KR20050103616A - Adhesives of polyurethan resin - Google Patents

Adhesives of polyurethan resin Download PDF

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KR20050103616A
KR20050103616A KR1020040028861A KR20040028861A KR20050103616A KR 20050103616 A KR20050103616 A KR 20050103616A KR 1020040028861 A KR1020040028861 A KR 1020040028861A KR 20040028861 A KR20040028861 A KR 20040028861A KR 20050103616 A KR20050103616 A KR 20050103616A
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polyurethane adhesive
polyurethane
weight
rubber
present
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KR1020040028861A
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KR100577078B1 (en
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조기현
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삼우고분자 주식회사
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L33/00Arrangements for connecting hoses to rigid members; Rigid hose connectors, i.e. single members engaging both hoses
    • F16L33/28Arrangements for connecting hoses to rigid members; Rigid hose connectors, i.e. single members engaging both hoses for hoses with one end terminating in a radial flange or collar
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02GINSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
    • H02G9/00Installations of electric cables or lines in or on the ground or water
    • H02G9/06Installations of electric cables or lines in or on the ground or water in underground tubes or conduits; Tubes or conduits therefor
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02GINSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
    • H02G9/00Installations of electric cables or lines in or on the ground or water
    • H02G9/10Installations of electric cables or lines in or on the ground or water in cable chambers, e.g. in manhole or in handhole

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

본 발명은 폴리우레탄 접착물에 관한 것이다.The present invention relates to a polyurethane adhesive.

본 발명의 폴리우레탄 접착물은 폴리머 폴리올, 유기디이소시아네이트, 쇄연장제, 중합용매 및 촉매제를 사용하여 제조된 폴리우레탄 접착물에 있어서, 상기 폴리우레탄 접착물 92∼96 중량%에 염화고무 2∼8 중량%와, 에틸렌 비닐 아세테이트 수지 1∼5 중량% 및 산제 0.2∼2 중량%로 이루어진 것을 특징으로 한다.The polyurethane adhesive of the present invention is a polyurethane adhesive prepared by using a polymer polyol, an organic diisocyanate, a chain extender, a polymerization solvent and a catalyst, wherein the polyurethane adhesive is 92 to 96% by weight of rubber chloride 2 to 8 wt%, ethylene vinyl acetate resin 1-5 wt% and powder 0.2-2 wt%.

본 발명은 프라이머를 처리하지 않은 EVA 발포체에 대한 접착력이 향상된 폴리우레탄 접착제를 제공하여, 다단계 공정에서 파생되는 프라이머 처리비용과 인건비가 절감되어 신발의 제조 경쟁력을 갖게 하는 효과가 있다.The present invention provides a polyurethane adhesive with improved adhesion to an EVA foam not treated with a primer, thereby reducing the primer processing cost and labor costs derived from a multi-step process, thereby making the shoe manufacturing competitive.

Description

폴리우레탄 접착물{Adhesives of polyurethan resin}Polyurethane adhesives

본 발명은 폴리우레탄 접착물에 관한 것으로, 보다 상세하게는 프라이머를 처리하지 않은 EVA 발포체에 선처리하지 않고도 접착될 수 있는, 종래 폴리우레탄 접착물에 염화고무, 에틸렌 비닐 아세테이트 수지 및 산제로 이루어진 폴리우레탄 접착물에 관한 것이다.FIELD OF THE INVENTION The present invention relates to polyurethane adhesives, and more particularly to polyurethanes consisting of rubber chloride, ethylene vinyl acetate resin and powder to conventional polyurethane adhesives, which can be adhered to pre-treated EVA foam without pretreatment. It relates to an adhesive.

폴리우레탄 수지는 1849년 독일의 울쯔와 호프만이 최초로 이소시아네이트와 히드록시 화합물의 반응을 발표하면서 알려지게 되었으며, 오토 바이에르에 의해 1937년 상업적인 용도로 나일론과 경쟁하기 위해서 폴리에스테르계 우레탄이 공업적으로 생산되기 시작하였고, 1957년에 이르러서는 가격적인 이점뿐만 아니라 폼의 물성을 향상시킨 아주 다양한 용도의 폴리에테르계 폴리올이 생산되기에 이르렀다.Polyurethane resins became known as the first reaction of isocyanate and hydroxy compounds in 1849 by German Ulz and Hoffmann.In 1937, Otto Bayer industrially produced polyester-based urethanes to compete with nylon for commercial use. By 1957, polyether-based polyols were produced for a wide variety of applications that not only improved cost but also improved the properties of foams.

