KR101181842B1 - Polyurethane adhesive composition for low polarity shoes material - Google Patents
Polyurethane adhesive composition for low polarity shoes material Download PDFInfo
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- KR101181842B1 KR101181842B1 KR1020100088489A KR20100088489A KR101181842B1 KR 101181842 B1 KR101181842 B1 KR 101181842B1 KR 1020100088489 A KR1020100088489 A KR 1020100088489A KR 20100088489 A KR20100088489 A KR 20100088489A KR 101181842 B1 KR101181842 B1 KR 101181842B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43C—FASTENINGS OR ATTACHMENTS OF FOOTWEAR; LACES IN GENERAL
- A43C19/00—Attachments for footwear, not provided for in other groups of this subclass
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
본 발명은 EVA 발포체 등과 같은 저극성 신발 소재의 접착력을 향상시킨 것을 특징으로 하는 저극성 신발 소재용 폴리우레탄 접착제 조성물에 관한 것으로, EVA 발포체 등과 같은 저극성 소재의 신발용 부품에 대한 초기 접착력, 후기 접착력, 초기 내열 및 후기 내열이 양호하며, 기 사용되는 반응형 폴리우레탄 접착제에 비해 향상된 접착제를 제공하여, 접착 불량률 감소 및 이를 통한 제조 원가 절감에 이바지하여 신발 제조 경쟁력 향상에 효과가 있을 것으로 기대된다. The present invention relates to a polyurethane adhesive composition for low-polar shoe material, characterized in that it improves the adhesion of low-polar shoe material, such as EVA foam, and the like, the initial adhesion to the low-polar material, such as EVA foam Adhesion, initial heat resistance and late heat resistance are good, and it is expected to be effective in improving shoe manufacturing competitiveness by reducing adhesive failure rate and reducing manufacturing cost by providing improved adhesives compared to the reactive polyurethane adhesives used. .
Description
본 발명은 저극성 신발 소재용 폴리우레탄 접착제 조성물에 관한 것으로, 더욱 상세하게는 EVA 발포체 등과 같은 저극성 신발 소재의 접착력을 향상시킨 것을 특징으로 하는 저극성 신발 소재용 폴리우레탄 접착제 조성물에 관한 것이다.
The present invention relates to a polyurethane adhesive composition for low-polar shoe material, and more particularly to a polyurethane adhesive composition for low-polar shoe material, characterized in that the adhesion of the low-polar shoe material, such as EVA foam.
최근 신발산업은 사람들의 건강에 대한 관심고조로 인한 걷기 열풍에 의해 다양한 종류의 기능성 신발들이 개발되고 있다. 이러한 기능성 신발들은 다양한 디자인의 개발은 물론이고, 특히 신발의 기능성이 중요시되어 에틸렌초산비닐공중합체(EVA) 소재와 같은 초경량을 요구하는 저극성 소재들이 주로 사용되고 있다.
Recently, the footwear industry has been developing various types of functional shoes due to the walking craze due to increased interest in people's health. These functional shoes, as well as the development of a variety of designs, in particular, the functionality of the shoes is important, low-polar materials that require ultra-light weight, such as ethylene vinyl acetate copolymer (EVA) material is mainly used.
상기와 같은 저극성 소재들은 폴리우레탄 접착제를 사용하면 접착력이 매우 낮아서 접착력을 향상시키기 위해 접착공정 전에 반드시 전처리 공정으로 발포체의 표면에 프라이머 처리를 하든지 또는 표면을 개질 시키는 방법 등을 사용하고 있지만 접착력이 지속적으로 유지되지 아니하고, 장시간이 경과되면 접착 성능이 떨어지는 문제점이 있었다.
The low-polar materials as described above are very low in adhesive strength when using a polyurethane adhesive, so in order to improve the adhesive strength, a pretreatment process is required to prime the surface of the foam or to modify the surface. Not continuously maintained, there was a problem that the adhesive performance is lowered after a long time.
상기와 같은 문제점들을 해결하기 위한 방안으로 저극성 소재에 적합한 폴리우레탄 접착제들이 다양하게 연구 개발되고 있으며, 이러한 기술들의 특허들을 살펴보면, In order to solve the above problems, various polyurethane adhesives suitable for low polar materials have been researched and developed. Looking at the patents of these technologies,
국내 공개특허공보 제1993-3243호에 (a) 수소첨가시킨 폴리부타디엔 글리콜과, 분자중에 2개 이상의 수산기를 갖는 폴리올, 및 폴리이소시아네이트를 반응시켜서 제조된 블록 폴리우레탄 폴리올, (b) 열가소성 폴리에스테르 우레탄 고무 및 (c) 가교제로서 폴리이소시아네이트 화합물로 이루어진 것을 특징으로 하는 폴리우레탄 접착제가 알려져 있지만 상기와 같은 특허의 경우에는 (a)의 프리폴리머를 제조하기위해서는 방향족 용제를 사용해야한다는 문제점을 가지고 있으며, 또한 제조상 복잡한 공정을 거쳐 생산하여야하며 이로 인한 제조 원가의 상승으로, 저가의 접착제를 요구하는 신발용 접착제로서는 문제점이 있으며, 또한 국내 등록특허공보 제577078호에 폴리머 폴리올, 유기디이소시아네이트, 쇄 연장제, 중합용매 및 촉매제를 사용하여 제조된 폴리우레탄 접착물에 있어서, 상기 폴리우레탄 접착물 92~96 중량%에 염화고무 2~8 중량%와, 에틸렌비닐아세테이트 수지 1~5 중량% 및 산제 0.2~2 중량%로 이루어진 것을 특징으로 하는 폴리우레탄 접착제가 알려져 있지만 상기와 같은 특허의 경우에는 분산된 염화고무의 영향으로 장시간 일광에 노출되었을 경우 변색의 문제점이 있으며 또한 염화고무의 용해를 위하여 방향족 용제를 사용해야 한다는 문제점을 가지고 있다. Block Polyurethane Polyol prepared by reacting (a) hydrogenated polybutadiene glycol with a polyol having two or more hydroxyl groups in a molecule, and polyisocyanate, and (b) thermoplastic polyester Polyurethane adhesives are known which consist of polyisocyanate compounds as urethane rubbers and (c) crosslinking agents. However, in the case of the above patents, there is a problem that an aromatic solvent must be used to prepare the prepolymer of (a). Due to the complicated manufacturing process, the production cost is increased, and as a result, there is a problem as an adhesive for shoes requiring a low-cost adhesive, and also in Korea Patent Publication No. 570078, a polymer polyol, an organic diisocyanate, a chain extender, Prepared using a polymerization solvent and a catalyst Polyurethane adhesive, characterized in that consisting of 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 in the polyurethane adhesive 92-96% by weight Urethane adhesives are known, but in the case of the above patent, there is a problem of discoloration when exposed to sunlight for a long time under the influence of dispersed rubber chloride, and also has the problem of using an aromatic solvent to dissolve the rubber chloride.
