KR102684233B1 - Waterborne polyurethane adhesive composition for water soluble label and its manufacturing method - Google Patents

Waterborne polyurethane adhesive composition for water soluble label and its manufacturing method Download PDF

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KR102684233B1
KR102684233B1 KR1020220027787A KR20220027787A KR102684233B1 KR 102684233 B1 KR102684233 B1 KR 102684233B1 KR 1020220027787 A KR1020220027787 A KR 1020220027787A KR 20220027787 A KR20220027787 A KR 20220027787A KR 102684233 B1 KR102684233 B1 KR 102684233B1
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water
dispersible polyurethane
adhesive composition
polyurethane
weight
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KR1020220027787A
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KR20230131361A (en
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김원식
이대호
한만충
이춘재
이민수
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주식회사 엠에스켐
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Priority to PCT/KR2022/003709 priority patent/WO2023167360A1/en
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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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/08—Fastening or securing by means not forming part of the material of the label itself
    • G09F3/10—Fastening or securing by means not forming part of the material of the label itself by an adhesive layer

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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)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

개시되는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물 및 그 제조 방법은, 아디프산과 1,4 부탄디올로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI) 혹은 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI)와, 디메틸올부타노익산(DMBA)과, 1,4-부탄디올(1,4-BD)과, 트리에틸아민(TEA)과, 에틸렌디아민(EDA)으로 중합된 수분산 폴리우레탄-우레아 접착수지; 및 아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI)와, 디메틸올부타노익산(DMBA)과, 트리에틸아민(TEA)으로 이용하여 제조된 수분산 폴리우레탄 점착부여제;를 포함함으로써, 접착수지와 점착부여제의 혼합비로 이형필름이 필요하지 않은 라벨용 접착제 조성물을 제공할 수 있고, 쉽게 가수분해가 진행되는 폴리에스터폴리올의 사용과 디메틸올부타노익산(DMBA)의 함량 조절을 통해 수해리성과 접착성을 동시에 충족시킬 수 있다.The disclosed water-dispersible polyurethane adhesive composition for labels and its manufacturing method include polyester polyol with a molecular weight of 2000 consisting of adipic acid and 1,4 butanediol, isophorone diisocyanate (IPDI) or dicyclohexylmethane-4, 4'-diisocyanate (H 12 MDI), dimethylolbutanoic acid (DMBA), 1,4-butanediol (1,4-BD), triethylamine (TEA), and ethylenediamine (EDA). Polymerized water-dispersed polyurethane-urea adhesive resin; and a water-dispersed poly produced using a polyester polyol with a molecular weight of 2000 composed of adipic acid and neopentyl glycol, isophorone diisocyanate (IPDI), dimethylolbutanoic acid (DMBA), and triethylamine (TEA). By including a urethane tackifier, it is possible to provide an adhesive composition for labels that does not require a release film due to the mixing ratio of adhesive resin and tackifier, and the use of polyester polyol, which is easily hydrolyzed, and dimethylolbutanoic acid. By adjusting the content of iksan (DMBA), water dissociation and adhesiveness can be achieved simultaneously.

Description

수해리성 라벨용 수분산 폴리우레탄 접착제 조성물 및 그 제조 방법{WATERBORNE POLYURETHANE ADHESIVE COMPOSITION FOR WATER SOLUBLE LABEL AND ITS MANUFACTURING METHOD}Water-dispersible polyurethane adhesive composition for water-dissociable labels and method for manufacturing the same {WATERBORNE POLYURETHANE ADHESIVE COMPOSITION FOR WATER SOLUBLE LABEL AND ITS MANUFACTURING METHOD}

본 발명(Disclosure)은, 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물 및 그 제조 방법에 관한 것으로, 구체적으로, PET병과 같은 플라스틱 포장재에 대하여 우수한 접착력을 발현하면서도 수분리 공정에서 잔사가 없이 쉽게 라벨이 분리되는 접착성과 수해리성을 동시에 충족시킬 수 있는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물 및 그 제조 방법에 관한 것이다.The present invention (Disclosure) relates to a water-dispersible polyurethane adhesive composition for water-dissociable labels and a method of manufacturing the same. Specifically, the present invention (Disclosure) relates to a water-dispersible polyurethane adhesive composition for labels and a method of manufacturing the same. Specifically, the present invention (Disclosure) relates to a water-dispersible polyurethane adhesive composition for labels, and specifically, to exhibit excellent adhesion to plastic packaging materials such as PET bottles, while easily labeling without residue during the water separation process. It relates to a water-dispersible polyurethane adhesive composition for water-dissociable labels that can simultaneously satisfy detachable adhesiveness and water-dissociability, and a method for manufacturing the same.

여기서는, 본 발명에 관한 배경기술이 제공되며, 이들이 반드시 공지기술을 의미하는 것은 아니다(This section provides background information related to the present disclosure which is not necessarily prior art).Here, background information related to the present invention is provided, and this does not necessarily mean prior art (This section provides background information related to the present disclosure which is not necessarily prior art).

과학 기술의 진보는 재료의 다양한 기능성과 강도를 요구하게 되었고, 단일소재로 이 문제를 해결하기 어렵기 때문에, 단일소재를 여러 개 조합한 재료가 개발되고 있다.Advances in science and technology have led to a need for diverse functionality and strength of materials, and because it is difficult to solve this problem with a single material, materials that combine multiple single materials are being developed.

여기에 사용되는 각 단일소재를 서로 붙이는 역할을 하는 물질이 접착제이며, 여러 금속 및 유기재료, 섬유, 플라스틱, 고무 세라믹 등이 접착제를 통하여 새로운 소재로 개발되고 있다.The substance that serves to attach each single material used here is an adhesive, and various metals, organic materials, fibers, plastics, rubber ceramics, etc. are being developed as new materials through adhesives.

이러한 접착은 동종 또는 이종간의 접촉면이 접착제에 의해 결합되는 것을 뜻하며, 산업현장이나 생활주변에서 그 사용이 크게 증가하고 있다.This type of adhesion means that contact surfaces of the same or different types are joined together by an adhesive, and its use is greatly increasing in industrial sites and everyday life.

최근에는 유화중합에 의한 친환경 수성접착제가 많이 사용되고 있는데 피착제에 부착되어 있을 때는 충분한 접착력을 나타내지만 제거시 잔사가 없이 쉽게 분리되는 특성이 요구된다. 특히 플라스틱 포장재와 관련된 환경 오염 문제 및 자원 재활용 측면에서 플라스틱 포장재의 재활용을 위하여 물을 이용하여 라벨을 쉽게 제거하는 수해리성 접착제에 대한 관심이 높아지고 있다.Recently, eco-friendly water-based adhesives using emulsion polymerization have been widely used. They exhibit sufficient adhesive strength when attached to an adherend, but require characteristics that allow them to be easily separated without leaving any residue when removed. In particular, in light of environmental pollution issues and resource recycling related to plastic packaging materials, interest in water-dissociable adhesives that easily remove labels using water for recycling of plastic packaging materials is increasing.

이에, 종래에 친수성기로서 카르복실레이트기 및/또는 설포네이트기를 함유하는 폴리이소시아네이트 중부가물의 수성용액 또는 분산액의 제조하는 기법이 제안되었는데, 분산액에 의한 접착제는 폴리우레탄 수지의 입자 직경이 작기는 하지만 실질적으로 계면활성제를 첨가하지 않아, 표면장력이 크며, 접착제 도포 시의 전연성, 또는 다공성 기재에 대한 침투성, 접착강도 등의 성능을 충분히 만족시키지 못하고, 접착제가 물에서 완전 해리되지 않아 잔여물이 남아, 이를 처리하는 후공정이 요구되는 문제점이 있다.Accordingly, a technique for preparing an aqueous solution or dispersion of a polyisocyanate polyadduct containing a carboxylate group and/or a sulfonate group as a hydrophilic group has been proposed in the past. Although the adhesive produced by the dispersion solution has a small particle diameter of the polyurethane resin, Substantially no surfactant is added, so the surface tension is high, and the performance such as malleability when applying the adhesive, penetration into porous substrates, and adhesive strength is not sufficiently satisfied, and the adhesive does not completely dissociate in water, leaving a residue. , there is a problem that requires a post-process to handle this.

이러한 문제점을 해결하기 위해, 물 속에서 완전 해리되어 잔류물이 전혀 없는 친환경 접착 조성물에 대한 연구 개발이 요구되고 있다.To solve these problems, research and development is required for an eco-friendly adhesive composition that completely dissociates in water and leaves no residue.

1. 한국공개특허공보 제10-2016-0143691호(2016.12.14.공개)1. Korean Patent Publication No. 10-2016-0143691 (published on December 14, 2016)

본 발명(Disclosure)은, 영구접착력을 부여하는 수분산 폴리우레탄-우레아 접착수지와, 초기접착력을 부여하는 수분산 폴리우레탄 점착부여제를 포함함으로써, 접착수지와 점착부여제의 혼합비로 이형필름이 필요하지 않은 라벨용 접착제 조성물을 제공할 수 있고, 접착제 성분이 가수분해 되어 잔사없이 라벨이 제거되어 접착력과 수해리성을 동시에 충족시킬 수 있는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물 및 그 제조 방법의 제공을 일 목적으로 한다.The present invention (Disclosure) includes a water-dispersed polyurethane-urea adhesive resin that provides permanent adhesive strength and a water-dispersed polyurethane tackifier that provides initial adhesive strength, so that the release film is formed by mixing the adhesive resin and the tackifier. A water-dispersible polyurethane adhesive composition for water-dissociable labels that can provide an adhesive composition for labels that is not required, and that can satisfy both adhesive strength and water-dissociability by removing the label without residue as the adhesive components are hydrolyzed, and a method for manufacturing the same. It is provided for the purpose of providing work.

