KR20070070855A - Hot-melt adhesive type water dispersible copolyester composition - Google Patents
Hot-melt adhesive type water dispersible copolyester composition Download PDFInfo
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- KR20070070855A KR20070070855A KR1020050133813A KR20050133813A KR20070070855A KR 20070070855 A KR20070070855 A KR 20070070855A KR 1020050133813 A KR1020050133813 A KR 1020050133813A KR 20050133813 A KR20050133813 A KR 20050133813A KR 20070070855 A KR20070070855 A KR 20070070855A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/50—Polyesters chemically modified by esterification by monohydric alcohols
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
Description
본 발명은 열용융 접착형 수분산성 코폴리에스테르 수지 조성물에 관한 것으로서, 더욱 상세하게는 설폰산 금속염기를 함유하는 디카르본산 또는 이들의 유도체, 디카르본산, 그리고 디올 성분을 공중합시킨 열용융 접착형 수분산성 코폴리에스테르 수지 조성물에 관한 것이다.The present invention relates to a hot melt adhesive type water dispersible copolyester resin composition, and more particularly, to a hot melt adhesive obtained by copolymerizing a dicarboxylic acid containing a sulfonic acid metal base or a derivative thereof, a dicarboxylic acid, and a diol component. It relates to a type water dispersible copolyester resin composition.
일반적으로 필름은 인쇄 후 내용물을 포장한 다음 열접착 등의 방법으로 마무리하여 포장 등의 용도로 사용하고 있다. 그러나 대부분의 필름이 수지 조성물로 이루어져 있어 필름 표면에 직접 인쇄가 불가능하고 그 자체로는 열접착이 어렵다.그래서 이러한 문제점을 해결하기 위하여 필름 제조시 다른 수지 조성물을 공압출하거나 또는 다른 수지 조성물을 필름 표면에 도포하는 등의 방법을 사용하여 왔다. 그러나 상기 방법에 의한 경우 필름과 공압출하거나 또는 필름에 도포되는 수지 조성물과 필름과의 수축차이 등에 의해 필름에 주름이 생기고, 인쇄잉크조성물과의 친화력 및 열접착성능 등의 물성이 부족하여 도포된 표면이 부스러지며, 도포된 필름은 투명성 또는 광택이 불량하고, 도포된 수지 조성물이 용융과 같은 재가 공 등이 불가능하므로 필름의 재생이 불가능하며, 또한 유기용매 사용으로 인한 환경오염 문제를 야기하는 등 여러 문제점이 지적되었다.In general, the film is used for packaging purposes by wrapping the contents after printing and then finishing by heat bonding or the like. However, most of the film is composed of a resin composition, which makes it impossible to directly print on the surface of the film and is difficult to heat bond by itself. The method of apply | coating to the surface has been used. However, according to the above method, wrinkles are formed on the film due to co-extrusion with the film or shrinkage difference between the resin composition and the film applied to the film, and the film has insufficient physical properties such as affinity with the printing ink composition and thermal adhesion performance. The surface is broken, the coated film is poor in transparency or gloss, and the coated resin composition cannot be reprocessed, such as melting, so that the film cannot be regenerated, and also causes environmental pollution problems due to the use of organic solvents. Several problems have been pointed out.