그리고 국내 공개특허공보 제2009-77006호에 극성 물질을 포함하는 제 1 성분 및 비극성 폴리올레핀(np-PO)과 폴리디엔-기재의 폴리우레탄 또는 폴리디올-기재의 폴리우레탄의 블렌드를 포함하는 제 2 성분을 포함하는 폴리우레탄 브렌드 조성물가 알려져 있지만 상기와 같은 특허의 경우에는 신발용 접착제가 요구하는 조건 중 가장 중요한 접착성 및 내열성 중 특히 내열성이 약한 문제가 있어 신발제조상의 문제점이 있으며, 또한 국내 등록특허공보 제297074호에 에틸렌기와 부틸렌기의 몰비가 30/70~ 70/30인 수산기 함유 폴리(에틸렌-부틸렌) 공중합체를 1~50몰% 함유하는 활성 수소기함유 화합물과 유기 디이소시아네이트를 반응시켜 수득한 폴리우레탄 접착제가 알려져 있지만 상기와 같은 특허의 경우에는 건조 조건이 통상 80℃이상에서 건조되어야만 안정한 접착력을 발현하므로, 통상 신발 공장의 건조 조건은 50~60℃이므로 신발용 접착제로서 적용하기는 문제점이 있다.
And in Korean Laid-Open Patent Publication No. 2009-77006, a second component comprising a blend of a first component comprising a polar material and a nonpolar polyolefin (np-PO) and a polydiene-based polyurethane or a polydiol-based polyurethane. Polyurethane blend composition containing the components are known, but in the case of the above patents, the most important of the conditions required for the adhesive for shoes, there is a problem in the shoe manufacturing, especially the weak heat resistance problem, and also registered in Korea Patent No. 297074 discloses an active hydrogen group-containing compound and an organic diisocyanate containing 1 to 50 mol% of a hydroxyl-containing poly (ethylene-butylene) copolymer having a molar ratio of ethylene and butylene groups of 30/70 to 70/30. Polyurethane adhesives obtained by the reaction are known, but in the case of the above patent, the drying conditions are usually stable only when dried at 80 ° C or higher. Since it exhibits an adhesive force, the drying conditions of a shoe factory is usually 50 ~ 60 ℃, there is a problem to apply as an adhesive for shoes.
따라서, 본 발명은 상기와 같은 문제점들을 해결하기 위한 방안으로 분자량이 다른 2가지 폴리올 및 폴리 부타디엔 폴리올의 적절한 배합과 2 종류의 쇄연장제를 사용하여 방향족 용제를 사용하지 않고 폴리우레탄을 제조하고, 특히 EVA 발포체 등과 같은 저극성 소재에 대한 접착력을 향상시킨 것을 특징으로 하는 저극성 신발 소재용 폴리우레탄 접착제 조성물을 제공함을 과제로 한다.
Therefore, the present invention is to solve the problems as described above to prepare a polyurethane without using an aromatic solvent using a suitable blend of two polyols and polybutadiene polyols having different molecular weight and two types of chain extender, In particular, it is an object of the present invention to provide a polyurethane adhesive composition for a low polar shoe material, which is characterized by improved adhesion to a low polar material such as an EVA foam.
상기의 과제를 달성하기 위한 본 발명은 폴리올과 유기 디이소시아네이트를 용제로 용해시키고, 쇄 연장제 및 촉매제를 첨가하여 합성한 폴리우레탄 접착제 조성물에 있어서, 상기 폴리올은 폴리에스테르 폴리올과 폴리부타디엔 폴리올의 혼합 폴리올인 것을 특징으로 하는 폴리우레탄 수지 접착제 조성물을 과제 해결 수단으로 한다.
The present invention for achieving the above object is a polyurethane adhesive composition synthesized by dissolving a polyol and organic diisocyanate with a solvent and adding a chain extender and a catalyst, wherein the polyol is a mixture of polyester polyol and polybutadiene polyol The polyurethane resin adhesive composition characterized by the polyol is a problem solving means.
그리고 상기 혼합 폴리올은 수평균 분자량이 2,000~3,000인 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000~5,000인 폴리에스테르 폴리올 50~70 중량부(b), 수평균 분자량이 2,000~3,000인 폴리부타디엔 폴리올(c) 10~20 중량부이고, And the mixed polyol is 100 parts by weight of polyester polyol (a) having a number average molecular weight of 2,000 to 3,000, 50 to 70 parts by weight (b) of polyester polyol having a number average molecular weight of 4,000 to 5,000 (b), number average molecular weight of 2,000 to 3,000 Phosphorus polybutadiene polyol (c) is 10 to 20 parts by weight,
상기 폴리에스테르 폴리올(a), (b)는 1,4-부탄디올과 아디핀산을 반응시킨 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올이며, The polyester polyols (a) and (b) are polyester polyols of 1,4-butanediol / adipic acid obtained by reacting 1,4-butanediol and adipic acid,
상기 쇄 연장제는 폴리에스테르 폴리올(a) 100 중량부에 대하여, 1.0~1.5 중량부이고, The chain extender is 1.0 to 1.5 parts by weight based on 100 parts by weight of the polyester polyol (a),
상기 유기 디이소시아네이트는 폴리에스테르 폴리올(a) 100 중량부에 대하여 13~15 중량부이며, The organic diisocyanate is 13 to 15 parts by weight based on 100 parts by weight of the polyester polyol (a),
상기 용제는 폴리우레탄 수지 접착제 조성물에 대하여 중량비로 60/40~20/80(용제/폴리우레탄 수지 접착제 조성물)인 것이 바람직하다.
It is preferable that the said solvent is 60 / 40-20 / 80 (solvent / polyurethane resin adhesive composition) with respect to a polyurethane resin adhesive composition by weight ratio.
본 발명은 EVA 발포체 등과 같은 저극성 소재의 신발용 부품에 대한 초기 접착력, 후기 접착력, 초기 내열 및 후기 내열이 양호하며, 기 사용되는 반응형 폴리우레탄 접착제에 비해 향상된 접착제를 제공하여, 접착 불량률 감소 및 이를 통한 제조 원가 절감에 이바지하여 신발 제조 경쟁력 향상에 효과가 있다.