여기서는, 본 발명의 전체적인 요약(Summary)이 제공되며, 이것이 본 발명의 외연을 제한하는 것으로 이해되어서는 아니 된다(This section provides a general summary of the disclosure and is not a comprehensive disclosure of its full scope or all of its features).Here, a general summary of the present invention is provided, and this should not be construed as limiting the scope of the present invention (This section provides a general summary of the disclosure and is not a comprehensive disclosure of its full scope or all of its features).

상기한 과제의 해결을 위해, 본 발명을 기술하는 여러 관점들 중 어느 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물은, 아디프산과 1,4 부탄디올로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI) 혹은 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI)와, 디메틸올부타노익산(DMBA)과, 1,4-부탄디올(1,4-BD)과, 트리에틸아민(TEA)과, 에틸렌디아민(EDA)으로 중합된 수분산 폴리우레탄-우레아 접착수지; 및 아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI)와, 디메틸올부타노익산(DMBA)과, 트리에틸아민(TEA)으로 이용하여 제조된 수분산 폴리우레탄 점착부여제;를 포함한다.In order to solve the above problem, a water-dispersible polyurethane adhesive composition for a water-dissociable label according to one aspect of the various aspects describing the present invention is a polyester having a molecular weight of 2000 consisting of adipic acid and 1,4 butanediol. Ester polyol, isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate (H 12 MDI), dimethylolbutanoic acid (DMBA), and 1,4-butanediol (1,4 -BD), triethylamine (TEA), and ethylenediamine (EDA), a water-dispersed polyurethane-urea adhesive resin polymerized; and a water-dispersed poly produced using a polyester polyol with a molecular weight of 2000 composed of adipic acid and neopentyl glycol, isophorone diisocyanate (IPDI), dimethylolbutanoic acid (DMBA), and triethylamine (TEA). Contains a urethane tackifier.

발명의 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물에서, 상기 수분산 폴리우레탄-우레아 접착수지와 상기 수분산 폴리우레탄 점착부여제의 중량비는, 1/9-5/5로 하여 혼합될 수 있다.In the water-dispersible polyurethane adhesive composition for water-dissociable labels according to one aspect of the invention, the weight ratio of the water-dispersible polyurethane-urea adhesive resin and the water-dispersible polyurethane tackifier is 1/9-5/5. It can be mixed.

발명의 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물에서, 상기 수분산 폴리우레탄-우레아 접착수지는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함될 수 있다.In the water-dispersible polyurethane adhesive composition for water-dissociable labels according to one aspect of the invention, the water-dispersible polyurethane-urea adhesive resin may contain 4-10% by weight of dimethylolbutanoic acid (DMBA). there is.

발명의 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물에서, 상기 수분산 폴리우레탄 점착부여제는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함될 수 있다.In the water-dispersible polyurethane adhesive composition for water-dissociable labels according to one aspect of the invention, the water-dispersible polyurethane tackifier may contain 4-10% by weight of dimethylolbutanoic acid (DMBA). .

발명의 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물에서, 상기 수분산 폴리우레탄-우레아 접착수지의 프리폴리머는, NCO/(OH+NH2) 몰비가 1.2-1.5의 범위로 제공될 수 있다.In the water-dispersible polyurethane adhesive composition for water-dissociable labels according to an aspect of the invention, the prepolymer of the water-dispersible polyurethane-urea adhesive resin has an NCO/(OH+NH 2 ) molar ratio in the range of 1.2-1.5. can be provided.

발명의 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물에서, 상기 수분산 폴리우레탄 점착부여제는, NCO/OH 몰비가 0.7-1.2의 범위로 제공될 수 있다.In the water-dispersible polyurethane adhesive composition for water-dissociable labels according to one aspect of the invention, the water-dispersible polyurethane tackifier may be provided at an NCO/OH molar ratio in the range of 0.7-1.2.

본 발명을 기술하는 여러 관점들 중 다른 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법은, 아디프산과 1,4 부탄디올로 이루어진 분자량 2000의 폴리에스터폴리올과, 디메틸올부타노익산과, 1,4-부탄디올을 이용하여 제 1 용융액을 제조하는 단계; 상기 제조된 제 1 용융액에 이소포론디이소시아네이트(IPDI) 혹은 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI)을 투입하여 프리폴리머를 제조하는 단계; 상기 제조된 프리폴리머에 트리에틸아민(TEA)을 투입하여 수분산된 프리폴리머를 제조하는 단계; 상기 제조된 수분산 프리폴리머에 에틸렌디아민(EDA)을 투입하여 수분산 폴리우레탄-우레아 접착수지를 제조하는 단계; 아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올과, 디메틸올부타노익산(DMBA)을 투입하여 제 2 용융액을 제조하는 단계; 상기 제조된 제 2 용융액에 이소포론디이소시아네이트(IPDI)를 투입하여 폴리머를 제조하는 단계; 상기 제조된 폴리머에 트리에틸아민(TEA)을 투입하여 수분산 폴리우레탄 점착부여제를 제조하는 단계; 및 상기 수분산 폴리우레탄-우레아 접착수지와 상기 수분산 폴리우레탄 점착부여제를 기 설정된 중량비로 혼합하여 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조하는 단계;를 포함한다.Among the various aspects describing the present invention, a method for producing a water-dispersible polyurethane adhesive composition for labels according to another aspect includes a polyester polyol with a molecular weight of 2000 consisting of adipic acid and 1,4 butanediol, and dimethyl Preparing a first melt using olbutanoic acid and 1,4-butanediol; Preparing a prepolymer by adding isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate (H 12 MDI) to the prepared first melt; Preparing a water-dispersed prepolymer by adding triethylamine (TEA) to the prepared prepolymer; Preparing a water-disperse polyurethane-urea adhesive resin by adding ethylenediamine (EDA) to the water-disperse prepolymer prepared above; Preparing a second melt by adding a polyester polyol with a molecular weight of 2000 consisting of adipic acid and neopentyl glycol and dimethylolbutanoic acid (DMBA); Preparing a polymer by adding isophorone diisocyanate (IPDI) to the prepared second melt; Preparing a water-dispersed polyurethane tackifier by adding triethylamine (TEA) to the prepared polymer; and mixing the water-dispersible polyurethane-urea adhesive resin and the water-dispersible polyurethane tackifier at a preset weight ratio to prepare a water-dispersible polyurethane adhesive composition for a water-dissociable label.

본 발명의 다른 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법에서, 상기 수분산 폴리우레탄-우레아 점착수지를 제조하는 단계는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함되고, 상기 프리폴리머의 NCO/(OH+NH2) 몰비가 1.2-1.5의 범위가 되도록 상기 수분산 폴리우레탄-우레아 접착수지를 제조할 수 있다.In the method for producing a water-dispersible polyurethane adhesive composition for a water-dissociable label according to another aspect of the present invention, the step of preparing the water-dispersible polyurethane-urea adhesive resin includes dimethylolbutanoic acid (DMBA). The water-dispersed polyurethane-urea adhesive resin can be prepared so that it is contained at 4-10% by weight, and the NCO/(OH+NH 2 ) molar ratio of the prepolymer is in the range of 1.2-1.5.

본 발명의 다른 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법에서, 상기 수분산 폴리우레탄 점착부여제를 제조하는 단계는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함되고, NCO/OH 몰비가 0.7-1.2의 범위가 되도록 상기 수분산 폴리우레탄 점착부여제를 제조할 수 있다.In the method for producing a water-dispersible polyurethane adhesive composition for a water-dissociable label according to another aspect of the present invention, the step of preparing the water-dispersible polyurethane tackifier includes dimethylolbutanoic acid (DMBA) The water-dispersed polyurethane tackifier can be prepared so that it is contained at -10% by weight and the NCO/OH molar ratio is in the range of 0.7-1.2.

본 발명의 다른 일 관점(aspect)에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법에서, 상기 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조하는 단계는, 상기 수분산 폴리우레탄-우레아 접착수지와 상기 수분산 폴리우레탄 점착부여제를 1/9-5/5의 중량비로 혼합할 수 있다.In the method for producing a water-dispersible polyurethane adhesive composition for a water-dissociable label according to another aspect of the present invention, the step of manufacturing the water-dispersible polyurethane adhesive composition for a water-dissociable label includes the water-dispersible polyurethane-urea The adhesive resin and the water-dispersed polyurethane tackifier can be mixed at a weight ratio of 1/9-5/5.

본 발명에 따르면, 영구접착력을 부여하는 수분산 폴리우레탄-우레아 접착수지와,초기접착력을 부여하는 수분산 폴리우레탄 점착부여제를 포함함으로써, 접착수지와 점착부여제의 혼합비로 이형필름이 필요하지 않은 라벨용 접착제 조성물을 제공할 수 있고, 쉽게 가수분해가 진행되는 폴리에스터폴리올의 사용과 디메틸부타노익산(DMBA)의 함량 조절을 통해 수해리성과 접착성을 동시에 충족시킬 수 있다.According to the present invention, by including a water-dispersed polyurethane-urea adhesive resin that provides permanent adhesive force and a water-dispersed polyurethane tackifier that provides initial adhesive force, a release film is not required due to the mixing ratio of the adhesive resin and the tackifier. An adhesive composition for labels can be provided, and water dissociability and adhesiveness can be achieved simultaneously through the use of polyester polyol, which is easily hydrolyzed, and by controlling the content of dimethylbutanoic acid (DMBA).