대한민국특허공고 제93-5141호, 일본특허공고 소47-4-873, 일본특허공고 소56-5476호, 일본특허공고 소56-88454호 및 일본특허공개 평4-226562호 등에서는 상기 필름코팅 수지 조성물에서 나타나는 문제점을 개선하기 위하여 설폰산 금속염기를 함유하는 디카르본산 또는 이들의 유도체를 또다른 디카르본산 또는 이들의 유도체 그리고 디올 성분과 공중합시켜 수분산성 코폴리에스테르 수지 조성물을 제조한 후, 이를 단독으로 또는 다른 첨가제와 함께 물 또는 물과 알코올의 혼합용매에 분산시켜 필름코팅용 수분산성 코폴리에스테르 수지 조성물을 제조하였다. 그러나 이러한 제조방법에 의해 제조된 수지의 유리전이온도(Tg)가 충분히 높은 경우 이를 필름 등에 코팅하면 도포층이 쉽게 부스러지거나 열접착성이 부족한 문제가 있고, 수지의 유리전이온도(Tg)가 낮을 경우 필름 등에 코팅한 후 도포된 필름을 쌓아놓거나 롤상으로 감아놓을 경우 필름들이 서로 점착되는 등의 문제가 있다.Korean Patent Publication No. 93-5141, Japanese Patent Publication No. 47-4-873, Japanese Patent Publication No. 56-5476, Japanese Patent Publication No. 56-88454, and Japanese Patent Publication No. 4-226562, etc. In order to improve the problems in the resin composition, a dicarboxylic acid or derivative thereof containing a sulfonic acid metal base is copolymerized with another dicarboxylic acid or a derivative thereof and a diol component to prepare a water dispersible copolyester resin composition. In addition, it was dispersed alone or in combination with other additives in water or a mixed solvent of water and alcohol to prepare a water-dispersible copolyester resin composition for film coating. However, if the glass transition temperature (Tg) of the resin produced by such a manufacturing method is sufficiently high, coating it on a film or the like has a problem that the coating layer is easily brittle or lacks thermal adhesiveness, and the glass transition temperature (Tg) of the resin is low. In this case, when the coated film is stacked or rolled up after being coated in a film or the like, the films are adhered to each other.
열용융형 접착제는 캐리어 유체없이 사용할 경우 접착층을 얇게 만들기 힘들고, 유기용제를 캐리어 유체로 사용하여 코팅 및 건조하여 접착층을 만들 경우 접착층을 얇게 만들 수는 있으나 유기용제에 의한 환경오염 및 작업환경에 악영향을 미쳐, 수용성이면서 열용융형인 접착제의 개발이 요구되어 왔다.Heat-melting adhesives are difficult to make the adhesive layer thin when used without carrier fluid, and can be made thin when the adhesive layer is made by coating and drying using organic solvent as carrier fluid, but adversely affects the environmental pollution and working environment by organic solvent In addition, the development of water-soluble and hot melt adhesives has been required.
이에 본 발명에서는, 광범위한 연구를 수행하여 디카르본산 및 설폰산 금속염기를 함유하는 디카르본산 또는 이들의 유도체를 디올 성분과 산성분 완충제하에서 공중합시켜 디에틸글리콜의 생성을 최소화하고, 원료의 조성을 조절하여 수분산 이 가능하면서도 결정성을 지닌 수지 조성물을 제조할 수 있었다.Accordingly, in the present invention, extensive research has been carried out to copolymerize dicarboxylic acid or a derivative thereof containing a dicarboxylic acid and sulfonic acid metal base under a diol component and an acid component buffer to minimize the production of diethyl glycol and to improve the composition of the raw material. It was possible to prepare a resin composition having crystallinity while being able to disperse by adjusting.
본 발명은 열용융형 수분산성 코폴리에스테르 수지 조성물에 관한 것으로서, 더욱 상세하게는 설폰산 금속염기를 함유하는 디카르본산 또는 이들의 유도체, 디카르본산, 그리고 디올 성분을 공중합시킨 열용융형 수분산성 코폴리에스테르 수지조성물에 관한 것으로 본 발명의 수분산성 코폴리에스테르 수지 조성물은 수분산성이 우수하면서도, 라미네이팅 적층제에 코팅 및 건조 후 용융 접착성이 우수하여 각종 재료에 대하여 견고하게 접착된다. The present invention relates to a hot melt water dispersible copolyester resin composition, and more particularly, to a hot melt moisture copolymer obtained by copolymerizing a dicarboxylic acid containing a sulfonic acid metal base or a derivative thereof, a dicarboxylic acid, and a diol component. The present invention relates to an acidic copolyester resin composition, wherein the water-dispersible copolyester resin composition of the present invention has excellent water dispersibility, and is excellent in melt adhesiveness after coating and drying on a laminating laminate, and thus firmly adheres to various materials.