The present invention has good initial adhesive strength, late adhesive strength, early heat resistance and late heat resistance to shoe parts of low polar materials such as EVA foam, and provides improved adhesives compared to the reactive polyurethane adhesives used, thereby reducing adhesion failure rates. And by contributing to the reduction of manufacturing costs through this is effective in improving the shoe manufacturing competitiveness.
상기의 효과를 달성하기 위한 본 발명은 저극성 신발 소재용 폴리우레탄 접착제 조성물에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.
The present invention for achieving the above effect relates to a polyurethane adhesive composition for low-polar shoes material, and only the parts necessary for understanding the technical configuration of the present invention will be described, the description of other parts will not distract from the gist of the present invention. Note that this will be omitted.
이하 본 발명에 따른 저극성 신발 소재용 폴리우레탄 접착제 조성물을 상세히 설명하면 다음과 같다.
Hereinafter, a polyurethane adhesive composition for a low polar shoe material according to the present invention will be described in detail.
본 발명은 폴리올과 유기 디이소시아네이트를 용제로 용해시키고, 쇄 연장제 및 촉매제를 첨가하여 합성한 폴리우레탄 접착제 조성물에 있어서, In the polyurethane adhesive composition synthesized by dissolving a polyol and an organic diisocyanate with a solvent and adding a chain extender and a catalyst,
상기 폴리올은 폴리에스테르 폴리올과 폴리부타디엔 폴리올의 혼합 폴리올이고, The polyol is a mixed polyol of a polyester polyol and a polybutadiene polyol,
상기 디올은 1,4 부탄디올과 1.6 헥산 디올의 혼합 디올인 것을 특징으로 하는 폴리우레탄 수지 접착제 조성물에 관한 것이다.
The diol is a polyurethane resin adhesive composition, characterized in that the mixed diol of 1,4 butanediol and 1.6 hexane diol.
본 발명은 유기 디이소시아네이트와 폴리 올레핀기(폴리부타디엔)를 포함한 2관능성 이하의 폴리올과 당 업계에서 주로 사용하는 폴리에스테르폴리올의 혼합 폴리올인 것이 특징이다.
The present invention is characterized in that it is a mixed polyol of a polyfunctional or less than bifunctional polyol containing an organic diisocyanate and a polyolefin group (polybutadiene) and a polyester polyol mainly used in the art.
이하, 본 발명에 따른 폴리우레탄 수지 접착제 조성물을 합성하기 위한 폴리우레탄 프리 폴리머의 구성성분을 상세히 설명하고자 한다.
Hereinafter, the components of the polyurethane prepolymer for synthesizing the polyurethane resin adhesive composition according to the present invention will be described in detail.
본 발명에서 사용하는 혼합 폴리올은 수평균 분자량이 2,000~3,000인 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000~5,000인 폴리에스테르 폴리올(b) 50~70 중량부, 수평균 분자량이 2,000~3,000인 폴리부타디엔 폴리올(c) 10~20 중량부인 것이 바람직하다.
The mixed polyols used in the present invention are 100 parts by weight of a polyester polyol (a) having a number average molecular weight of 2,000 to 3,000, 50 to 70 parts by weight of a polyester polyol (b) having a number average molecular weight of 4,000 to 5,000, and a number average molecular weight of It is preferable that it is 10-20 weight part of polybutadiene polyols (c) which are 2,000-3,000.
본 발명에서 상기 폴리에스테르 폴리올(a), (b)는 접착성, 내열성 내구성이 양호한 폴리에스테르 폴리올이며, 폴리에스테르 폴리올의 구체적인 예로서는 에틸렌 글리콜(이하, EG로 약칭함), 디에틸렌 글리콜,디프로필렌 글리콜, 1,2-프로판디올, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 1,4-부탄디올, 네오펜틸 글리콜(이하, NPG로 약칭함), 1,2-펜탄디올, 1,3-펜탄디올, 1,4-펜탄디올, 1,5-펜탄디올, 2-메틸-1.5-펜탄디올, 3-메틸-1,5-펜탄디올, 1,6-헥산디올, 2,2,4-트리메틸-1,3-프로판디올, 2-에틸-1,3-헥산디올, 2,2-디에틸-1,3-프로판디올, 2-n-부틸-2-에틸-1,3-프로판디올, 비스페놀 A의 에틸렌 옥사이드 부가물, 비스페놀 A의 프로필렌 옥사이드 부가물 등의 소위 저분자 글리콜류 및 이들의 혼합물과 숙신산, 아디핀산, 세바스산, 아젤라산, 프탈산, 이소프탈산, 테레프탈산, 푸마르산, 말레산, 옥살산, 나프틸렌디카복실산 등의 디카복실, 이들의 산 에스테르, 산 무수물의 탈수축합반응으로 수득한, 양 말단 수산기를 갖는 폴리에스테르인 것이 바람직하다.
In the present invention, the polyester polyols (a) and (b) are polyester polyols having good adhesion and heat resistance durability. Specific examples of the polyester polyols include ethylene glycol (hereinafter, abbreviated as EG), diethylene glycol, and dipropylene. Glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol (hereinafter abbreviated as NPG), 1,2- Pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1.5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol , 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl So-called low molecular glycols such as -1,3-propanediol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A, and mixtures thereof and succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, Terephthalic Acid, That the dry acid, maleic acid, oxalic acid, and naphthyl carboxylic acid such as tolylene of dicarboxylic acids, esters thereof, polyesters having a, hydroxyl group at both terminals obtained by the dehydration condensation reaction of an acid anhydride is preferred.
본 발명에서 사용하는 폴리에스테르 폴리올(a),(b)는 각각 1,4-부탄디올과 아디핀산을 반응시킨 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올인 것이 가장 바람직하다.
The polyester polyols (a) and (b) used in the present invention are most preferably polyester polyols of 1,4-butanediol / adipic acid obtained by reacting 1,4-butanediol and adipic acid, respectively.
그리고 수평균 분자량이 2,000~3,000인 폴리에스테르 폴리올(a)는 수산기가42~56이며, 접착력 및 내변색성이 우수한 특성이 있으며, 그 혼합량은 100 중량부를 기준으로 한다. 상기 폴리에스테르 폴리올(a)는 수평균 분자량이 2,000 미만이 될 경우에는 하드 세그먼트의 증가로 인하여 접착력이 저하 될 우려가 있고, 3,000을 초과할 경우에는 소프트 세그먼트의 함량 증가로 인하여 내열성이 저하할 우려가 있다.
