 1,
Wherein the weight ratio of the ethylene copolymer to the rubber is from 2: 8 to 8: 2. The method according to claim 1,
The rubber is a high cis selected from at least one of i) styrene-butadiene rubber, and ii) high cis 1,4-isoprene rubber, and high cis 1,4-butadiene rubber. ) Rubber composition for sole bonding. The method according to claim 1,
Wherein the vulcanizing agent is a sulfur or sulfur mixture. The method according to claim 1,
Wherein the vulcanizing agent is 0.1 to 5.0 parts by weight based on 100 parts by weight of the polymer base material. A polymer substrate comprising an ethylene copolymer and a rubber having a melting point of 35 to 90 캜; And a vulcanizing agent, on an outsole sheet; And
The outsole sheet and the foamed midsole preform in which the bonding sheet is laminated are manufactured from a sole with an outsole and a midsole formed integrally using a sole mold, the outsole sheet having the bonding sheet laminated on the bottom of the sole mold, Placing a foamed midsole preform having a surface temperature of 120 to 150 占 폚 immediately after being taken out from the compression molding die, pressurizing the foamed preform at room temperature, and then demolding the sole. 9. The method of claim 8,
Wherein the thickness of the outsole sheet and the bonding sheet is 70:30 to 95: 5. 9. The method of claim 8,
Wherein the step of laminating the bonding sheet on an outsole sheet is performed for 10 to 20 minutes under a temperature of 150 to 160 캜. 9. The method of claim 8,
Wherein the pressing is performed for 3 to 10 minutes. A process for producing a foamed midsole preform according to any one of claims 8 to 11, characterized in that the ethylene copolymer in the bonding sheet melted by the high temperature of the surface of the foamed midsole preform forms a bridge structure between the outsole sheet and the foamed midsole Wherein the bonding strength between the bonding sheet and the foamed midsole is 4.0 to 5.0 kg / cm 2 and the bonding strength between the bonding sheet and the bonding sheet is 5.0 to 6.0 kg / cm 2 . delete
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