또한, 접착 후 빠른 결정화를 통한 접착층의 내열성, 유기용매에 대한 내화학성, 내가수분해성, 기계적 강도 및 접착층의 외부 노출 시의 비점착성(tack-free)이 우수하고, 외부응력(열충격) 및 내부응력(기초수지의 결정화에 따른 수축현상)에 의한 저항력(치수안정성)이 확보되어 있으며, 우수한 탄성 및 굴곡성이 있다. 이러한 특성으로 인하여, 상기 조성물은 PVC, PET, PC, PMMA 계의 필름형태와 철, 알루미늄, 구리 및 각종 합금(예: 스테인레스 강, 주석 플레이트, EGI 강 시트 등) 및 종이류 등과의 라미네이팅 적층체에서 접착층으로서 유용하다. 또한, 상기 기재 이외의 적층제에서도 접착층으로서 유용하다.In addition, it is excellent in heat resistance of the adhesive layer through rapid crystallization after adhesion, chemical resistance to organic solvents, hydrolysis resistance, mechanical strength and tack-free at the external exposure of the adhesive layer, external stress (thermal shock) and internal Resistance (dimension stability) due to stress (shrinkage due to crystallization of base resin) is secured, and has excellent elasticity and flexibility. Due to these properties, the composition can be used in laminating laminates of PVC, PET, PC, PMMA-based films and iron, aluminum, copper and various alloys (e.g. stainless steel, tin plates, EGI steel sheets, etc.) and papers. It is useful as an adhesive layer. Moreover, it is useful as an adhesive layer also in lamination agents other than the said base material.
본 발명에 따른 열용융 접착형 수분산성 코폴리에스테르 수지 조성물은,The hot melt adhesive type water dispersible copolyester resin composition according to the present invention,
(a) 설폰산 금속염기를 함유하지 않는 디카르복실산 100중량부 및 설폰산 금속염기를 함유하는 디카르본산 5~30중량부를 포함하는 산 성분;(a) an acid component comprising 100 parts by weight of a dicarboxylic acid containing no sulfonic acid metal base and 5 to 30 parts by weight of dicarboxylic acid containing a sulfonic acid metal base;
(b) 디올 성분 20~100중량부; 및(b) 20 to 100 parts by weight of the diol component; And
(c) 산성분 완충제 전체 산 성분 함량 대비 0.1~0.4몰% (c) 0.1-0.4 mol% of the total acid component content of the acid component buffer
를 포함하는 것을 특징으로 한다.Characterized in that it comprises a.
여기서, 상기 (c)산성분 완충제 화합물은 아세트산나트륨, 탄산수소나트륨, 탄산나트륨, 인산수소나트륨, 붕산나트륨, 칼륨수소프탈산 및 이들의 혼합물로 이루어지는 군으로부터 선택된, 약산의 염(짝염기) 형태의 화합물인 것이 바람직하다.Wherein the acid component buffer compound (c) is a salt (pair) form of a weak acid, selected from the group consisting of sodium acetate, sodium bicarbonate, sodium carbonate, sodium hydrogen phosphate, sodium borate, potassium hydrogen phthalic acid, and mixtures thereof. It is preferable.
또한, 상기 수지 조성물은 물과 용매 성분을 100:0 내지 50:50 비율로 혼합하여 제조된 혼합용매를 더욱 포함하는 것이 바람직한데, 상기 용매 성분은 메탄올, 에탄올, 이소프로필 알코올, 노말프로필 알코올 등의 탄소원자수 1 내지 15의 1가 알코올, 에틸렌글리콜 모노부틸 에테르, 디에틸렌글리콜 모노부틸 에테르 등의 에틸렌글리콜류, 디에틸렌글리콜류 및 아세톤 및 메틸에틸케톤 등의 케톤류로부터 선택되는 것을 특징으로 한다.In addition, the resin composition preferably further comprises a mixed solvent prepared by mixing water and a solvent component in a ratio of 100: 0 to 50:50, wherein the solvent component is methanol, ethanol, isopropyl alcohol, normal propyl alcohol, or the like. It is characterized in that it is selected from ethylene glycols such as monovalent alcohols having 1 to 15 carbon atoms, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ketones such as diethylene glycol and acetone and methyl ethyl ketone.