The polyester polyol (a) having a number average molecular weight of 2,000 to 3,000 has a hydroxyl value of 42 to 56, and has excellent adhesive strength and discoloration resistance, and the mixing amount thereof is based on 100 parts by weight. When the polyester polyol (a) has a number average molecular weight of less than 2,000, there is a concern that the adhesive strength may decrease due to the increase of hard segments, and when the number average molecular weight exceeds 3,000, the heat resistance may decrease due to the increase of the content of the soft segment. There is.
또한 수평균 분자량이 4,000~5,000인 폴리에스테를 폴리올(b)는 수산기가20~35이며 우수한 초기 부착력을 부여하며, 그 혼합량은 50~70 중량부인 것이 바람직하다. 폴리에스테르 폴리올(b)의 혼합량이 50 중량부 미만이 될 경우에는 상기 폴리머의 특성 발휘가 어려우며, 70 중량부를 초과할 경우에는 높은 분자량의 영향으로 반응 속도가 상대적으로 빨라져 즉시 부착력 소멸을 촉진하는 우려가 있다. 상기 폴리에스테르 폴리올(b)는 수평균 분자량이 4,000 미만이 될 경우에는 특성 발휘가 어려울 것이며, 5,000을 초과할 경우에는 즉시 부착력 소멸을 촉진, 접착력 및 내열성 저하 될 우려가 있다.
In addition, the polyol (b) having a polyester having a number average molecular weight of 4,000 to 5,000 has a hydroxyl value of 20 to 35 and gives excellent initial adhesion, and the mixing amount thereof is preferably 50 to 70 parts by weight. When the blending amount of the polyester polyol (b) is less than 50 parts by weight, it is difficult to exhibit the properties of the polymer, and when it exceeds 70 parts by weight, the reaction rate is relatively faster due to the influence of high molecular weight, which promotes the immediate disappearance of adhesion. There is. When the polyester polyol (b) has a number average molecular weight of less than 4,000, it will be difficult to exhibit its properties, and if it exceeds 5,000, there is a possibility of promoting the disappearance of adhesion immediately, deteriorating adhesion and heat resistance.
그리고 수평균 분자량이 2,000~3,000인 폴리부타디엔 폴리올(c)는 그 혼합량이 10~20 중량부인 것이 바람직하다. 폴리부타디엔 폴리올(c)의 혼합량이 10 중량부 미만이 될 경우에는 부타디엔 폴리올의 특성인 저극성 소재에 대한 접착력증가가 미비하며, 20 중량부를 초과할 경우에는 저극성 인자의 증가로 인한 상분리 현상이 발생 될 우려가 있다. 상기 폴리부타디엔 폴리올(c)는 수평균 분자량이 2,000 미만이 될 경우에는 첨가량이 증가하여 상분리 현상이 발생 될 우려가 있고, 3,000 이상이 될 경우에는 투입량이 줄어들어 부타디엔 폴리올의 특성을 발휘하기 어렵다.
And it is preferable that the mixed amount of the polybutadiene polyol (c) whose number average molecular weights are 2,000-3,000 is 10-20 weight part. When the amount of the polybutadiene polyol (c) is less than 10 parts by weight, the increase in adhesion to the low polar material, which is a characteristic of the butadiene polyol, is insignificant. There is a risk of occurrence. When the polybutadiene polyol (c) has a number average molecular weight of less than 2,000, the amount of addition may increase, and phase separation may occur. When the amount exceeds 3,000, the amount of the polybutadiene polyol is hard to exhibit the properties of butadiene polyol.
본 발명에서 사용하는 폴리올레핀기를 포함한 폴리올 즉, 하이드록시 말단의 폴리 부타디엔 폴리올(c)는 유연한 세그먼트를 형성하는 것으로 관능성기는 1.9~2.5인 것이 바람직하다.
The polyol containing the polyolefin group used by this invention, ie, the polybutadiene polyol (c) of a hydroxyl terminal forms a flexible segment, and it is preferable that a functional group is 1.9-2.5.
그러나 상기의 폴리부타디엔 폴리올(c)는 저극성을 가지기 때문에 높은 극성을 가지는 폴리에스테르 폴리올(a), (b)와는 상용성이 나쁘므로 상기의 혼합 범위 내에서 혼합하여야 한다.
However, since the polybutadiene polyol (c) has a low polarity, it is poorly compatible with the polyester polyols (a) and (b) having high polarity, so it must be mixed within the above mixing range.
상기 하이드록시 말단 폴리 부타디엔 폴리올은 구체적으로 예컨대 사토머사의 제품인 크라졸 시리즈아케마사의 poly bd 시리즈, 미쓰비시 케미칼의 polytail 시리즈 등이 있다.
Specific examples of the hydroxy-terminated polybutadiene polyol include, for example, a poly bd series of Krasol series Akema, a polytail series of Mitsubishi Chemical, etc., manufactured by Satomer.
본 발명에 사용하는 유기 디이소시아네이트는 폴리에스테르 폴리올(a) 100 중량부에 대하여, 13~15 중량부인 것이 바람직하다. 유기 디이소시아네이트의 사용량이 13 중량부 미만이면, 충분한 폴리우레탄이 합성되지 않을 우려가 있고, 15 중량부를 초과할 경우에는 미반응의 유기 디이소시아네이트가 잔류할 우려가 있다. 그리고 본 발명에서 상기의 유기 디이소시아네이트 투입 시 급격한 점도 상승을 방지하기 위하여 단계적으로 투입하며 첫 번째 투입량은 NCO/OH 대비 유기 디이소시아네이트 투입량의 약 95%를 먼저 투입 후 1시간 이내에 용제를 적정량 투입한다. 그 이후 나머지 유기 디이소시아네이트 첨가량은 2~3회 분할하여 2시간 간격으로 투입하며 또한 용제도 유기 디이소시아네이트와 함께 분할 투입하여 급격한 점도 상승에 대한 과부하를 방지한다.