폴리우레탄의 제조방법은 폴리머 폴리올과 유기 디이소시아네이트를 반응시킨 폴리우레탄 전중합체(PU prepolymer)에 친수성기를 도입하고, 이를 이온화시켜 물에서 분산시키고, 쇄연장제를 첨가한 다음 폴리아민으로 쇄연장하여 제조하는 방법(일본 특허공개 평 5-43642호)와 폴리우레탄 전중합체를 다량의 유화제를 사용하여 강제적으로 분산시키는 방법(일본특허공고 소39-5989호)가 알려져 있다.Polyurethane production method is prepared by introducing a hydrophilic group into the polyurethane prepolymer (polymer prepolymer) reacted with a polymer polyol and organic diisocyanate, ionized it to disperse in water, add chain extender and then chain extend with polyamine (Japanese Patent Application Laid-Open No. 5-43642) and a method of forcibly dispersing a polyurethane prepolymer using a large amount of emulsifier (Japanese Patent Publication No. 39-5989) are known.

일반적으로 상기 폴리머 폴리올에는 폴리에스테르 폴리올, 폴리카보네이트 폴리올 및 폴리에테르 폴리올 등이 사용되며, 유기 디이소시아네이트는 헥사메틸렌 디이소시아네이트, 이소포론 디이소시아네이트, 4,4'-디사이클로헥실메탄 디이소시아네이트, 2,4-톨릴렌 디이소시아네이트, 2,6-톨릴렌 디이소시아네이트, 4,4'-디페닐메탄 디이소시아네이트, p-페닐렌 디이소시아네이트, 크실릴렌 디이소시아네이트 및 1,5-나프틸렌 디이소시아네이트 등이 사용된다.Generally, the polymer polyol may be polyester polyol, polycarbonate polyol, polyether polyol, and the like, and organic diisocyanate may be hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate and the like Used.

또한, 쇄연장제로는 디올, 트리올, 펜타올, 디아민 및 아미노 알콜을 사용하며, 유기용매는 케톤류, 에테르류, 에스테르류 및 방향족 탄화수소를 사용한다.In addition, diols, triols, pentaols, diamines and amino alcohols are used as chain extenders, and organic solvents include ketones, ethers, esters and aromatic hydrocarbons.

그 밖에 촉매제로 유기 주석 화합물, 유기 티탄 화합물 및 3급 아민을 사용하는 것으로 알려져 있다.In addition, it is known to use an organic tin compound, an organic titanium compound, and a tertiary amine as a catalyst.

현재, 폴리우레탄은 기간 산업의 필수 불가결한 고분자 재료로써 건물 단열재로부터 시작하여 자동차, 일반 기계, 선박, 가구, 신발, 의류 등의 넓은 제품 영역을 이루고 있으며 접착제, 코팅,장, 엔지니어링 플라스틱 등의 형태로 산업분야에서 널리 사용되고 있다. Currently, polyurethane is an indispensable polymer material for the core industry, starting from building insulation and forming a wide range of products such as automobiles, general machinery, ships, furniture, shoes, and clothing, and in the form of adhesives, coatings, sheets, engineering plastics, etc. It is widely used in the industrial field.

그러나, 신발에 사용되는 에틸렌 비닐 아세테이트 발포체(이하 EVA 발포체)의 경우, 폴리우레탄 접착제와의 접착력이 매우 낮아서 신발제조 공정에서 겉창으로 사용하는 고무 또는 피혁 등과의 접착을 위해서는, 발포체의 표면에 접착력을 향상시켜주기 위한 프라이머를 먼저 처리한 후 수성 혹은 유성의 접착제를 사용하여 접착해야 하는 문제점이 있었다.However, in the case of ethylene vinyl acetate foam (hereinafter referred to as EVA foam) used in shoes, the adhesive strength with the polyurethane adhesive is very low, so that the adhesive force is applied to the surface of the foam for adhesion with rubber or leather used as outsole in the shoe manufacturing process. There was a problem that the first to treat the primer to improve and then adhere using an aqueous or oily adhesive.

이를 도 1에 간략하게 나타내었다. This is briefly shown in FIG.