도 1은 본 발명의 다른 실시예에 따라 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조하는 과정을 나타낸 플로우차트이고,
도 2는 본 발명에 따라 접착수지 제조예 1의 DSC를 나타내는 도면이며,
도 3은 본 발명에 따라 제조한 수해리성 라벨용 접착조성물의 수해리 결과, 라벨지와 PET가 분리되는 현상을 나타내는 도면이다.1 is a flow chart showing the process of manufacturing a water-dispersible polyurethane adhesive composition for a water-dissociable label according to another embodiment of the present invention;
Figure 2 is a diagram showing the DSC of adhesive resin preparation example 1 according to the present invention;
Figure 3 is a diagram showing the separation of label paper and PET as a result of water dissociation of the water-dissociable adhesive composition for labels prepared according to the present invention.

이하, 본 발명에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물 및 그 제조 방법을 구현한 실시형태를 도면을 참조하여 자세히 설명한다.Hereinafter, an embodiment embodying the water-dispersible polyurethane adhesive composition for a water-dissociable label and its manufacturing method according to the present invention will be described in detail with reference to the drawings.

다만, 본 발명의 본질적인(intrinsic) 기술적 사상은 이하에서 설명되는 실시형태에 의해 그 실시 가능 형태가 제한된다고 할 수는 없고, 본 발명의 본질적인(intrinsic) 기술적 사상에 기초하여 통상의 기술자에 의해 이하에서 설명되는 실시형태를 치환 또는 변경의 방법으로 용이하게 제안될 수 있는 범위를 포섭함을 밝힌다.However, the essential technical idea of the present invention cannot be said to be limited to the embodiments described below, and based on the essential technical idea of the present invention, it cannot be said that the possible embodiments are limited by the embodiments described below. It is disclosed that the embodiment described in covers the scope that can be easily proposed by way of replacement or change.

또한, 이하에서 사용되는 용어는 설명의 편의를 위하여 선택한 것이므로, 본 발명의 본질적인(intrinsic) 기술적 사상을 파악하는 데 있어서, 사전적 의미에 제한되지 않고 본 발명의 기술적 사상에 부합되는 의미로 적절히 해석되어야 할 것이다.In addition, the terms used below are selected for convenience of explanation, so in understanding the essential technical idea of the present invention, they are not limited to dictionary meanings and are appropriately interpreted as meanings that correspond to the technical idea of the present invention. It should be.

이하, 첨부된 도면을 참조하여 본 발명의 실시예를 상세히 설명하기로 한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

먼저, 본 발명의 일 실시예에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물은 수분산 폴리우레탄-우레아 접착수지와, 수분산폴리우레탄 점착부여제 등을 포함할 수 있다.First, the water-dispersible polyurethane adhesive composition for water-dissociable labels according to an embodiment of the present invention may include a water-dispersible polyurethane-urea adhesive resin, a water-dispersible polyurethane tackifier, etc.

여기에서, 수분산폴리우레탄-우레아 접착수지는 접착제의 영구접착력을 부여하기 위해 포함되는 것으로, 낮은 융점으로 인해 낮은 접착 온도가 가능한 장점이 있다.Here, the water-dispersed polyurethane-urea adhesive resin is included to provide permanent adhesion to the adhesive, and has the advantage of low adhesion temperature due to its low melting point.

예를 들면, 아디프산과 1,4 부탄디올로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI) 혹은 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI)와, 디메틸올부타노익산(Dimethylol Buthanoic Acid, DMBA)과, 1,4-부탄디올(1,4-BD)과, 트리에틸아민(TEA)과, 에틸렌디아민(EDA)으로 중합될 수 있다.For example, polyester polyol with a molecular weight of 2000 consisting of adipic acid and 1,4 butanediol, isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate (H 12 MDI), and dimethylol. It can be polymerized with Dimethylol Buthanoic Acid (DMBA), 1,4-butanediol (1,4-BD), triethylamine (TEA), and ethylenediamine (EDA).

이러한 수분산 폴리우레탄-우레아 접착수지는 융점 50-60 ℃의 핫멜트 형태의 접착제 특성을 제공할 수 있다.This water-dispersed polyurethane-urea adhesive resin can provide adhesive properties in the form of a hot melt with a melting point of 50-60°C.

그리고, 수분산 폴리우레탄-우레아 접착수지 내 프리폴리머의 NCO/(OH+NH2) 몰비는 1.2-1.5의 범위로 제공될 수 있는데, NCO/(OH+NH2) 몰비가 1.2 미만인 경우 최종 수분산 폴리우레탄-우레아수지의 분자량이 작아져 수분산 폴리우레탄 접착제의 코팅 후 건조 시에 점착성이 발현되어 이형필름이 필요한 문제점이 있고, NCO/(OH+NH2) 몰비가 1.5를 초과할 경우 최종 폴리우레탄-우레아수지의 하드시스먼트(Hard segment)의 함량이 높아지고 상대적으로 소프트시그먼트(Soft segment)의 결정화도가 낮아져 수분산 폴리우레탄 접착제의 접착강도가 떨어지는 문제점이 있다.In addition, the NCO/(OH+NH 2 ) molar ratio of the prepolymer in the water-dispersed polyurethane-urea adhesive resin can be provided in the range of 1.2-1.5. If the NCO/(OH+NH 2 ) molar ratio is less than 1.2, the final water dispersion There is a problem in that the molecular weight of polyurethane-urea resin is small, and adhesiveness develops when drying after coating with a water-dispersed polyurethane adhesive, requiring a release film. If the NCO/(OH+NH 2 ) molar ratio exceeds 1.5, the final poly There is a problem in that the adhesive strength of the water-dispersed polyurethane adhesive decreases as the content of the hard segment of the urethane-urea resin increases and the crystallinity of the soft segment relatively decreases.

또한, 수분산 폴리우레탄-우레아 접착수지에서 디메틸올부타노익산(DMBA)은 4-10 중량%로 하여 포함될 수 있는데, 디메틸올부타노익산(DMBA)이 4 중량% 미만일 경우 수해리성이 낮은 문제점이 있고, 디메틸올부타노익산(DMBA)이 10 중량%를 초과할 경우 접착수지 구조의 불균일성의 증가로 결정화도가 낮아 접착력이 떨어지는 문제점이 있다.In addition, in the water-dispersed polyurethane-urea adhesive resin, dimethylolbutanoic acid (DMBA) can be included at 4-10% by weight, but when dimethylolbutanoic acid (DMBA) is less than 4% by weight, water dissociability is low. In addition, when dimethylolbutanoic acid (DMBA) exceeds 10% by weight, the non-uniformity of the adhesive resin structure increases and the degree of crystallinity is low, leading to a decrease in adhesive strength.

바람직하게는, 상술한 바와 같은 수분산 폴리우레탄-우레아 접착수지 프리폴리머의 NCO/(OH+NH2) 몰비는 1.25-1.4로 하고, 디메틸올부타노익산(DMBA)은 4-6 중량%로 하여 포함될 경우 수분산 폴리우레탄 접착제의 접착력과 수해리성을 현저하게 향상시킬 수 있다.Preferably, the NCO/(OH+NH 2 ) molar ratio of the water-dispersed polyurethane-urea adhesive resin prepolymer as described above is set to 1.25-1.4, and the dimethylolbutanoic acid (DMBA) is set to 4-6% by weight. When included, it can significantly improve the adhesion and water dissociability of water-dispersed polyurethane adhesive.

수분산 폴리우레탄 점착부여제는 접착제의 초기접착력을 부여하기 위해 포함되는 것으로, 예를 들면, 아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI)와, 디메틸올부타노익산(DMBA)과, 트리에틸아민(TEA)을 이용하여 제조될 수 있다.A water-dispersible polyurethane tackifier is included to provide the initial adhesion of the adhesive. For example, polyester polyol with a molecular weight of 2000 consisting of adipic acid and neopentyl glycol, isophorone diisocyanate (IPDI), and dimethyl It can be manufactured using olbutanoic acid (DMBA) and triethylamine (TEA).

그리고, 수분산 폴리우레탄 점착부여제 내 폴리머의 NCO/OH 몰비는 0.7-1.2의 범위로 제공될 수 있는데, NCO/OH 몰비가 0.7 미만인 경우 점착성이 커서 수분산 폴리우레탄-우레아 접착수지와 혼합 시 점착성으로 인한 이형필름이 필요한 문제점이 있고, NCO/OH 몰비가 1.2를 초과할 경우 과량의 NCO로 인해 수분산 폴리우레탄 접착제의 시간에 따른 가교반응에 의한 점도가 상승하는 문제점이 있다.In addition, the NCO/OH molar ratio of the polymer in the water-dispersed polyurethane tackifier can be provided in the range of 0.7-1.2, and when the NCO/OH molar ratio is less than 0.7, the adhesiveness is large when mixed with the water-dispersed polyurethane-urea adhesive resin. There is a problem that a release film is required due to adhesiveness, and when the NCO/OH molar ratio exceeds 1.2, there is a problem that the viscosity of the water-dispersed polyurethane adhesive increases due to crosslinking reaction over time due to excessive NCO.

또한, 수분산 폴리우레탄 점착부여제에서 디메틸올부타노익산(DMBA)은 4-10 중량%로 하여 포함될 수 있는데, 디메틸올부타노익산(DMBA)이 4 중량% 미만일 경우 수해리성이 낮은 문제점이 있고, 디메틸올부타노익산(DMBA)이 10 중량%를 초과할 경우 점착성이 낮은 문제점이 있다.In addition, dimethylolbutanoic acid (DMBA) can be included at 4-10% by weight in the water-dispersed polyurethane tackifier, but if dimethylolbutanoic acid (DMBA) is less than 4% by weight, there is a problem of low water dissociability. There is a problem of low adhesion when dimethylolbutanoic acid (DMBA) exceeds 10% by weight.