It is preferable that the organic diisocyanate used for this invention is 13-15 weight part with respect to 100 weight part of polyester polyols (a). When the usage-amount of organic diisocyanate is less than 13 weight part, sufficient polyurethane may not be synthesize | combined, and when it exceeds 15 weight part, there exists a possibility that unreacted organic diisocyanate may remain. In the present invention, the organic diisocyanate is added stepwise to prevent a sudden increase in viscosity, and the first amount is about 95% of the organic diisocyanate amount compared to NCO / OH, and an appropriate amount of the solvent is added within 1 hour after the first. . After that, the remaining amount of the organic diisocyanate added is divided into two to three times, and is added at intervals of two hours, and the solvent is also added in combination with the organic diisocyanate to prevent an overload on a sudden increase in viscosity.
본 발명에 사용하는 유기 디이소시아네이트는 지방족, 방향족 디이소시아네이트로서, 헥사메틸렌 디이소시아네이트,이소프론 디이소시아네이트(이하 IPDI로 약칭함), 메틸 사이클로 헥산 디이소시아네이트, 크실렌 디이소시아네이트, 디페닐 메탄 디이소시아네이트, 1,5-나프탈렌 디이소시아네이트, 2,4-톨루엔 디이소시아네이트, 2,6-톨루엔 디이소시아네이트등 중에서 하나 또는 그 이상을 선택하는 사용하는 것이 바람직하다.
Organic diisocyanates used in the present invention are aliphatic and aromatic diisocyanates, such as hexamethylene diisocyanate, isopron diisocyanate (hereinafter abbreviated as IPDI), methyl cyclohexane diisocyanate, xylene diisocyanate, diphenyl methane diisocyanate, 1 Preference is given to using one or more selected from among, 5-naphthalene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and the like.
또한 본 발명에 사용되는 쇄 연장제는 폴리우레탄 엘라스토머의 탄성이 향상되기 때문에, 물성상 더욱 바람직하다.
In addition, the chain extender used in the present invention is more preferable in terms of physical properties because the elasticity of the polyurethane elastomer is improved.
상기 쇄 연장제는 폴리에스테르 폴리올(a) 100 중량부에 대하여, 1.0~1.5 중량부인 것이 바람직하다. 쇄 연장제의 혼합량이 1.0 중량부 미만이 될 경우에는 폴리우레탄의 합성시 충분한 쇄 연장 반응이 일어나지 않을 우려가 있고, 1.5 중량부를 초과할 경우에는 쇄 연장제가 하드세그먼트의 역할을 하여 우레탄 및 우레아가 지나치게 딱딱해져 원하는 물성을 얻기 어려우며 또한 용제에 쉽게 용해가 되지 않을 우려가 있다.
It is preferable that the said chain extender is 1.0-1.5 weight part with respect to 100 weight part of polyester polyols (a). If the amount of the chain extender is less than 1.0 part by weight, there is a fear that sufficient chain extension reaction does not occur during the synthesis of polyurethane. If the amount of the chain extender exceeds 1.5 parts by weight, the chain extender acts as a hard segment so that the urethane and urea It is too hard to obtain the desired physical properties and there is a fear that it is not easily dissolved in the solvent.
본 발명에서 사용 가능한 쇄 연장제는 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 트리프로필렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 1,4-부탄디올, 2,3-부탄디올, 3-메틸-1,5-펜탄디올, 네오펜틸글리콜, 2-메틸-1,3-프로판디올, 2-메틸-2-프로필-1,3-프로판디올, 2-부틸-2-에틸-1,3-프로판디올, 1,5-펜탄디올, 1,6-헥산디올, 2-메틸-2,4-펜탄디올, 1,3-펜탄디올, 2-에틸-1,3-헥산디올, 2,5-디메틸-2,5-헥산디올, 2-부틸-2-헥실-1,3-프로판디올, 1,8-옥탄디올,2-메틸-1,8-옥탄디올, 1,9-노난디올 등의 지방족 글리콜, 비스히드록시메틸시클로헥산 등의 지환족 글리콜, 자일릴렌글리콜, 비스히드록시에톡시벤젠 등의 방향 고리를 갖는 글리콜 중에서 2종을 선택하여 사용하는 것이 바람직하다.
The chain extenders usable in the present invention are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3- Propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl- Aliphatic glycols such as 1,8-octanediol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, and glycols having aromatic rings such as xylylene glycol and bishydroxyethoxybenzene It is preferable to select and use.
본 발명에 따른 폴리우레탄계 수지를 합성하는 데에는 공지의 소위 폴리우레탄화 촉매제를 사용할 수 있으며, 폴리에스테르 폴리올(a) 100 중량부에 대하여, 0.02~0.05 중량부인 것이 바람직하다. 촉매제의 혼합량이 상기에서 한정한 범위 미만이 될 경우에는 반응속도가 느리고, 상기에서 한정한 범위를 초과할 경우에는 급격한 반응으로 인해 반응수율이 저하할 우려가 있다.
Known so-called polyurethane catalysts can be used to synthesize the polyurethane-based resin according to the present invention, and it is preferably 0.02 to 0.05 parts by weight based on 100 parts by weight of the polyester polyol (a). When the mixing amount of the catalyst is less than the range defined above, the reaction rate is slow, and when it exceeds the range defined above, there is a fear that the reaction yield is lowered due to a sudden reaction.
구체적으로는 디부틸주석 디라우레이트 등의 유기 금속 화합물, 트리에틸렌디아민 등의 유기 아민 및 그의 염 등이 있다
Specific examples include organometallic compounds such as dibutyltin dilaurate, organic amines such as triethylenediamine, and salts thereof.
이어서 상기 우레탄 프리폴리머를 지방족 용제를 부가하여 지방족 용제에 희석된 우레탄 프리폴리머를 형성한다. 상기 용제는 종래의 환경 문제의 주요인이 되는 방향족 용제가 아닌 에틸아세테이트, 부틸아세테이트 등의 에스테르계 용제와, 메탄올, 이소프로판올, 부탄올 등의 알코올계 용제 및 아세톤, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤계 용제를 포함하고 있으며, 이들 용제 중에서 선택된 하나 또는 둘 이상을 혼합하여 사용할 수 있다.
The urethane prepolymer is then added to an aliphatic solvent to form a urethane prepolymer diluted with an aliphatic solvent. The solvents are ester solvents such as ethyl acetate and butyl acetate, which are not aromatic solvents, which are the main causes of conventional environmental problems, alcohol solvents such as methanol, isopropanol and butanol, and acetone, methyl ethyl ketone, and methyl isobutyl ketone. It contains a ketone solvent, it can be used by mixing one or two or more selected from these solvents.