도 1에 도시된 바와 같이, EVA 수지와 형광안료 및 톨루엔, DMF, MEK 등으로 이루어진 선처리제로 EVA 발포체의 피접착면에 프라이머를 도포하고, 열 건조실에서 건조시키는 A 공정과, 상기 건조된 프라이머에 선처리제를 적층되게 도포하고 열 건조실에 건조시키는 B 공정과, 상기 적층되어 건조된 프라이머에 폴리우레탄 접착제를 도포하는 C 공정 및 상기 폴리우레탄이 도포된 EVA 발포체를 압착하여 접착시키는 D 공정으로 이루어져 있다.As shown in FIG. 1, the primer A is applied to the adhered surface of the EVA foam with a pretreatment agent composed of an EVA resin, a fluorescent pigment, and toluene, DMF, MEK, and the like, and dried in a thermal drying chamber, and to the dried primer. It consists of the process B which apply | coats a pretreatment agent to be laminated | stacked, and dries in a thermal drying chamber, the process C which apply | coats a polyurethane adhesive to the said laminated and dried primer, and the D process which crimps | bonds and adheres the said polyurethane foam coated EVA foam .

이와같은 다단계 공정은 여건상 프라이머 처리비용과 많은 인건비가 요구되어 신발의 제조원가를 상승시키는 문제점이 있었다.Such a multi-step process has a problem in that the cost of the primer treatment and a lot of labor costs are required to increase the manufacturing cost of the shoe.

상기와 같은 문제점을 해결하기 위하여, 본 발명자는 프라이머를 처리하지 않은 EVA 발포체에 대한 접착력이 향상된 폴리우레탄 접착제를 개발하여, EVA 발포체 접착에 대한 다단계 공정을 단순화하고, 인건비를 절감하고자 하였다.In order to solve the above problems, the present inventors have developed a polyurethane adhesive with improved adhesion to the EVA foam not treated with a primer, to simplify the multi-step process for EVA foam adhesion, and to reduce labor costs.

보다 구체적으로는 신발 중창용으로 사용하는 EVA 발포체과 겉창용으로 사용하는 고무 또는 피혁 등을 간편하게 접착할 수 있는 폴리우레탄 접착물을 개발하는 것이다. More specifically, it is to develop a polyurethane adhesive that can easily adhere to the EVA foam used for the shoe midsole and the rubber or leather used for the outsole.

이에, 본 발명의 목적은 종래 폴리우레탄 접착물에 염화고무, 에틸렌 비닐 아세테이트 수지 및 산제로 이루어진 폴리우레탄 접착물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a polyurethane adhesive consisting of rubber chloride, ethylene vinyl acetate resin and powder to a conventional polyurethane adhesive.

상기와 같은 목적을 달성하기 위하여, 본 발명은 폴리머 폴리올, 유기디이소시아네이트, 쇄연장제, 중합용매 및 촉매제를 사용하여 제조된 폴리우레탄 접착물에 있어서, 상기 폴리우레탄 접착물 92∼96 중량%에 염화고무 2∼8 중량%와, 에틸렌 비닐 아세테이트 수지 1∼5 중량% 및 산제 0.2∼2 중량%로 이루어진 폴리우레탄 접착물을 제공한다.In order to achieve the above object, the present invention is a polyurethane adhesive prepared by using a polymer polyol, an organic diisocyanate, a chain extender, a polymerization solvent and a catalyst, in the polyurethane adhesive 92 to 96% by weight A polyurethane adhesive comprising 2 to 8% by weight of rubber chloride, 1 to 5% by weight of ethylene vinyl acetate resin and 0.2 to 2% by weight of powder is provided.

또한, 염화고무는 염소화된 부틸고무, 폴리에틸렌 고무 또는 폴리프로필렌 고무인 것을 특징으로 한다.In addition, the chlorinated rubber is characterized in that the chlorinated butyl rubber, polyethylene rubber or polypropylene rubber.

아울러, 산제는 카르복실산, 술폰산 또는 인산인 것을 특징으로 한다.     In addition, the powder is characterized in that the carboxylic acid, sulfonic acid or phosphoric acid.

이하, 본 발명을 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.