바람직하게는, 상술한 바와 같은 수분산 폴리우레탄 점착부여제의 NCO/OH 몰비는 0.9-1.0으로 하고, 디메틸올부타노익산(DMBA)은 4-6 중량%로 하여 포함될 경우 수분산 폴리우레탄 접착제의 초기접착력 부여와 수해리성을 현저하게 향상시킬 수 있다.Preferably, the NCO/OH molar ratio of the water-dispersible polyurethane tackifier as described above is set to 0.9-1.0, and dimethylolbutanoic acid (DMBA) is included at 4-6% by weight to form a water-dispersed polyurethane adhesive. It can significantly improve initial adhesion and water dissociation.

상술한 바와 같은 수분산 폴리우레탄-우레아 접착수지와 수분산 폴리우레탄 점착부여제는 1/9-5/5의 중량비로 혼합될 수 있는데, 1/9 중량비 미만일 경우 수분산 폴리우레탄-우레아 접착수지의 결정화로 인해 시간에 지남에 따라 수축으로 인한 접착강도가 약화되는 문제점이 있고, 5/5 중량비를 초과할 경우 수분산 폴리우레탄 접착제의 코팅 후 건조 시에 점착성이 발현되는 문제점이 있다.As described above, the water-dispersible polyurethane-urea adhesive resin and the water-dispersible polyurethane tackifier can be mixed at a weight ratio of 1/9-5/5. If the weight ratio is less than 1/9, the water-dispersible polyurethane-urea adhesive resin There is a problem in that the adhesive strength weakens due to shrinkage over time due to crystallization, and when the weight ratio exceeds 5/5, there is a problem in that adhesiveness develops when drying after coating with the water-dispersed polyurethane adhesive.

바람직하게는, 접착제의 특성을 향상시키기 위해 수분산 폴리우레탄-우레아 접착수지와 수분산 폴리우레탄 점착부여제는 2/8-3/7의 중량비로 혼합될 수 있다.Preferably, to improve the properties of the adhesive, the water-dispersed polyurethane-urea adhesive resin and the water-dispersed polyurethane tackifier may be mixed at a weight ratio of 2/8-3/7.

따라서, 본 발명의 일 실시예에서는 영구접착력을 부여하는 수분산 폴리우레탄-우레아 접착수지와, 초기접착력을 부여하는 수분산 폴리우레탄 점착부여제를 포함함으로써, 접착수지와 점착부여제의 혼합비로 이형필름이 필요하지 않은 라벨용 접착제 조성물을 제공할 수 있고, 가수분해가 잘 진행되는 폴리에스터 폴리올의 사용과 디메틸올부타노익산(DMBA)의 함량 조절을 통해 수해리성과 접착성을 동시에 충족시킬 수 있다.Therefore, in one embodiment of the present invention, a water-dispersed polyurethane-urea adhesive resin that provides permanent adhesive force and a water-dispersed polyurethane tackifier that provides initial adhesive force are included, thereby enabling release at a mixing ratio of the adhesive resin and the tackifier. An adhesive composition for labels that does not require a film can be provided, and water dissociability and adhesiveness can be achieved simultaneously through the use of polyester polyol, which hydrolyzes well, and control of the content of dimethylolbutanoic acid (DMBA). there is.

한편, 도 1은 본 발명의 다른 실시예에 따라 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조하는 과정을 나타낸 플로우차트이다. Meanwhile, Figure 1 is a flow chart showing the process of manufacturing a water-dispersible polyurethane adhesive composition for a water-dissociable label according to another embodiment of the present invention.

도 1을 참조하면, 아디프산과 1,4 부탄디올로 이루어진 분자량 2000의 폴리에스터폴리올과, 디메틸올부타노익산과, 1,4-부탄디올을 이용하여 제 1 용융액을 제조할 수 있다(단계110).Referring to Figure 1, the first melt can be prepared using a polyester polyol with a molecular weight of 2000 consisting of adipic acid and 1,4 butanediol, dimethylolbutanoic acid, and 1,4-butanediol (step 110). .

예를 들면, 교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 수평균분자량 2000의 폴리부틸렌아디페이트 190-210 중량부와, 디메틸올부타노익산 10-15 중량부와, 1,4-부탄디올 3-4 중량부를 투입한 후 온도를 100-110℃로 높여 용융하여 분자량 2000의 폴리에스터폴리올 용융액(제 1 용융액)을 제조할 수 있다.For example, 190-210 parts by weight of polybutylene adipate with a number average molecular weight of 2000 and dimethylolbutanoic acid were added to a 1 liter four-necked flask equipped with a stirrer, cooler, thermometer, temperature controller, nitrogen inlet, and dropping funnel. After adding 10-15 parts by weight and 3-4 parts by weight of 1,4-butanediol, the temperature is raised to 100-110°C and melted to prepare a polyester polyol melt (first melt) with a molecular weight of 2000.

그리고, 제조된 폴리에스터폴리올 용융액에 이소포론디이소시아네이트(IPDI) 혹은 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI)와, 촉매를 투입하여 프리폴리머를 제조할 수 있다(단계120).Then, a prepolymer can be prepared by adding isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate (H 12 MDI) and a catalyst to the prepared polyester polyol melt (step 120). .

예를 들면, 제조된 폴리에스터폴리올 용융액을 온도 75-80℃로 냉각시키고, 적하깔대기를 이용하여 이소포론디이소시아네이트(IPDI) 67-72 중량부 또는 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI) 75-80 중량부를 메틸에틸케톤(MEK) 58-62 중량부에 녹여 투입하며, 여기에 비스무스 2-에틸헥사노에이트 0.2-0.3 중량부를 메틸에틸케톤(MEK) 18-22 중량부에 용해시켜 투입한 후, 교반속도 300-350rpm으로 1.5-2시간 동안 반응시켜 이소시아네이트 말단기를 가지면서 NCO/(OH+NH2) 작용기의 몰비가 1.2-1.5인 프리폴리머를 제조할 수 있다.For example, the prepared polyester polyol melt was cooled to a temperature of 75-80°C, and 67-72 parts by weight of isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate was added using a dropping funnel. (H 12 MDI) 75-80 parts by weight is dissolved in 58-62 parts by weight of methyl ethyl ketone (MEK) and added, and 0.2-0.3 parts by weight of bismuth 2-ethylhexanoate is added in 18-22 parts by weight of methyl ethyl ketone (MEK). After dissolving and adding it to the solution, it can be reacted at a stirring speed of 300-350 rpm for 1.5-2 hours to prepare a prepolymer having an isocyanate end group and a molar ratio of NCO/(OH+NH 2 ) functional groups of 1.2-1.5.

다음에, 제조된 프리폴리머에 트리에틸아민(TEA)을 투입하여 디메틸올부타노익산을 중화한 후, 고속 혼합으로 물에 수분산시켜 수분산된 프리폴리머를 제조할 수 있다(단계130).Next, triethylamine (TEA) is added to the prepared prepolymer to neutralize dimethylolbutanoic acid, and then dispersed in water by high-speed mixing to prepare a water-dispersed prepolymer (step 130).

예를 들면, 프리폴리머를 온도 45-50℃로 냉각한 후에, 트리에틸아민(TEA) 10-11 중량부를 메틸에틸케톤(MEK) 18-22 중량부에 녹여 투입하고, 1-1.5시간 동안 반응하여 디메틸올부타노익산(DMBA)을 중화시키며, 증류수 600-610 중량부를 상온에서 600-700rpm 범위로 교반하면서 중화시킨 프리폴리머를 투입하여 수분산된 프리폴리머를 수득할 수 있다.For example, after cooling the prepolymer to a temperature of 45-50°C, 10-11 parts by weight of triethylamine (TEA) was dissolved in 18-22 parts by weight of methyl ethyl ketone (MEK) and added, and reacted for 1-1.5 hours. Dimethylolbutanoic acid (DMBA) is neutralized, and a water-dispersed prepolymer can be obtained by adding 600-610 parts by weight of distilled water and adding the neutralized prepolymer while stirring at 600-700 rpm at room temperature.

또한, 수분산 프리폴리머에 에틸렌디아민(EDA)을 투입하여 수분산 폴리우레탄-우레아 접착수지를 제조할 수 있다(단계140).Additionally, water-dispersed polyurethane-urea adhesive resin can be prepared by adding ethylenediamine (EDA) to the water-dispersed prepolymer (step 140).

예를 들면, 에틸렌디아민(EDA) 3-4 중량부를 증류수 95-105 중량부에 녹인 수용액을 수분산된 프리폴리머에 적하깔대기를 이용하여 상온에서 18-22분 동안 투입하고, 1-1.5시간 동안 반응시킨 후에, 진공으로 메틸에틸케톤(MEK)을 제거하여 디메틸올부타노익산(DMBA) 4-10 중량%, 고형분 함량 28-32 중량%인 수분산 폴리우레탄-우레아 접착수지를 제조할 수 있다.For example, an aqueous solution of 3-4 parts by weight of ethylenediamine (EDA) dissolved in 95-105 parts by weight of distilled water was added to the water-dispersed prepolymer using a dropping funnel at room temperature for 18-22 minutes, and reacted for 1-1.5 hours. After doing so, methyl ethyl ketone (MEK) can be removed in vacuum to prepare a water-dispersed polyurethane-urea adhesive resin containing 4-10% by weight of dimethylolbutanoic acid (DMBA) and 28-32% by weight of solid content.

한편, 폴리우레탄 점착부여제는 다음과 같은 과정으로 제조할 수 있는데, 먼저 아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올과, 디메틸부타노익산(DMBA)을 투입하여 제 2 용융액을 제조할 수 있다(단계150).Meanwhile, the polyurethane tackifier can be manufactured by the following process. First, a polyester polyol with a molecular weight of 2000 consisting of adipic acid and neopentyl glycol and dimethylbutanoic acid (DMBA) are added to prepare a second melt. You can do it (step 150).