이때, 상기 본 발명에 적합한 폴리우레탄계 접착제 조성물을 얻기 위해 사용되는 용제는 폴리우레탄 수지 접착제 조성물에 대하여 중량비로 90/10~40/60 (용제/폴리우레탄 수지 접착제 조성물)인 것이 바람직하여, 그리고 85/15~50/50(용제/폴리우레탄 수지 접착제 조성물)인 것이 더욱 바람직하다.
At this time, it is preferable that the solvent used to obtain the polyurethane adhesive composition suitable for the present invention is 90/10 to 40/60 (solvent / polyurethane resin adhesive composition) in a weight ratio with respect to the polyurethane resin adhesive composition, and 85 It is still more preferable that it is / 15-50 / 50 (solvent / polyurethane resin adhesive composition).
상기의 방법으로 제조된 폴리우레탄 수지는 접착제 및 도료분야에서 이용될 수 있으나, 특히 신발 제조용 접착제로서의 제반 물성을 충족시키고 있으므로 신발 접착제용으로 매우 유용하겠다.
Polyurethane resin prepared by the above method can be used in the adhesive and paint field, but it is particularly useful for shoe adhesives because it satisfies all the physical properties as an adhesive for manufacturing shoes.
이와 같은 본 발명을 실시 예에 의거하여 상세히 설명하겠는 바, 본 발명이 실시 예에 한정되는 것은 아니다.
Although the present invention will be described in detail with reference to Examples, the present invention is not limited to Examples.
1. 저극성 신발 소재용 폴리우레탄 접착제 조성물의 제조
1. Preparation of Polyurethane Adhesive Compositions for Low Polar Footwear Materials
(실시 예 1) (Example 1)
콘덴서, 교반기, 온도계가 달린 4구 플라스크에 수평균 분자량이 2,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(b) 50 중량부, 수평균 분자량이 2,000인 폴리부타디엔 폴리올(c) 10 중량부와, 쇄 연장제인 1,4 부탄디올 0.5 중량부, 1.6 헥산 디올 0.5 중량부를 투입하고, 질소 분위기 하에 온도 80~90℃로 승온 교반 후, 헥사메틸렌디이소시아네이트 13 중량부 및 촉매제인 디부틸주석 디라우레이트 0.02 중량부를 투입한 후 85±1℃에서 8시간 반응시켜 폴리우레탄 접착제 조성물을 제조하였다. 100 parts by weight of polyester polyol (a) of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 and a 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 in a four-necked flask equipped with a condenser, a stirrer and a thermometer. 50 parts by weight of a polyester polyol (b), 10 parts by weight of a polybutadiene polyol (c) having a number average molecular weight of 2,000, 0.5 parts by weight of 1,4 butanediol as a chain extender, and 0.5 parts by weight of 1.6 hexanediol were added thereto. After stirring at a temperature of 80 ° C to 90 ° C under stirring, 13 parts by weight of hexamethylene diisocyanate and 0.02 parts by weight of dibutyltin dilaurate as a catalyst were added and reacted at 85 ± 1 ° C for 8 hours to prepare a polyurethane adhesive composition.
상기에서 단 상기의 이소시아네이트 투입 시 급격한 점도 상승을 방지하기 위하여 단계적으로 투입하며 첫 번째 투입량은 NCO/OH 대비 약 95%인 12.3중량부 투입 후 1시간 이내로 용제 50중량부 투입한다. 그 이후는 나머지 이소시야네이트 량은 2번 분할하여 2시간 간격으로 투입하며 또한 용제도 이소시아네이트와 함께 분할 투입하여 급격한 점도 상승에 대한 과부하를 방지한다.
In the above, the above isocyanate is added in steps to prevent a sharp increase in viscosity, and the first input amount is 50 parts by weight of solvent within 1 hour after 12.3 parts by weight, which is about 95% of NCO / OH. After that, the remaining amount of isocyanate is divided into two and added at intervals of two hours, and the solvent is also added into the isocyanate with the isocyanate to prevent an overload on a sharp increase in viscosity.
(실시 예 2) (Example 2)
상기 실시 예 1과 동일한 장치에 수평균 분자량이 2,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(b) 70 중량부, 수평균 분자량이 2,000인 폴리부타디엔 폴리올(c) 20 중량부와, 쇄 연장제인 1,4 부탄디올 0.8 중량부, 1.6 헥산 디올 0.7 중량부를 투입하고, 질소 분위기 하에 온도 80~90℃로 승온 교반 후, 헥사메틸렌디이소시아네이트 15 중량부 및 촉매제인 디부틸주석 디라우레이트 0.02 중량부를 투입한 후 85±1℃에서 6시간 반응시켜 폴리우레탄 접착제 조성물을 제조하였다.
100 parts by weight of polyester polyol (a) of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 in the same apparatus as in Example 1, and polyester of 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 70 parts by weight of polyol (b), 20 parts by weight of polybutadiene polyol (c) having a number average molecular weight of 2,000, 0.8 parts by weight of 1,4 butanediol as a chain extender, and 0.7 parts by weight of 1.6 hexanediol were added thereto, and a temperature of 80 was obtained under a nitrogen atmosphere. After stirring at a temperature of ˜90 ° C., 15 parts by weight of hexamethylene diisocyanate and 0.02 part by weight of dibutyltin dilaurate as a catalyst were added thereto, followed by reaction at 85 ± 1 ° C. for 6 hours to prepare a polyurethane adhesive composition.
(비교 예 1) (Comparative Example 1)
상기 실시 예 1과 동일한 장치에 수평균 분자량이 2,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(b) 75 중량부와 쇄 연장제인 1,4 부탄디올 0.8 중량부, 1.6 헥산 디올 0.7 중량부를 투입하고, 질소 분위기 하에 온도 80~90℃로 승온 교반 후, 헥사메틸렌디이소시아네이트 15 중량부 및 촉매제인 디부틸주석 디라우레이트 0.02 중량부를 투입한 후 85±1℃에서 6시간 반응시켜 폴리우레탄 접착제 조성물을 제조하였다.
100 parts by weight of polyester polyol (a) of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 in the same apparatus as in Example 1, and polyester of 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 75 parts by weight of polyol (b), 0.8 parts by weight of 1,4 butanediol as a chain extender, and 0.7 parts by weight of 1.6 hexanediol were added thereto, followed by stirring at a temperature of 80 to 90 ° C. under a nitrogen atmosphere, and then 15 parts by weight of hexamethylene diisocyanate and a catalyst. 0.02 parts by weight of phosphorus dibutyltin dilaurate was added and reacted at 85 ± 1 ° C. for 6 hours to prepare a polyurethane adhesive composition.