본 발명에서 상기 염화고무는 무색, 무취, 내산성, 내알카리성, 난연성이 우수한 고무수지로서, 유연성 및 용융 유동성이 풍부하고 다른 수지와의 혼합이 용이하여 본 발명에서는 반경질 또는 연질염화비닐용의 비이동성 가소제의 용도로 전체 중량 기준으로 2∼8 중량%이 사용된다.The rubber chloride in the present invention is a rubber resin excellent in colorless, odorless, acid resistance, alkali resistance, flame retardancy, rich in flexibility and melt flowability and easy to mix with other resins in the present invention, the ratio for semi-rigid or soft vinyl chloride 2-8% by weight, based on the total weight, of mobile plasticizers is used.

이는, 염화고무가 8 중량% 이상이 되면 첨가량에 비해 가소제의 효과가 저감되고, 2 중량% 이하로 사용하면 가소제로서의 효과가 미미하기 때문이다.This is because when the amount of rubber chloride is 8% by weight or more, the effect of the plasticizer is reduced compared to the amount added, and when used at 2% by weight or less, the effect as a plasticizer is insignificant.

본 발명에서는 상기 염화고무로 염소화된 부틸고무, 폴리에틸렌 고무 또는 폴리프로필렌 고무를 사용한다.In the present invention, butyl rubber, polyethylene rubber or polypropylene rubber chlorinated with the above chlorinated rubber is used.

그리고, 상기 에틸렌 비닐 아세테이트(EVA)는 동종 피착재(EVA 발포체)와의 접착을 보다 용이하게 하고자 사용하는 데, 유기용제를 사용하여 겔화된 것을 사용하는 것이 바람직하다.In addition, the ethylene vinyl acetate (EVA) is used to facilitate adhesion with the same type of adherend (EVA foam), it is preferable to use a gelled using an organic solvent.

본 발명에서는 에틸렌 비닐 아세테이트 수지를 전체 중량기준으로 1∼5 중량%이 사용된다.In the present invention, 1 to 5% by weight of ethylene vinyl acetate resin is used based on the total weight.

이는, 에틸렌 비닐 아세테이트를 전체 중량을 기준으로 5 중량% 이상이 되면, 전체적으로 폴리우레탄 특성의 접착력이 저하되고, 1 중량% 이하가 되면 사용 효과가 미미하게 된다.When the ethylene vinyl acetate is 5% by weight or more based on the total weight, the adhesive force of the polyurethane properties as a whole is lowered, and when it is 1% by weight or less, the use effect is insignificant.

이때, 상기 유기용제는 톨루엔, 벤젠, 크실렌, 메틸에틸케톤, 이소부틸메틸케톤, 에틸아세테이트, 부틸아세테이트, n-펜탄, n-헥산, 시클로헥산, 메틸시클로헥산, 디클로로메탄 및 트리클로로에틸렌 중에서 선택된 1종 혹은 2종 이상의 용제를 사용한다.In this case, the organic solvent is selected from toluene, benzene, xylene, methyl ethyl ketone, isobutyl methyl ketone, ethyl acetate, butyl acetate, n-pentane, n-hexane, cyclohexane, methylcyclohexane, dichloromethane and trichloroethylene Use one or two or more solvents.

또한, 산제(Acid)는 폴리우레탄 접착물의 폴리머 입자의 표면에 이온성기를 존재하게 하여, 전기적인 상호 인력에 의해 분자입자를 안정화시키고, 접착력 및 유연성에 영향을 주는 데, 카르복실산, 술폰산 또는 인산계 산제를 사용하는 것이 바람직하고, 전체 중량 대비 0.2∼2 중량%가 되게 사용한다.In addition, the acid makes ionic groups exist on the surface of the polymer particles of the polyurethane adhesive, thereby stabilizing the molecular particles by electrical mutual attraction and affecting adhesion and flexibility, such as carboxylic acid, sulfonic acid or It is preferable to use a phosphate powder, and it is used so that it may become 0.2 to 2 weight% with respect to the total weight.

이는 종래 폴리우레탄 제조과정에서 이미 산제가 이오노머(ionomer)로 충분히 사용되어져서, 2 중량% 이상이면 점도가 증가되어 작업성이 저감되고, 0.2중량% 이하가 되면 그 효과가 미미하기 때문이다.This is because the powder is already sufficiently used as an ionomer in the conventional polyurethane manufacturing process, and the viscosity is increased if it is 2% by weight or more, and the workability is reduced, and the effect is insignificant when it is 0.2% by weight or less.

이하, 본 발명을 실시예에 의거하여 보다 상세히 설명하고자 한다. Hereinafter, the present invention will be described in more detail with reference to Examples.

단, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.However, this invention is not limited by the following Example.