예를 들면, 교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 아디프산과 네오펜틸글리콜로 이루어진 수평균분자량 2000의 폴리에스터폴리올 220-230 중량부와, 디메틸올부타노익산(DMBA) 12-16 중량부를 투입한 후 온도를 100-110℃로 높여 용융할 수 있다. 여기에서, 아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올은 예를 들면, 폴리네오프로필렌아디페이트 등을 포함할 수 있다.For example, in a 1 liter four-necked flask equipped with a stirrer, cooler, thermometer, temperature controller, nitrogen inlet, dropping funnel, etc., 220-230 parts by weight of polyester polyol with a number average molecular weight of 2000 consisting of adipic acid and neopentyl glycol and , it can be melted by adding 12-16 parts by weight of dimethylolbutanoic acid (DMBA) and then raising the temperature to 100-110°C. Here, the polyester polyol with a molecular weight of 2000 composed of adipic acid and neopentyl glycol may include, for example, polyneopropylene adipate.

그리고, 상기 단계 150에서 제조된 용융액에 이소포론디이소시아네이트(IPDI)를 투입하여 폴리머를 제조할 수 있다(단계160).In addition, isophorone diisocyanate (IPDI) can be added to the melt prepared in step 150 to produce a polymer (step 160).

예를 들면, 제조된 용융액을 온도 75-80℃로 냉각시키고, 적하깔대기를 이용하여 이소포론디이소시아네이트(IPDI) 45-50 중량부를 메틸에틸케톤(MEK) 48-52 중량부에 녹여 투입하였으며, 여기에 비스무스 2-에틸헥사노에이트 0.2-0.3 중량부를 메틸에틸케톤(MEK) 8-12 중량부에 용해시켜 투입한 후, 교반속도 300-350rpm으로 2-2.5시간 동안 반응시켜 폴리머를 제조할 수 있다.For example, the prepared melt was cooled to a temperature of 75-80°C, and 45-50 parts by weight of isophorone diisocyanate (IPDI) was dissolved in 48-52 parts by weight of methyl ethyl ketone (MEK) using a dropping funnel. The polymer can be prepared by dissolving 0.2-0.3 parts by weight of bismuth 2-ethylhexanoate in 8-12 parts by weight of methyl ethyl ketone (MEK) and reacting for 2-2.5 hours at a stirring speed of 300-350 rpm. there is.

또한, 제조된 폴리머에 트리에틸아민(TEA)을 투입하여 디메틸올부타노익산을 중화한 후, 고속혼합으로 물에 분산시켜 수분산 폴리우레탄 점착부여제를 제조할 수 있다(단계170).In addition, triethylamine (TEA) is added to the prepared polymer to neutralize dimethylolbutanoic acid, and then dispersed in water by high-speed mixing to prepare a water-dispersed polyurethane tackifier (step 170).

예를 들면, 제조된 폴리머를 온도 45-50℃로 냉각한 후에, 트리에틸아민(TEA) 8-12 중량부를 메틸에틸케톤(MEK) 18-22 중량부에 녹여 투입하고, 1-1.5시간 동안 반응하여 디메틸올부타노익산(DMBA)을 중화시키며, 증류수 660-700 중량부를 상온에서 600-700rpm의 범위로 교반하면서 중화시킨 폴리머를 투입한 후에, 진공으로 메틸에틸케톤(MEK)을 제거하여 디메틸올부타노익산(DMBA) 4-6 중량%, 고형분 함량 28-32중량%, 작용기의 NCO/OH 몰비가 0.9-1.0인 수분산 폴리우레탄 점착부여제를 제조할 수 있다.For example, after cooling the prepared polymer to a temperature of 45-50°C, 8-12 parts by weight of triethylamine (TEA) was dissolved in 18-22 parts by weight of methyl ethyl ketone (MEK) and added, and incubated for 1-1.5 hours. Dimethylolbutanoic acid (DMBA) is reacted to neutralize, and 660-700 parts by weight of distilled water is added to the neutralized polymer while stirring at room temperature at 600-700 rpm, and then methyl ethyl ketone (MEK) is removed in vacuum to form dimethyl A water-dispersed polyurethane tackifier containing 4-6% by weight of olbutanoic acid (DMBA), a solid content of 28-32% by weight, and an NCO/OH molar ratio of the functional group of 0.9-1.0 can be prepared.

다음에, 상술한 바와 같은 과정을 통해 제조된 수분산 폴리우레탄-우레아 접착수지와 수분산 폴리우레탄 점착부여제를 기 설정된 중량비로 혼합하여 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조할 수 있다(단계180) 여기에서, 수분산 폴리우레탄-우레아 접착수지와 수분산 폴리우레탄 점착부여제는 1/9-5/5의 중량비로 혼합될 수 있다.Next, a water-dispersible polyurethane adhesive composition for a water-dissociable label can be prepared by mixing the water-dispersible polyurethane-urea adhesive resin prepared through the above-described process and the water-dispersible polyurethane tackifier at a preset weight ratio. (Step 180) Here, the water-dispersed polyurethane-urea adhesive resin and the water-dispersed polyurethane tackifier can be mixed at a weight ratio of 1/9-5/5.

따라서, 본 발명의 다른 실시예에서는 영구접착력을 부여하는 수분산 폴리우레탄-우레아 접착수지와, 초기접착력을 부여하는 수분산 폴리우레탄 점착부여제를 포함함으로써, 접착수지와 점착부여제의 혼합비로 이형필름이 필요하지 않은 라벨용 접착제 조성물을 제공할 수 있고, 쉽게 가수분해가 진행되는 폴리에스터폴리올의 사용과 디메틸올부타노익산(DMBA)의 함량 조절을 통해 수해리성과 접착성을 동시에 충족시킬 수 있다Therefore, in another embodiment of the present invention, by including a water-dispersed polyurethane-urea adhesive resin that provides permanent adhesive force and a water-dispersed polyurethane tackifier that provides initial adhesive force, release is achieved by the mixing ratio of the adhesive resin and the tackifier. An adhesive composition for labels that does not require a film can be provided, and water dissociability and adhesiveness can be achieved simultaneously through the use of easily hydrolyzed polyester polyol and control of the content of dimethylolbutanoic acid (DMBA). there is

다음에, 상술한 바와 같은 과정에 따라 제조되는 접착수지와 점착부여제의 다양한 실시예에 대해 설명하고, 접착수지 및 점착부여제를 다양한 중량비율에 따라 혼합한 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 특성에 대해 설명하기로 한다.Next, various examples of adhesive resins and tackifiers prepared according to the above-described process will be described, and water-dispersible polyurethane adhesives for water-dissociable labels in which adhesive resins and tackifiers are mixed at various weight ratios. The characteristics of the composition will be described.

[접착수지 제조예 1][Adhesive resin manufacturing example 1]

교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 수평균분자량 2000의 폴리부틸렌아디페이트 209g과, 디메틸부타노익산 13.9g과, 1,4-부탄디올 3.6g을 투입한 후 온도를 100℃로 높여 용융하였다.In a 1-liter four-necked flask equipped with a stirrer, cooler, thermometer, temperature controller, nitrogen inlet, and dropping funnel, 209 g of polybutylene adipate with a number average molecular weight of 2000, 13.9 g of dimethylbutanoic acid, and 1,4-butanediol were added. After adding 3.6g, the temperature was raised to 100°C and melted.

이러한 용융액을 온도 80℃로 냉각시키고, 적하깔대기를 이용하여 이소포론디이소시아네이트 69g을 메틸에틸케톤 60g에 녹여 투입하였으며, 여기에 비스무스 2-에틸헥사노에이트 0.26g을 메틸에틸케톤 20g에 용해시켜 투입한 후, 교반속도 300rpm으로 2시간 동안 반응시켜 이소시아네이트 말단기를 가지면서 NCO/(OH+NH2) 작용기의 몰비가 1.25인 프리폴리머를 제조하였다.This melt was cooled to a temperature of 80°C, and 69 g of isophorone diisocyanate was dissolved in 60 g of methyl ethyl ketone and added using a dropping funnel, and 0.26 g of bismuth 2-ethylhexanoate was dissolved in 20 g of methyl ethyl ketone and added thereto. Then, the mixture was reacted at a stirring speed of 300 rpm for 2 hours to prepare a prepolymer having an isocyanate end group and a molar ratio of NCO/(OH+NH 2 ) functional groups of 1.25.

상술한 바와 같은 과정을 통해 제조된 프리폴리머를 온도 50℃로 냉각한 후에, 트리에틸아민 10.28g을 메틸에틸케톤 20g에 녹여 투입하고, 1시간 동안 반응하여 디메틸올부타노익산을 중화시키며, 증류수 607g을 상온에서 600rpm 이상으로 교반하면서 중화시킨 프리폴리머를 투입하여 수분산된 프리폴리머를 수득하였다.After cooling the prepolymer prepared through the above-described process to a temperature of 50°C, 10.28 g of triethylamine was dissolved in 20 g of methyl ethyl ketone and added, reacted for 1 hour to neutralize dimethylolbutanoic acid, and 607 g of distilled water was added. The neutralized prepolymer was added while stirring at over 600 rpm at room temperature to obtain a water-dispersed prepolymer.

다음에, 에틸렌디아민 3.54g을 증류수 100g에 녹인 수용액을 수분산된 프리폴리머에 적하깔대기를 이용하여 상온에서 20분 동안 투입하고, 1시간 동안 반응시킨 후에, 진공으로 메틸에틸케톤을 제거하여 디메틸올부타노익산 5 중량%, 고형분 함량 30 중량%, 작용기의 NCO/(OH+NH2) 몰비가 1인 수분산 폴리우레탄-우레아 접착수지를 제조하였다.Next, an aqueous solution of 3.54 g of ethylenediamine dissolved in 100 g of distilled water was added to the water-dispersed prepolymer using a dropping funnel at room temperature for 20 minutes. After reaction for 1 hour, methyl ethyl ketone was removed in vacuum to form dimethylolbutane. A water-dispersed polyurethane-urea adhesive resin containing 5% by weight of noic acid, 30% by weight of solid content, and a functional group NCO/(OH+NH 2 ) molar ratio of 1 was prepared.