(비교 예 2) (Comparative Example 2)
상기 비교 예 1과 동일한 장치에 수평균 분자량이 2,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(b) 40 중량부, 수평균 분자량이 2,000인 폴리부타디엔 폴리올(c) 25 중량부와 쇄 연장제인 1,4 부탄디올 0.5 중량부, 1.6 헥산 디올 0.5 중량부를 투입하고, 질소 분위기 하에 온도 80~90℃로 승온 교반 후, 헥사메틸렌디이소시아네이트 13 중량부 및 촉매제인 디부틸주석 디라우레이트 0.02 중량부를 투입한 후 85±1℃에서 6시간 반응시켜 폴리우레탄 접착제 조성물을 제조하였다.
100 parts by weight of a polyester polyol (a) of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 in the same apparatus as Comparative Example 1, and a polyester of 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 40 parts by weight of polyol (b), 25 parts by weight of polybutadiene polyol (c) having a number average molecular weight of 2,000, 0.5 parts by weight of 1,4 butanediol as a chain extender, and 0.5 parts by weight of 1.6 hexanediol were added, and the temperature was 80 to 80 ° C under a nitrogen atmosphere. After stirring at an elevated temperature of 90 ° C., 13 parts by weight of hexamethylene diisocyanate and 0.02 part by weight of dibutyltin dilaurate as a catalyst were added thereto, followed by reaction at 85 ± 1 ° C. for 6 hours to prepare a polyurethane adhesive composition.
(비교 예 3) (Comparative Example 3)
상기 비교 예 1과 동일한 장치에 수평균 분자량이 2,000인 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000인 1,4-부탄디올/아디핀산의 폴리에스테를 폴리올(b) 65 중량부, 수평균 분자량이 2,000인 폴리부타디엔 폴리올(c) 5 중량부와, 쇄 연장제인 1,4 부탄디올 0.5 중량부, 1.6 헥산 디올 0.5 중량부를 투입하고, 질소 분위기 하에 온도 80~90℃로 승온 교반 후, 헥사메틸렌디이소시아네이트 13 중량부 및 촉매제인 디부틸주석 디라우레이트 0.02 중량부를 투입한 후 85±1℃에서 6시간 반응시켜 폴리우레탄 접착제 조성물을 제조하였다.
100 parts by weight of polyester polyol (a) of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 in the same apparatus as Comparative Example 1, and polyester of 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 65 parts by weight of a polyol (b), 5 parts by weight of a polybutadiene polyol (c) having a number average molecular weight of 2,000, 0.5 parts by weight of 1,4 butanediol as a chain extender, and 0.5 parts by weight of 1.6 hexanediol were added thereto under a nitrogen atmosphere. After stirring at 80 ° C to 90 ° C, 13 parts by weight of hexamethylene diisocyanate and 0.02 parts by weight of dibutyltin dilaurate as a catalyst were added, and then reacted at 85 ± 1 ° C for 6 hours to prepare a polyurethane adhesive composition.
상기 실시 예 1, 2 및 비교 예 1~3의 방법에 의해 폴리우레탄 접착제 조성물의 제조반응은 적외선 분광 분석에 의해 2270cm-1 이소시아네이트 피크가 사라지면 반응을 종결하였다. 상기의 방법에 의해 제조된 폴리우레탄 수지 접착제는 4,000~6,000CPS(25℃), 15~18중량% 고형분인 결과물을 수득하였다.
The preparation reaction of the polyurethane adhesive composition by the method of Examples 1 and 2 and Comparative Examples 1 to 3 was terminated when the 2270 cm -1 isocyanate peak disappeared by infrared spectroscopy. Polyurethane resin adhesive prepared by the above method was obtained a product of 4,000 ~ 6,000 CPS (25 ℃), 15 to 18% by weight solids.
2. 저극성 신발 소재용 폴리우레탄 접착제 조성물의 평가
2. Evaluation of Polyurethane Adhesive Compositions for Low Polar Footwear Materials
상기 실시 예 1, 2 및 비교 예 1~3의 방법에 의해 제조한 폴리우레탄 접착제 조성물은 아래의 시험방법에 따라 EVA 발포체에 대한 접착력을 비교평가한 결과는 아래 [표 1], [표 2]의 내용과 같다.
Polyurethane adhesive composition prepared by the method of Examples 1, 2 and Comparative Examples 1 to 3 according to the test method described below the comparative evaluation of the adhesion to the EVA foam is the following [Table 1], [Table 2] Is the same as
가. 접착 시편의 제조end. Preparation of Adhesive Specimen
20×100mm의 크기에 EVA 폼에 신발용 EVA 프라이머(PR 907 화승 T&C)를 브러쉬를 이용하여 3회 도포 후 60℃×7분간 송풍 건조 오븐에서 건조하였다.
EVA primer (PR 907 Hwaseung T & C) was applied to EVA foam at a size of 20 × 100 mm three times using a brush, and then dried in a blow drying oven at 60 ° C. for 7 minutes.
상기 시험편 및 고무 시험편에 상기 실시 예 1, 2 및 비교 예 1~3을 브러쉬를 이용하여 각 3회 도포 후 60℃×5 분간 건조 후 건조한 고무 시편과 EVA 시편의 접착면을 접합하여 약 60kg/25mm 롤(roll) 압착하여 시험편을 제작하였다. 이때 동일 시험에 사용하는 시험시편은 각 실시 예 별로, 초기 및 후기 접착력 시험항목별로 각각 4개씩을 사용하였고, 초기 및 후기 내열 시험항목별로 각각 1개씩을 사용하였다.
Examples 1, 2 and Comparative Examples 1 to 3 were applied to the test specimen and the rubber test specimen three times using a brush, and then dried at 60 ° C. for 5 minutes, and then bonded to the adhesive surface of the dried rubber specimen and the EVA specimen, about 60 kg / The test piece was produced by crimping 25 mm rolls. At this time, the test specimens used in the same test was used for each of the four examples, each of the initial and late adhesive strength test items, one each for the initial and late heat resistance test items.
나. 초기 및 후기 접착력I. Early and late adhesion
상기 가의 방법에 의해 제조한 4개의 접착시편을 실온에서 30분간 및 24시간 방치한 후 만능인장 시험기(인스트론사 모델명 1011)를 사용하여 50±10mm/분의 인장속도로 박리하여 접착 강도를 측정하였으며, 시험결과의 평균값을 아래 [표 1]에 나타내었다.The four adhesive specimens prepared by the above method were left at room temperature for 30 minutes and 24 hours, and then peeled at a tensile rate of 50 ± 10 mm / min using a universal tensile tester (Instron model name 1011) to measure the adhesive strength. The average value of the test results is shown in [Table 1] below.