바람직하게는, 상기 수지 조성물은 30℃에서 측정한 고유점도가 0.2~0.6dl/g이며, 유리전이온도(Tg)가 -30 내지 10℃, 결정화온도(Tc)가 50~80℃, 용융온도(Tm)가 110~150℃인 것을 특징으로 한다.Preferably, the resin composition has an intrinsic viscosity of 0.2 to 0.6 dl / g measured at 30 ° C, a glass transition temperature (Tg) of -30 to 10 ° C, a crystallization temperature (Tc) of 50 to 80 ° C, and a melting temperature (Tm) is characterized in that 110 ~ 150 ℃.
이하, 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다. Hereinafter, the present invention will be described in more detail.
본 발명은 설폰산 금속염기를 함유하는 디카르본산 또는 이들의 유도체, 디카르본산, 그리고 디올 성분을 공중합시킨 수지조성물에 있어서, 디카르본산 100중 량부에 상기 설폰산 금속염기를 함유하는 디카르본산 또는 이들의 유도체로 이루어진 디카르본산 화합물 5~30중량부, 디올 성분 20~100중량부를 첨가하여 공중합시킨 코폴리에스테르 수지 조성물을 특징으로 한다.The present invention relates to a dicarboxylic acid containing a sulfonic acid metal base or a derivative thereof, a dicarboxylic acid, and a resin composition obtained by copolymerizing a diol component. It is characterized by a copolyester resin composition copolymerized by adding 5 to 30 parts by weight of a dicarboxylic acid compound composed of a main acid or a derivative thereof and 20 to 100 parts by weight of a diol component.
본 발명에 사용된 산 성분 완충제 화합물은 약산의 염(짝염기) 형태의 화합물로 아세트산나트륨, 탄산수소나트륨, 탄산나트륨, 인산수소이나트륨, 붕산나트륨, 칼륨수소프탈산 및 이들의 혼합물로 이루어진 군을 갖는 것으로, 함량은 전체 산 성분 함량 대비 0.1 ~ 0.4몰%이다.The acid component buffer compound used in the present invention is a compound in the form of a salt (pair base) of weak acid and has a group consisting of sodium acetate, sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate, sodium borate, potassium hydrogen phthalic acid, and mixtures thereof. The content is 0.1 to 0.4 mol% relative to the total acid component content.
이하, 하기 실시예를 통하여 본 발명을 좀 더 구체적으로 설명하지만, 이에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.
실시예 1Example 1
온도 조절이 가능한 칼럼과 응축기가 설치되어 있는 반응기에 디메틸테레프탈레이트(100g), 5-소디오 설포디메틸 이소프탈레이트(15g), 세바식산,(50g), 에틸렌 글리콜(40g), 1,4-부탄디올(30g)을 투입한 후 교반하면서 반응기의 내부 온도를 150℃까지 서서히 승온시켰다. 그리고 촉매로서 아연 아세테이트(0.2g) 및 테트라부틸 티타네이트(0.1g), 소디움 아세테이트(2g)를 투입하고, 다시 교반하면서 235℃까지 승온한 다음, 이 온도에서 에스테르화 반응을 계속 진행시켰다. 반응 중 반응 부산물로 메탄올이 유출되기 시작하면 컬럼의 온도를 100℃로 유지시켜 디카르본산이나 디올 성분성분이 승화되거나 증발되어 나오지 않도록 하였다. 5시간 정도 반응을 계속 진행하면 물과 메탄올이 더 이상 유출되지 않았고 반응물도 백색의 불 투명 상태에서 담황색의 투명한 올리고머가 생성되어 에스테르화 반응이 종결되었음을 확인할 수 있었다.Dimethyl terephthalate (100 g), 5-sodio sulfodimethyl isophthalate (15 g), sebacic acid (50 g), ethylene glycol (40 g), 1,4-butanediol in a reactor equipped with a temperature-controlled column and a condenser After adding (30 g), the internal temperature of the reactor was gradually raised to 150 ° C while stirring. Zinc acetate (0.2 g), tetrabutyl titanate (0.1 g) and sodium acetate (2 g) were added as catalysts, and the temperature was raised to 235 ° C while stirring again, and then the esterification reaction was continued at this temperature. When methanol began to flow out as a reaction by-product during the reaction, the temperature of the column was maintained at 100 ° C. to prevent dicarboxylic acid or diol components from subliming or evaporating. When the reaction was continued for about 5 hours, water and methanol were no longer leaked, and the reaction product was confirmed to be a light yellow transparent oligomer in a white opaque state to terminate the esterification reaction.