도 2는 본 발명에 따라 접착수지 제조예 1의 DSC를 나타내는 도면으로, 상술한 바와 같이 제조된 수분산 폴리우레탄-우레아 접착수지의 소프트시그먼트 융점은 약 50℃이며, 용융열은 15.88J/g으로 나타났다.Figure 2 is a diagram showing the DSC of Adhesive Resin Preparation Example 1 according to the present invention. The soft segment melting point of the water-dispersed polyurethane-urea adhesive resin prepared as described above is about 50°C, and the heat of fusion is 15.88J/ appeared as g.

[접착수지 제조예 2][Adhesive resin manufacturing example 2]

교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 수평균분자량 2000의 폴리부틸렌아디페이트 192g과, 디메틸올부타노익산 13.9g과, 1,4-부탄디올 3.42g을 투입한 후 온도를 100℃로 높여 용융하였다.In a 1 liter four-necked flask equipped with a stirrer, cooler, thermometer, temperature controller, nitrogen inlet, and dropping funnel, 192 g of polybutylene adipate with a number average molecular weight of 2000, 13.9 g of dimethylolbutanoic acid, and 1,4- After adding 3.42 g of butanediol, the temperature was raised to 100°C and melted.

이러한 용융액을 온도 80℃로 냉각시키고, 적하깔대기를 이용하여 디시클로헥실메탄-4,4'-디이소시아네이트 77.23g을 메틸에틸케톤 60g에 녹여 투입하였으며, 여기에 비스무스 2-에틸헥사노에이트 0.26g을 메틸에틸케톤 20g에 용해시켜 투입한 후, 교반속도 300rpm으로 2시간 동안 반응시켜 이소시아네이트 말단기를 가지면서 NCO/(OH+NH2) 작용기의 몰비가 1.25인 프리폴리머를 제조하였다.This melt was cooled to a temperature of 80°C, and 77.23 g of dicyclohexylmethane-4,4'-diisocyanate was dissolved in 60 g of methyl ethyl ketone and added using a dropping funnel, and 0.26 g of bismuth 2-ethylhexanoate was added thereto. was dissolved in 20 g of methyl ethyl ketone and reacted at a stirring speed of 300 rpm for 2 hours to prepare a prepolymer having an isocyanate end group and a molar ratio of NCO/(OH+NH 2 ) functional groups of 1.25.

상술한 바와 같은 과정을 통해 제조된 프리폴리머를 온도 50℃로 냉각한 후에, 트리에틸아민 10.28g을 메틸에틸케톤 20g에 녹여 투입하고, 1시간 동안 반응하여 디메틸올부타노익산을 중화시키며, 증류수 607g을 상온에서 600rpm 이상으로 교반하면서 중화시킨 프리폴리머를 투입하여 수분산된 프리폴리머를 수득하였다.After cooling the prepolymer prepared through the above-described process to a temperature of 50°C, 10.28 g of triethylamine was dissolved in 20 g of methyl ethyl ketone and added, reacted for 1 hour to neutralize dimethylolbutanoic acid, and 607 g of distilled water was added. The neutralized prepolymer was added while stirring at over 600 rpm at room temperature to obtain a water-dispersed prepolymer.

다음에, 에틸렌디아민 3.54g을 증류수 100g에 녹인 수용액을 수분산된 프리폴리머에 적하깔대기를 이용하여 상온에서 20분 동안 투입하고, 1시간 동안 반응시킨 후에, 진공으로 메틸에틸케톤을 제거하여 디메틸올부타노익산 5 중량%, 고형분 함량 30 중량%, 작용기의 NCO/(OH+NH2) 몰비가 1인 수분산 폴리우레탄-우레아 접착수지를 제조하였다.Next, an aqueous solution of 3.54 g of ethylenediamine dissolved in 100 g of distilled water was added to the water-dispersed prepolymer using a dropping funnel at room temperature for 20 minutes. After reaction for 1 hour, methyl ethyl ketone was removed in vacuum to form dimethylolbutane. A water-dispersed polyurethane-urea adhesive resin containing 5% by weight of noic acid, 30% by weight of solid content, and a functional group NCO/(OH+NH 2 ) molar ratio of 1 was prepared.

상술한 바와 같이 제조된 수분산 폴리우레탄-우레아 접착수지의 소프트시그먼트 융점은 약 60℃이며, 용융열은 18.5J/g으로 나타났다.The soft segment melting point of the water-dispersed polyurethane-urea adhesive resin prepared as described above was approximately 60°C, and the heat of fusion was 18.5 J/g.

[접착수지 제조예 3][Adhesive resin manufacturing example 3]

교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 수평균분자량 2000의 폴리부틸렌아디페이트 182g과, 디메틸올부타노익산 13.5g과, 1,4-부탄디올 3.14g을 투입한 후 온도를 100℃로 높여 용융하였다.182 g of polybutylene adipate with a number average molecular weight of 2000, 13.5 g of dimethylolbutanoic acid, and 1,4- After adding 3.14 g of butanediol, the temperature was raised to 100°C and melted.

이러한 용융액을 온도 80℃로 냉각시키고, 적하깔대기를 이용하여 이소포론디이소시아네이트 82g을 메틸에틸케톤 60g에 녹여 투입하였으며, 여기에 비스무스 2-에틸헥사노에이트 0.26g을 메틸에틸케톤 20g에 용해시켜 투입한 후, 교반속도 300rpm으로 2시간 동안 반응시켜 이소시아네이트 말단기를 가지면서 NCO/(OH+NH2) 작용기의 몰비가 1.7인 프리폴리머를 제조하였다.This melt was cooled to a temperature of 80°C, and 82 g of isophorone diisocyanate was dissolved in 60 g of methyl ethyl ketone and added using a dropping funnel, and 0.26 g of bismuth 2-ethylhexanoate was dissolved in 20 g of methyl ethyl ketone and added thereto. Then, the mixture was reacted at a stirring speed of 300 rpm for 2 hours to prepare a prepolymer having an isocyanate end group and a molar ratio of NCO/(OH+NH 2 ) functional groups of 1.7.

상술한 바와 같은 과정을 통해 제조된 프리폴리머를 온도 50℃로 냉각한 후에, 트리에틸아민 9.22g을 메틸에틸케톤 20g에 녹여 투입하고, 1시간 동안 반응하여 디메틸올부타노익산을 중화시키며, 증류수 626g을 상온에서 600rpm 이상으로 교반하면서 중화시킨 프리폴리머를 투입하여 수분산된 프리폴리머를 수득하였다.After cooling the prepolymer prepared through the above-described process to a temperature of 50°C, 9.22 g of triethylamine was dissolved in 20 g of methyl ethyl ketone and added, reacted for 1 hour to neutralize dimethylolbutanoic acid, and 626 g of distilled water was added. The neutralized prepolymer was added while stirring at over 600 rpm at room temperature to obtain a water-dispersed prepolymer.

다음에, 에틸렌디아민 9.13g을 증류수 100g에 녹인 수용액을 수분산된 프리폴리머에 적하깔대기를 이용하여 상온에서 20분 동안 투입하고, 1시간 동안 반응시킨 후에, 진공으로 메틸에틸케톤을 제거하여 디메틸올부타노익산 4.5 중량%, 고형분 함량 30 중량%, 작용기의 NCO/(OH+NH2) 몰비가 1인 수분산 폴리우레탄-우레아 접착수지를 제조하였다.Next, an aqueous solution of 9.13 g of ethylenediamine dissolved in 100 g of distilled water was added to the water-dispersed prepolymer using a dropping funnel at room temperature for 20 minutes. After reacting for 1 hour, methyl ethyl ketone was removed in vacuum to form dimethylolbutane. A water-dispersed polyurethane-urea adhesive resin was prepared with 4.5% by weight of noic acid, 30% by weight of solid content, and a molar ratio of NCO/(OH+NH 2 ) of the functional group of 1.

상술한 바와 같이 제조된 수분산 폴리우레탄-우레아 접착수지의 소프트시그먼트 융점은 약 50℃이며, 용융열은 0.84J/g으로 나타났다.The soft segment melting point of the water-dispersed polyurethane-urea adhesive resin prepared as described above was approximately 50°C, and the heat of fusion was 0.84 J/g.

[접착수지 제조예 4][Adhesive resin manufacturing example 4]

교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 수평균분자량 2000의 폴리부틸렌아디페이트 201g과, 디메틸올부타노익산 10.6g과, 1,4-부탄디올 3.6g을 투입한 후 온도를 100℃로 높여 용융하였다.201 g of polybutylene adipate with a number average molecular weight of 2000, 10.6 g of dimethylolbutanoic acid, and 1,4- After adding 3.6 g of butanediol, the temperature was raised to 100°C and melted.

이러한 용융액을 온도 80℃로 냉각시키고, 적하깔대기를 이용하여 디시클로헥실메탄-4,4'-디이소시아네이트 69.7g을 메틸에틸케톤 60g에 녹여 투입하였으며, 여기에 비스무스 2-에틸헥사노에이트 0.26g을 메틸에틸케톤 20g에 용해시켜 투입한 후, 교반속도 300rpm으로 2시간 동안 반응시켜 이소시아네이트 말단기를 가지면서 NCO/(OH+NH2) 작용기의 몰비가 1.25인 프리폴리머를 제조하였다.This melt was cooled to a temperature of 80°C, and 69.7 g of dicyclohexylmethane-4,4'-diisocyanate was dissolved in 60 g of methyl ethyl ketone and added using a dropping funnel, and 0.26 g of bismuth 2-ethylhexanoate was added thereto. was dissolved in 20 g of methyl ethyl ketone and reacted at a stirring speed of 300 rpm for 2 hours to prepare a prepolymer having an isocyanate end group and a molar ratio of NCO/(OH+NH 2 ) functional groups of 1.25.