[실시예]EXAMPLE

1,4-부탄디올(1,4-BG 1420) 178g과 에틸렌글리콜(EG 1220) 20g, 헥사메틸렌 디이소시아네이트(HMDI) 18g, 톨루엔 817g, 메틸에틸케톤(MEK) 408g, 2-하이드록시에틸메타크릴레이트(2-HEMA) 59g을 배합비로 하고, 통상의 폴리우레탄 제조 공정을 수행하여, 본 발명에 사용할 폴리우레탄 접착제를 준비하였다.178 g of 1,4-butanediol (1,4-BG 1420) and 20 g of ethylene glycol (EG 1220), 18 g of hexamethylene diisocyanate (HMDI), 817 g of toluene, 408 g of methyl ethyl ketone (MEK), 2-hydroxyethyl methacryl A polyurethane adhesive for use in the present invention was prepared by carrying out a conventional polyurethane production process with 59 g of rate (2-HEMA) as a compounding ratio.

이때, 상기 폴리우레탄 접착제의 기본적인 물성은 점도(25℃ 기준)가 4,500±200 cps이였고, 전체 중량 기준으로 고형분은 19±0.5%였다.At this time, the basic physical properties of the polyurethane adhesive was a viscosity (based on 25 ℃) was 4,500 ± 200 cps, the solid content was 19 ± 0.5% based on the total weight.

그리고, 상기 폴리우레탄 접착제 282g에 염화고무 10.5g, EVA(Nodilled poly , 톨루엔) 6g, 아세트산 1.5g을 균일하게 혼합하고 24시간동안 방치숙성하여 반응을 시켜 본 발명의 폴리우레탄 접착물을 완성하였다.Then, 10.5 g of rubber chloride, 6 g of EVA (Nodilled poly, toluene), and 1.5 g of acetic acid were uniformly mixed with the polyurethane adhesive 282 g, and left to mature for 24 hours to complete the polyurethane adhesive of the present invention.

[실험예]Experimental Example

본 실험은 본 발명에 따른 폴리우레탄 수지가 EVA 발포체에 프라이머 공정을 거치지 않고 접착되는 지의 여부를 확인하고자 수행하였다.This experiment was performed to determine whether the polyurethane resin according to the present invention is bonded to the EVA foam without going through a primer process.

1. 접착시편 제조1. Preparation of Adhesive Specimen

본 실험에 사용되는 피착재는 EVA 스폰지를 연마하고 톨루엔으로 세척한 다음 시편으로 사용하였다.The adherend used in this experiment was used as a specimen after polishing the EVA sponge, washed with toluene.

2. 접착2. Adhesion

상기 준비된 EVA 시편(비중 0.15∼0.3) 위에 상기 실시예의 폴리우레탄 수지를 도포하고 프레스로 압착하고 3분동안 건조한 다음, 5분 경과후의 초기 접착력과 24시간 경과후의 접착력에 대한 물성을 측정하였다.The polyurethane resin of the above example was applied onto the prepared EVA specimens (specific gravity 0.15 to 0.3), pressed in a press, dried for 3 minutes, and then measured for physical properties for initial adhesion after 5 minutes and after 24 hours.

이때, 건조는 60℃로 유지되는 열 건조실에서 건조하였다.At this time, the drying was dried in a thermal drying chamber maintained at 60 ℃.

구분division 실시예Example 물성(㎏f/㎝)Physical property (kgf / cm) 초기 접착력(5분)Initial adhesion (5 minutes) 4.9 (재질 파괘)4.9 (Material Patua) 후기 접착력(24시간)Late adhesion (24 hours) 5.0 이상 (재질 파괘)     5.0 or more (material Patua)

일반적으로 EVA 발포체에 프라이머를 처리한 다음 폴리우레탄 수지를 접착하였을 경우에는 접착력이 초기에는 2.0∼3.0 ㎏f/㎝이고, 후기에는 3.0∼4.0 ㎏f/㎝정도이기 때문에, 본 발명의 접착력이 우수함을 알 수 있었다.In general, when the polyurethane resin is bonded to the EVA foam after the primer is treated, the adhesive strength is initially 2.0 to 3.0 kgf / cm, and later is about 3.0 to 4.0 kgf / cm, and thus the adhesive strength of the present invention is excellent. And it was found.