올리고머 상태의 반응물에 다시 촉매로서 안티모니 옥사이드(0.3g)를 첨가한 후, 반응물이 비산되지 않도록 유의하면서 서서히 진공을 가하고 승온시켜 반응기 내분의 압력이 1 토르(torr)를 유지하고 반응물의 온도는 265℃가 되도록하여 2시간동안 반응을 진행시켜 수분산성 코폴리에스테르 수지 조성물을 제조하였다. 이때 반응 부산물로서 상기에서 투입한 디올 성분인 에틸렌 글리콜과 1,4-부탄디올이 유출되었다. 이렇게 하여 얻어진 수분산성 코폴리에스테르 수지 조성물은 오스트발트 점도계를 사용하여 30℃에서 측정한 고유점도가 0.50 dl/g 이었으며, 시차주사열량분석기를 이용하여 측정한 유리전이온도(Tg)는 -25℃, 결정화온도(Tc)는 80℃, 용융온도(Tm)는 125℃이었다.After addition of antimony oxide (0.3 g) as a catalyst to the reactant in the oligomer state, the vacuum was gradually heated and heated up while being careful not to scatter the reactant to maintain a pressure of 1 torr in the reactor and the temperature of the reactant was The reaction was carried out for 2 hours at 265 ° C. to prepare a water dispersible copolyester resin composition. At this time, ethylene glycol and 1,4-butanediol, which were the diol components introduced above, were leaked as reaction by-products. The water-dispersible copolyester resin composition thus obtained had an intrinsic viscosity of 0.50 dl / g measured at 30 ° C. using an Ostwald viscometer, and the glass transition temperature (Tg) measured using a differential scanning calorimeter was -25 ° C. The crystallization temperature (Tc) was 80 ° C and the melting temperature (Tm) was 125 ° C.
그리고나서 상기에서 얻은 코폴리에스테르 수지조성물(25g)을 물(70g)과 이소프로필 알코올(5g)의 혼합용매에 넣고, 80℃에서 3시간동안 교반하여 담황색의 투명한 수분산성 코폴리에스테르 분산액을 제조하였으며, 브룩필드 점도계로 측정한 30℃에서의 고유점도는 250 cps이었다.Then, the copolyester resin composition (25 g) obtained above was added to a mixed solvent of water (70 g) and isopropyl alcohol (5 g), and stirred at 80 ° C. for 3 hours to prepare a pale yellow transparent water dispersible copolyester dispersion. The intrinsic viscosity at 30 ° C. measured with a Brookfield viscometer was 250 cps.
이를 188um PET 필름 위에 바코터로 20um 두께로 코팅한 후, 3분간 120℃에서 열풍건조하였다. 이와 같은 방법으로 접착층이 형성된 PET 필름을 다른 188 um PET 필름위에 위치시킨 후, Dry Laminator로 온도 130℃, 속도 2m/min, 하중 3kgf로 라미네이팅하여 접착강도를 표 1과 같이 평가하였다.It was coated with a bar coater on a 188um PET film with a thickness of 20um, and then hot air dried at 120 ° C for 3 minutes. After placing the PET film on which the adhesive layer was formed in this manner on another 188 um PET film, the adhesive strength was evaluated by laminating at a temperature of 130 ° C., a speed of 2 m / min, and a load of 3 kgf with a dry laminator, as shown in Table 1 below.