상술한 바와 같은 과정을 통해 제조된 프리폴리머를 온도 50℃로 냉각한 후에, 트리에틸아민 7.27g을 메틸에틸케톤 20g에 녹여 투입하고, 1시간 동안 반응하여 디메틸올부타노익산을 중화시키며, 증류수 594g을 상온에서 600rpm 이상으로 교반하면서 중화시킨 프리폴리머를 투입하여 수분산된 프리폴리머를 수득하였다.After cooling the prepolymer prepared through the above-described process to a temperature of 50°C, 7.27 g of triethylamine was dissolved in 20 g of methyl ethyl ketone and added, reacted for 1 hour to neutralize dimethylolbutanoic acid, and 594 g of distilled water was added. The neutralized prepolymer was added while stirring at over 600 rpm at room temperature to obtain a water-dispersed prepolymer.

다음에, 에틸렌디아민 3.19g을 증류수 100g에 녹인 수용액을 수분산된 프리폴리머에 적하깔대기를 이용하여 상온에서 20분 동안 투입하고, 1시간 동안 반응시킨 후에, 진공으로 메틸에틸케톤을 제거하여 디메틸올부타노익산 3.6 중량%, 고형분 함량 30 중량%, 작용기의 NCO/(OH+NH2) 몰비가 1인 수분산 폴리우레탄-우레아 접착수지를 제조하였다.Next, an aqueous solution of 3.19 g of ethylenediamine dissolved in 100 g of distilled water was added to the water-dispersed prepolymer using a dropping funnel at room temperature for 20 minutes. After reaction for 1 hour, methyl ethyl ketone was removed in vacuum to form dimethylolbutane. A water-dispersed polyurethane-urea adhesive resin was prepared with 3.6% by weight of noic acid, 30% by weight of solid content, and a molar ratio of NCO/(OH+NH 2 ) of the functional group of 1.

상술한 바와 같이 제조된 수분산 폴리우레탄-우레아 접착수지의 소프트시그먼트 융점은 약 55℃이며, 용융열은 23.2J/g으로 나타났다.The soft segment melting point of the water-dispersed polyurethane-urea adhesive resin prepared as described above was approximately 55°C, and the heat of fusion was 23.2 J/g.

[점착부여제 제조예 1][Tackifier Preparation Example 1]

교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 수평균분자량 2000의 폴리네오프로필렌아디페이트 224g과, 디메틸올부타노익산 15.1g을 투입한 후 온도를 100℃로 높여 용융하였다.224 g of polyneopropylene adipate with a number average molecular weight of 2000 and 15.1 g of dimethylolbutanoic acid were added to a 1 liter four-necked flask equipped with a stirrer, cooler, thermometer, temperature controller, nitrogen inlet, and dropping funnel, and then the temperature was adjusted. It was melted by raising the temperature to 100℃.

이러한 용융액을 온도 80℃로 냉각시키고, 적하깔대기를 이용하여 이소포론디이소시아네이트 47.6g을 메틸에틸케톤 50g에 녹여 투입하였으며, 여기에 비스무스 2-에틸헥사노에이트 0.26g을 메틸에틸케톤 10g에 용해시켜 투입한 후, 교반속도 300rpm으로 2시간 동안 반응시켜 폴리머를 제조하였다.This melt was cooled to a temperature of 80°C, and 47.6 g of isophorone diisocyanate was dissolved in 50 g of methyl ethyl ketone using a dropping funnel, and 0.26 g of bismuth 2-ethylhexanoate was dissolved in 10 g of methyl ethyl ketone. After addition, the polymer was prepared by reacting for 2 hours at a stirring speed of 300 rpm.

상술한 바와 같이 제조된 폴리머를 온도 50℃로 냉각한 후에, 트리에틸아민 10g을 메틸에틸케톤 20g에 녹여 투입하고, 1시간 동안 반응하여 디메틸올부타노익산을 중화시키며, 증류수 696g을 상온에서 600rpm 이상으로 교반하면서 중화시킨 폴리머를 투입하였다.After cooling the polymer prepared as described above to a temperature of 50°C, 10 g of triethylamine was dissolved in 20 g of methyl ethyl ketone and added, reacted for 1 hour to neutralize dimethylolbutanoic acid, and 696 g of distilled water was added at 600 rpm at room temperature. The neutralized polymer was added while stirring.

다음에, 진공으로 메틸에틸케톤을 제거하여 디메틸올부타노익산 5 중량%, 고형분 함량 30 중량%, 작용기의 NCO/OH 몰비가 1인 수분산 폴리우레탄 점착부여제를 제조하였다.Next, methyl ethyl ketone was removed in vacuum to prepare a water-dispersed polyurethane tackifier containing 5% by weight of dimethylolbutanoic acid, 30% by weight of solid content, and an NCO/OH molar ratio of the functional group of 1.

[점착부여제 제조예 2][Tackifier Preparation Example 2]

교반기, 냉각기, 온도계, 온도 컨트롤러, 질소유입구, 적하깔대기 등이 장착된 1ℓ의 4구 플라스크에 수평균분자량 2000의 폴리네오프로필렌아디페이트 224g과, 디메틸올부타노익산 12.8g을 투입한 후 온도를 100℃로 높여 용융하였다.224 g of polyneopropylene adipate with a number average molecular weight of 2000 and 12.8 g of dimethylolbutanoic acid were added to a 1 liter four-necked flask equipped with a stirrer, cooler, thermometer, temperature controller, nitrogen inlet, and dropping funnel, and then the temperature was adjusted. It was melted by raising it to 100℃.

이러한 용융액을 온도 80℃로 냉각시키고, 적하깔대기를 이용하여 이소포론디이소시아네이트 39.7g을 메틸에틸케톤 50g에 녹여 투입하였으며, 여기에 비스무스 2-에틸헥사노에이트 0.26g을 메틸에틸케톤 10g에 용해시켜 투입한 후, 교반속도 300rpm으로 2시간 동안 반응시켜 폴리머를 제조하였다.This melt was cooled to a temperature of 80°C, and 39.7 g of isophorone diisocyanate was dissolved in 50 g of methyl ethyl ketone using a dropping funnel, and 0.26 g of bismuth 2-ethylhexanoate was dissolved in 10 g of methyl ethyl ketone. After addition, the polymer was prepared by reacting for 2 hours at a stirring speed of 300 rpm.

상술한 바와 같이 제조된 폴리머를 온도 50℃로 냉각한 후에, 트리에틸아민 8.7g을 메틸에틸케톤 20g에 녹여 투입하고, 1시간 동안 반응하여 디메틸올부타노익산을 중화시키며, 증류수 666g을 상온에서 600rpm 이상으로 교반하면서 중화시킨 폴리머를 투입하였다.After cooling the polymer prepared as described above to a temperature of 50°C, 8.7 g of triethylamine was dissolved in 20 g of methyl ethyl ketone and added, reacted for 1 hour to neutralize dimethylolbutanoic acid, and 666 g of distilled water was added at room temperature. The neutralized polymer was added while stirring at over 600 rpm.

다음에, 진공으로 메틸에틸케톤을 제거하여 디메틸올부타노익산 4.5 중량%, 고형분 함량 30 중량%, 작용기의 NCO/OH 몰비가 0.9인 수분산 폴리우레탄 점착부여제를 제조하였다.Next, methyl ethyl ketone was removed in vacuum to prepare a water-dispersed polyurethane tackifier containing 4.5% by weight of dimethylolbutanoic acid, a solid content of 30% by weight, and an NCO/OH molar ratio of the functional group of 0.9.

[수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조예 및 그 특성][Manufacture example of water-dispersible polyurethane adhesive composition for water-dissociable labels and its characteristics]

상술한 바와 같은 과정을 통해 제조된 수분산 폴리우레탄-우레아 접착수지와 수분산 폴리우레탄 점착부여제를 아래의 표 1에 도시된 바와 같이 다양한 중량비율로 혼합하여 본 발명의 실시예에 따른 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조하였다.The water-dispersible polyurethane-urea adhesive resin prepared through the above-described process and the water-dispersed polyurethane tackifier were mixed in various weight ratios as shown in Table 1 below to obtain water dissociability according to an embodiment of the present invention. A water-dispersible polyurethane adhesive composition for labels was prepared.

상술한 바와 같이 제조된 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 코로나처리된 80㎛ 백색합성지(OPP)에 코팅한 후, 110℃에서 1분간 건조하고, 10㎛의 접착면을 제조하였다.The water-dispersible polyurethane adhesive composition for water-dissociable labels prepared as described above was coated on corona-treated 80㎛ white synthetic paper (OPP), dried at 110°C for 1 minute, and a 10㎛ adhesive surface was prepared.

그리고, 코팅된 접착면의 점착성 여부를 손으로 확인하였고, 코팅된 접착면에 80㎛ 폴리에틸렌 테레프탈레이트(PET)를 90℃에서 4bar의 압력으로 5초간 압착하여 접착 시편을 수득하였다.Then, the adhesiveness of the coated adhesive surface was checked by hand, and an adhesive specimen was obtained by pressing 80㎛ polyethylene terephthalate (PET) on the coated adhesive surface for 5 seconds at 90°C with a pressure of 4 bar.

이러한 접착 시편을 25mm폭으로 절단하여 180ㅀ 박리테스트를 진행하였고, 그 접착력은 초기접착력과 120시간 후의 접착력으로 측정하였다. 여기에서, 도 3은 본 발명에 따라 제조한 수해리성 라벨용 접착조성물의 수해리 결과, 라벨지와 PET가 분리되는 현상을 나타내는 도면이다.These adhesive specimens were cut to a width of 25 mm and subjected to a 180° peel test, and the adhesive strength was measured as the initial adhesive strength and the adhesive strength after 120 hours. Here, Figure 3 is a diagram showing the phenomenon of separation of label paper and PET as a result of water dissociation of the water-dissociable adhesive composition for labels prepared according to the present invention.