다. 초기 및 후기 내열성All. Early and late heat resistance
초기 내열성은 상기 시험편을 압착 후 실온에서 30분간 방치한 후 EVA 폼 끝에 500g의 추를 매달고 80에서 30분간 방치, 180°박리 크리프(creep) 실험을 행하여 추가 박리된 길이 또는 완전 박리된 시간을 측정하였다. 그리고 후기 내열성은 상기 시험편을 압착 후 실온에서 24시간 방치한 후 EVA 폼 끝에 500g의 추를 매달고 100℃에서 30분간 방치, 180°박리 크리프(creep) 실험을 행하여 추가 박리된 시간을 측정하였으며, 시험결과는 아래 [표 2]에 나타내었다.
Initial heat resistance after pressing the specimen for 30 minutes at room temperature, suspended the end of the EVA foam 500g weight, left for 80 to 30 minutes, 180 ° peeling creep test to measure the additional peeled length or complete peeling time It was. And the latent heat resistance was pressed for 24 hours at room temperature after crimping the test specimen, suspended 500g weight on the end of the EVA foam and left for 30 minutes at 100 ℃, 180 ° peeling creep test was performed to measure the additional peeled time. The results are shown in [Table 2] below.
저극성 신발 소재용 폴리우레탄 접착제 조성물을 시험한 결과 실시 예 1, 2는 상기 [표 1]에 나타난 바와 같이, 비교 예 1~3에 비해 초기 접착력 및 후기 접착력이 우수한 것으로 나타났다,
As a result of testing the polyurethane adhesive composition for low-polar shoes material, Examples 1 and 2, as shown in the above [Table 1], it was found that the initial adhesion and the late adhesion is superior to Comparative Examples 1 to 3,
그리고 실시 예 1, 2는 상기 [표 2]에 나타난 바와 같이, 비교 예 1~3에 비해 초기 접착력 및 후기 접착력이 우수한 것으로 나타났다,
And Examples 1 and 2, as shown in the above [Table 2], compared to Comparative Examples 1 to 3 was found to be excellent in the initial adhesive force and the late adhesive force,
비교 예 2의 경우에는 실시 예 1, 2에 비해 초기 접착력 및 후기 접착력의 물성은 비슷하지만 초기 내열성 및 후기 내열성의 물성이 떨어지는 것으로 나타났다.
In Comparative Example 2, the physical properties of the initial adhesive force and the late adhesive force were similar to those of Examples 1 and 2, but the physical properties of the initial heat resistance and the late heat resistance were inferior.
상술한 바와 같이, 본 발명에 따른 저극성 신발 소재용 폴리우레탄 접착제 조성물은 상기의 바람직한 실시 예를 통해 설명하고, 그 우수성을 확인하였지만 해당 기술 분야의 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, the polyurethane adhesive composition for low polarity shoe material according to the present invention has been described through the above-described preferred embodiment, and confirmed the superiority, but those skilled in the art will be able to understand the present invention described in the following claims. It will be understood that various modifications and variations can be made in the present invention without departing from the spirit and scope.
Claims (6)
상기 폴리올은 폴리에스테르 폴리올과 폴리부타디엔 폴리올의 혼합 폴리올로서, 수평균 분자량이 2,000~3,000인 폴리에스테르 폴리올(a) 100 중량부, 수평균 분자량이 4,000~5,000인 폴리에스테르 폴리올(b) 50~70 중량부, 수평균 분자량이 2,000~3,000인 폴리부타디엔 폴리올(c) 10~20 중량부로 이루어지고,
그리고, 상기 폴리에스테르 폴리올(a) 및 폴리에스테르 폴리올(b)는 1,4-부탄디올과 아디핀산을 반응시킨 1,4-부탄디올/아디핀산의 폴리에스테르 폴리올이며,
상기 폴리에스테르 폴리올(a) 100 중량부에 대하여, 유기 디이소시아네이트 13~15 중량부, 쇄 연장제 1.0~1.5 중량부이고,
상기 용제는 폴리우레탄 수지 접착제 조성물에 대하여, 중량비로 90/10~40/60 (용제/폴리우레탄 수지 접착제 조성물)인 것을 특징으로 하는 폴리우레탄 수지 접착제 조성물.In a polyurethane adhesive composition synthesized by dissolving a polyol and an organic diisocyanate with a solvent and adding a chain extender and a catalyst,
The polyol is a mixed polyol of a polyester polyol and a polybutadiene polyol, 100 parts by weight of a polyester polyol (a) having a number average molecular weight of 2,000 to 3,000, and a polyester polyol (b) of 50 to 70 having a number average molecular weight of 4,000 to 5,000 Part by weight, polybutadiene polyol (c) having a number average molecular weight of 2,000 to 3,000 of 10 to 20 parts by weight,
The polyester polyol (a) and the polyester polyol (b) are polyester polyols of 1,4-butanediol / adipic acid obtained by reacting 1,4-butanediol and adipic acid,
It is 13-15 weight part of organic diisocyanate, 1.0-1.5 weight part of chain extenders with respect to 100 weight part of said polyester polyols (a),
The said solvent is 90/10-40/60 (solvent / polyurethane resin adhesive composition) by weight ratio with respect to a polyurethane resin adhesive composition, The polyurethane resin adhesive composition characterized by the above-mentioned.
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| JPH1060260A (en) | 1996-08-22 | 1998-03-03 | Sakata Corp | Room temperature curable aqueous polyurethane resin composition and use thereof |
| JPH11241057A (en) | 1997-12-22 | 1999-09-07 | Sanyo Chem Ind Ltd | Two-component dry-laminating adhesive |
| JP2001011413A (en) | 1999-06-25 | 2001-01-16 | Daicel Chem Ind Ltd | Adhesive composition and laminate |
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| JPH1060260A (en) | 1996-08-22 | 1998-03-03 | Sakata Corp | Room temperature curable aqueous polyurethane resin composition and use thereof |
| JPH11241057A (en) | 1997-12-22 | 1999-09-07 | Sanyo Chem Ind Ltd | Two-component dry-laminating adhesive |
| JP2001011413A (en) | 1999-06-25 | 2001-01-16 | Daicel Chem Ind Ltd | Adhesive composition and laminate |
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