따라서, EVA 발포체의 프라이머 공정에서 1㎏당 3 달러(US)가 소요되는 선처리제를 사용하지 않아 신발 30만족을 생산시 월 27,000달러를 절감할 수 있게 된다.Therefore, when using a pre-processing agent that takes $ 3 per kg (US) in the primer process of the EVA foam, it is possible to save $ 27,000 per month when producing 300,000 shoes.

또한, 종래 4단계 이상의 다단계 공정을 단 2공정으로 해결할 수 있으므로, 신발제조 특성상 수작업으로 인한 인건비 지출을 절약할 수 있게 된다.In addition, the conventional four-step multi-step process can be solved in just two steps, it is possible to save labor costs due to manual labor due to the shoe manufacturing characteristics.

이상과 같이, 본 발명은 프라이머를 처리하지 않은 EVA 발포체에 대한 접착력이 향상된 폴리우레탄 접착제를 제공하여, 다단계 공정에서 파생되는 프라이머 처리비용과 인건비가 절감되어 신발의 제조 경쟁력을 갖게 하는 효과가 있다.As described above, the present invention provides a polyurethane adhesive having improved adhesion to the EVA foam not treated with a primer, thereby reducing the primer processing cost and labor costs derived from the multi-step process, thereby making the shoe manufacturing competitive.

도 1은 종래 EVA 발포체에 프라이머를 도포시킨 다음, 폴리우레탄 접착제를 도포하여 다른 피착재와 접착시키는 공정을 간략하게 나타낸 공정도1 is a process diagram briefly illustrating a process of applying a primer to a conventional EVA foam, and then applying a polyurethane adhesive to bond with another adherend.

도 2는 본 발명의 실시예에 따른 공정을 간략하게 나타낸 공정도2 is a process diagram briefly showing a process according to an embodiment of the present invention.

Claims (3)

폴리머 폴리올, 유기디이소시아네이트, 쇄연장제, 중합용매 및 촉매제를 사용하여 제조된 폴리우레탄 접착물에 있어서,Polyurethane adhesives prepared using polymer polyols, organic diisocyanates, chain extenders, polymerization solvents and catalysts, 상기 폴리우레탄 접착물 92∼96 중량%에92-96% by weight of the polyurethane adhesive 염화고무 2∼8 중량%와, 2 to 8% by weight of rubber chloride, 에틸렌 비닐 아세테이트 수지 1∼5 중량% 및 1-5% by weight of ethylene vinyl acetate resin and 산제 0.2∼2 중량%로 이루어진 것을 특징으로 하는 폴리우레탄 접착물.A polyurethane adhesive comprising 0.2 to 2% by weight of powder. 제 1 항에 있어서,The method of claim 1, 상기 염화고무는 염소화된 부틸고무, 폴리에틸렌 고무 또는 폴리프로필렌 고무인 것을 특징으로 하는 폴리우레탄 접착물.The polyurethane chloride is a polyurethane adhesive, characterized in that the chlorinated butyl rubber, polyethylene rubber or polypropylene rubber. 제 1 항에 있어서,The method of claim 1, 상기 산제는 카르복실산, 술폰산 또는 인산인 것을 특징으로 하는 폴리우레탄 접착물.The powder is a polyurethane adhesive, characterized in that the carboxylic acid, sulfonic acid or phosphoric acid.
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KR102067263B1 (en) * 2018-12-28 2020-01-17 주식회사 그린폴리머 Adhesive film for eco-adhesive body
WO2020048040A1 (en) * 2018-09-03 2020-03-12 万华化学集团股份有限公司 Aqueous polyurethane-polyvinyl acetate resin, preparation method therefor and use thereof

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CN103215003B (en) * 2013-04-19 2014-12-10 厦门朝富人造革有限公司 Thermoplastic polyurethane foaming resin mucilage glue as well as preparation method and use thereof, and product
KR20230055657A (en) 2021-10-19 2023-04-26 한국신발피혁연구원 Composition of adhesive for shoes with excellent durability and adhesion

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DE4222530A1 (en) * 1992-07-09 1994-01-13 Hoechst Ag Polyurethane dispersions

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WO2020048040A1 (en) * 2018-09-03 2020-03-12 万华化学集团股份有限公司 Aqueous polyurethane-polyvinyl acetate resin, preparation method therefor and use thereof
KR102067263B1 (en) * 2018-12-28 2020-01-17 주식회사 그린폴리머 Adhesive film for eco-adhesive body

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