접착강도 측정에 사용된 기기는 UTM(INSTRON, Load Cell 200kgf, 헤드속도 20mm/min)으로 T-peel 180℃ 박리강도를 측정하였다.The instrument used for measuring the adhesive strength was measured T-peel 180 ℃ peel strength by UTM (INSTRON, Load Cell 200kgf, head speed 20mm / min).
실시예 2Example 2
상기 실시예 1과 동일한 방법에 의해 코폴리에스테르 수지조성물을 제조하였으며, 코폴리에스테르 수지조성물(60g)을 물(105g)과 부틸카비톨(35g)의 혼합 용매에 넣고, 80℃에서 3시간동안 교반하여 흰색의 분산액을 제조하였다.A copolyester resin composition was prepared in the same manner as in Example 1, the copolyester resin composition (60 g) was added to a mixed solvent of water (105 g) and butyl carbitol (35 g), and the mixture was heated at 80 ° C. for 3 hours. Stirring gave a white dispersion.
실시예 3Example 3
상기 실시예 1과 동일한 방법에 의해 코폴리에스테르 수지조성물을 제조하였으며, 코폴리에스테르 수지조성물(60g)을 물(105g)과 부틸셀로솔브(35g)의 혼합 용매에 넣고, 80℃에서 3시간동안 교반하여 흰색의 분산액을 제조하였다.A copolyester resin composition was prepared in the same manner as in Example 1, and the copolyester resin composition (60 g) was added to a mixed solvent of water (105 g) and butyl cellosolve (35 g), and the mixture was heated at 80 ° C. for 3 hours. Stirred for to prepare a white dispersion.
실시예 4Example 4
상기 실시예 1과 동일한 방법에 의해 코폴리에스테르 수지조성물을 제조하였으며, 코폴리에스테르 수지조성물(60g)을 물(105g)과 에틸 알코올(35g)의 혼합 용매에 넣고, 80℃에서 3시간동안 교반하여 흰색의 분산액을 제조하였다.A copolyester resin composition was prepared in the same manner as in Example 1, and the copolyester resin composition (60 g) was added to a mixed solvent of water (105 g) and ethyl alcohol (35 g) and stirred at 80 ° C. for 3 hours. To prepare a white dispersion.
전술한 바와 같이, 본 발명은 열용융 접착형 수분산성 코폴리에스테르 수지 조성물에 관한 것으로서, 더욱 상세하게는 설폰산 금속염기를 함유하는 디카르본산 또는 이들의 유도체, 디카르본산, 그리고 디올 성분을 공중합시킨 열용융 접착형 수분산성 코폴리에스테르 수지조성물에 관한 것으로서, 본 발명의 수분산성 코폴리에스테르 수지조성물은 수분산성이 우수하면서도 라미네이팅 적층제에 코팅 및 건조 후 용융 접착성이 우수하여 각종 재료에 대하여 견고하게 접착된다. As described above, the present invention relates to a hot melt adhesive water-dispersible copolyester resin composition, and more particularly, to a dicarboxylic acid containing a sulfonic acid metal base or a derivative thereof, a dicarboxylic acid, and a diol component. The present invention relates to a copolymerized hot melt adhesive type water dispersible copolyester resin composition, wherein the water dispersible copolyester resin composition of the present invention has excellent water dispersibility and excellent melt adhesiveness after coating and drying on a laminating laminate. It is firmly glued against.