또한, 접착 시편을 6-8mm의 크기로 분쇄하였고, 분쇄된 접착 시편 100개를 80-90℃로 가열된 2 중량%의 수산화나트륨 수용액에 넣은 후 20분간 교반하였으며, 이 후 박리가 되어 수산화나트륨 수용액에 부유하는 합성지의 수와 침강된 박리된 PET 플레이크에 접착제 잔사가 남았는지의 여부를 확인하여 수해리성을 평가하였다.In addition, the adhesive specimens were crushed to a size of 6-8 mm, and 100 crushed adhesive specimens were placed in a 2% by weight aqueous sodium hydroxide solution heated to 80-90°C and stirred for 20 minutes, and then peeled to form sodium hydroxide. Water dissociation was evaluated by checking the number of synthetic papers floating in the aqueous solution and whether adhesive residue remained in the precipitated peeled PET flakes.

종합적으로 접착면에 점착성이 없는 것, 초기접착력 및 120시간 후 접착력이 50kgf/25mm이상이며, 박리된 시편의 수가 95개 이상인 것, 박리된 합성지나 PET 표면에 접착성분의 잔사가 없는 것이 수해리성 접착제로 적합한 것으로 판단하였고, 그 결과는 상기 표 1에 나타낸 바와 같다.Overall, water dissociation is indicated by no adhesiveness on the adhesive surface, initial adhesive strength and adhesive strength after 120 hours of more than 50kgf/25mm, number of peeled specimens of more than 95, and no adhesive residue on the surface of peeled synthetic paper or PET. It was judged to be suitable as an adhesive, and the results are as shown in Table 1 above.

Claims (10)

아디프산과 1,4 부탄디올로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI) 혹은 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI)와, 디메틸올부타노익산(DMBA)과, 1,4-부탄디올(1,4-BD)과, 트리에틸아민(TEA)과, 에틸렌디아민(EDA)으로 중합된 수분산 폴리우레탄-우레아 접착수지; 및
아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올과, 이소포론디이소시아네이트(IPDI)와, 디메틸올부타노익산(DMBA)과, 트리에틸아민(TEA)으로 이용하여 제조된 수분산 폴리우레탄 점착부여제;
를 포함하는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물.Polyester polyol with a molecular weight of 2000 consisting of adipic acid and 1,4 butanediol, isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate (H 12 MDI), and dimethylolbutanoic acid ( A water-dispersed polyurethane-urea adhesive resin polymerized with DMBA), 1,4-butanediol (1,4-BD), triethylamine (TEA), and ethylenediamine (EDA); and
Water-dispersed polyurethane produced using polyester polyol with a molecular weight of 2000 composed of adipic acid and neopentyl glycol, isophorone diisocyanate (IPDI), dimethylolbutanoic acid (DMBA), and triethylamine (TEA). Tackifier;
A water-dispersible polyurethane adhesive composition for water-dissociable labels containing. 청구항 1에 있어서,
상기 수분산 폴리우레탄-우레아 접착수지와 상기 수분산 폴리우레탄 점착부여제의 중량비는, 1/9-5/5로 하여 혼합되는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물.In claim 1,
A water-dispersible polyurethane adhesive composition for a water-dissociable label wherein the water-dispersible polyurethane-urea adhesive resin and the water-dispersible polyurethane tackifier are mixed at a weight ratio of 1/9-5/5. 청구항 1에 있어서,
상기 수분산 폴리우레탄-우레아 접착수지는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함되는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물.In claim 1,
The water-dispersible polyurethane-urea adhesive resin is a water-dispersible polyurethane adhesive composition for labels containing 4-10% by weight of dimethylolbutanoic acid (DMBA). 청구항 1에 있어서,
상기 수분산 폴리우레탄 점착부여제는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함되는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물.In claim 1,
The water-dispersible polyurethane tackifier is a water-dispersible polyurethane adhesive composition for labels containing 4-10% by weight of dimethylolbutanoic acid (DMBA). 청구항 1에 있어서,
상기 수분산 폴리우레탄-우레아 접착수지를 제조하기 위한 프리폴리머는, NCO/(OH+NH2) 몰비가 1.2-1.5의 범위로 제공되는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물.In claim 1,
The prepolymer for producing the water-dispersible polyurethane-urea adhesive resin is a water-dispersible polyurethane adhesive composition for labels, wherein the NCO/(OH+NH 2 ) molar ratio is in the range of 1.2-1.5. 청구항 1에 있어서,
상기 수분산 폴리우레탄 점착부여제는, NCO/OH 몰비가 0.7-1.2의 범위로 제공되는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물.In claim 1,
The water-dispersible polyurethane tackifier is a water-dispersible polyurethane adhesive composition for a water-dissociable label, wherein the NCO/OH molar ratio is in the range of 0.7-1.2. 아디프산과 1,4 부탄디올로 이루어진 분자량 2000의 폴리에스터폴리올과, 디메틸올부타노익산과, 1,4-부탄디올을 이용하여 제 1 용융액을 제조하는 단계;
상기 제조된 제 1 용융액에 이소포론디이소시아네이트(IPDI) 혹은 디시클로헥실메탄-4,4'-디이소시아네이트(H12MDI)을 투입하여 프리폴리머를 제조하는 단계;
상기 제조된 프리폴리머에 트리에틸아민(TEA)을 투입하여 수분산된 프리폴리머를 제조하는 단계;
상기 제조된 수분산 프리폴리머에 에틸렌디아민(EDA)을 투입하여 수분산 폴리우레탄-우레아 접착수지를 제조하는 단계;
아디프산과 네오펜틸글리콜로 이루어진 분자량 2000의 폴리에스터폴리올과, 디메틸올부타노익산(DMBA)을 투입하여 제 2 용융액을 제조하는 단계;
상기 제조된 제 2 용융액에 이소포론디이소시아네이트(IPDI)를 투입하여 폴리머를 제조하는 단계;
상기 제조된 폴리머에 트리에틸아민(TEA)을 투입하여 수분산 폴리우레탄 점착부여제를 제조하는 단계; 및
상기 수분산 폴리우레탄-우레아 접착수지와 상기 수분산 폴리우레탄 점착부여제를 기 설정된 중량비로 혼합하여 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조하는 단계;
를 포함하는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법.Preparing a first melt using a polyester polyol with a molecular weight of 2000 consisting of adipic acid and 1,4 butanediol, dimethylolbutanoic acid, and 1,4-butanediol;
Preparing a prepolymer by adding isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate (H 12 MDI) to the prepared first melt;
Preparing a water-dispersed prepolymer by adding triethylamine (TEA) to the prepared prepolymer;
Preparing a water-disperse polyurethane-urea adhesive resin by adding ethylenediamine (EDA) to the water-disperse prepolymer prepared above;
Preparing a second melt by adding a polyester polyol with a molecular weight of 2000 consisting of adipic acid and neopentyl glycol and dimethylolbutanoic acid (DMBA);
Preparing a polymer by adding isophorone diisocyanate (IPDI) to the prepared second melt;
Preparing a water-dispersed polyurethane tackifier by adding triethylamine (TEA) to the prepared polymer; and
Mixing the water-dispersible polyurethane-urea adhesive resin and the water-dispersible polyurethane tackifier at a preset weight ratio to prepare a water-dispersible polyurethane adhesive composition for a water-dissociable label;
A method for producing a water-dispersible polyurethane adhesive composition for water-dissociable labels, comprising: 청구항 7에 있어서,
상기 수분산 폴리우레탄-우레아 접착수지를 제조하는 단계는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함되고, 상기 프리폴리머의 NCO/(OH+NH2) 몰비가 1.2-1.5의 범위가 되도록 상기 수분산 폴리우레탄-우레아 접착수지를 제조하는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법.In claim 7,
In the step of preparing the water-dispersed polyurethane-urea adhesive resin, dimethylolbutanoic acid (DMBA) is included at 4-10% by weight, and the NCO/(OH+NH 2 ) molar ratio of the prepolymer is 1.2-1.5. A method for producing a water-dispersible polyurethane adhesive composition for a water-dissociable label, wherein the water-dispersible polyurethane-urea adhesive resin is produced in the range of. 청구항 7에 있어서,
상기 수분산 폴리우레탄 점착부여제를 제조하는 단계는, 디메틸올부타노익산(DMBA)이 4-10 중량%로 하여 포함되고, NCO/OH 몰비가 0.7-1.2의 범위가 되도록 상기 수분산 폴리우레탄 점착부여제를 제조하는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법.In claim 7,
In the step of preparing the water-dispersed polyurethane tackifier, dimethylolbutanoic acid (DMBA) is included at 4-10% by weight, and the water-dispersed polyurethane is added so that the NCO / OH molar ratio is in the range of 0.7-1.2. Method for producing a water-dispersible polyurethane adhesive composition for water-dissociable labels using a tackifier. 청구항 7에 있어서,
상기 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물을 제조하는 단계는, 상기 수분산 폴리우레탄-우레아 접착수지와 상기 수분산 폴리우레탄 점착부여제를 1/9-5/5의 중량비로 혼합하는 수해리성 라벨용 수분산 폴리우레탄 접착제 조성물의 제조 방법.In claim 7,
The step of preparing the water-dispersible polyurethane adhesive composition for labels includes mixing the water-dispersible polyurethane-urea adhesive resin and the water-dispersible polyurethane tackifier at a weight ratio of 1/9-5/5. Method for producing a water-dispersible polyurethane adhesive composition for labels.
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