또한, 접착 후 빠른 결정화를 통한 접착층의 내열성, 유기용매에 대한 내화학성, 내가수분해성, 기계적 강도 및 접착층의 외부 노출 시의 비점착성(tack-free)이 우수하고, 외부응력(열충격) 및 내부응력(기초수지의 결정화에 따른 수축현상)에 의한 저항력(치수안정성)이 확보되어 있으며, 우수한 탄성 및 굴곡성이 있다. 이러한 특성으로 인하여, 상기 조성물은 PVC, PET, PC, PMMA 계의 필름형태와 철, 알루미늄, 구리 및 각종 합금(예: 스테인레스 강, 주석 플레이트, EGI 강 시트 등) 및 종이류 등과의 라미네이팅 적층체에서 접착층으로서 유용하다. 또한, 상기 기재 이외의 적층제에서도 접착층으로서 유용하다.In addition, it is excellent in heat resistance of the adhesive layer through rapid crystallization after adhesion, chemical resistance to organic solvents, hydrolysis resistance, mechanical strength and tack-free at the external exposure of the adhesive layer, external stress (thermal shock) and internal Resistance (dimension stability) due to stress (shrinkage due to crystallization of base resin) is secured, and has excellent elasticity and flexibility. Due to these properties, the composition can be used in laminating laminates of PVC, PET, PC, PMMA-based films and iron, aluminum, copper and various alloys (e.g. stainless steel, tin plates, EGI steel sheets, etc.) and papers. It is useful as an adhesive layer. Moreover, it is useful as an adhesive layer also in lamination agents other than the said base material.
이상에서는 본 발명의 특정의 바람직한 실시예에 대하여 설명하였으나, 본 발명은 상술한 특정의 실시예에 한정되지 아니하며, 특허청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변형 실시가 가능한 것은 물론이고, 그와 같은 변형은 청구 범위 기재의 범위 내에 있게 된다.While specific embodiments of the present invention have been described above, the present invention is not limited to the above-described specific embodiments, and the technical field to which the present invention pertains without departing from the spirit of the present invention as claimed in the claims. Anyone of ordinary skill in the art can make various modifications, as well as such modifications are within the scope of the claims.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050133813A KR20070070855A (en) | 2005-12-29 | 2005-12-29 | Hot-melt adhesive type water dispersible copolyester composition |
| CNA2006100902453A CN1990808A (en) | 2005-12-29 | 2006-07-07 | Hot melt adhesive water -dispersible copolyester composition |
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| KR1020050133813A KR20070070855A (en) | 2005-12-29 | 2005-12-29 | Hot-melt adhesive type water dispersible copolyester composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464959A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Water dispersible wax-bearing hot melt adhesive composition |
| CN105506773A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | High-strength medium-shrinkage polyester industrial yarn and preparation method thereof |
| CN105506774A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | Low-color-difference polyester differential shrinkage composite yarn and preparation method thereof |
| CN105506772A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | Heat-resistant polyester activated industrial yarn and preparation method thereof |
| KR20180003276A (en) * | 2016-06-30 | 2018-01-09 | 코오롱인더스트리 주식회사 | Thermal shrinking polyester based film, Method of manufacturing thereof and Label comprising thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603562B (en) * | 2015-12-29 | 2017-12-12 | 江苏恒力化纤股份有限公司 | A kind of heat-resistance polyester industrial yarn and preparation method thereof |
-
2005
- 2005-12-29 KR KR1020050133813A patent/KR20070070855A/en not_active Application Discontinuation
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2006
- 2006-07-07 CN CNA2006100902453A patent/CN1990808A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464959A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Water dispersible wax-bearing hot melt adhesive composition |
| CN105506773A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | High-strength medium-shrinkage polyester industrial yarn and preparation method thereof |
| CN105506774A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | Low-color-difference polyester differential shrinkage composite yarn and preparation method thereof |
| CN105506772A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | Heat-resistant polyester activated industrial yarn and preparation method thereof |
| KR20180003276A (en) * | 2016-06-30 | 2018-01-09 | 코오롱인더스트리 주식회사 | Thermal shrinking polyester based film, Method of manufacturing thereof and Label comprising thereof |
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| CN1990808A (en) | 2007-07-04 |
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