KR101255033B1 - Method of manufacturing hydrophilic polyurethane resin used in coating for surface treatment - Google Patents
Method of manufacturing hydrophilic polyurethane resin used in coating for surface treatment Download PDFInfo
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- KR101255033B1 KR101255033B1 KR1020110018825A KR20110018825A KR101255033B1 KR 101255033 B1 KR101255033 B1 KR 101255033B1 KR 1020110018825 A KR1020110018825 A KR 1020110018825A KR 20110018825 A KR20110018825 A KR 20110018825A KR 101255033 B1 KR101255033 B1 KR 101255033B1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
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- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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Abstract
본 발명은 표면처리코팅용 친수성 폴리우레탄 수지의 제조방법에 관한 것으로서, 보다 구체적으로 본 발명은 (ⅰ) 중합반응에 사용되는 전량의 폴리에스테르폴리올, 중합반응에 사용되는 전량의 폴리에틸렌폴리올, 중합반응에 사용되는 전량대비 20~50중량%의 쇄연장제 및 불활성 유기용매를 중합반응기에 투입하여 혼합한 다음, 상기 중합반응기에 폴리에스테르폴리올, 폴리에틸렌폴리올 및 쇄연장제가 혼합된 혼합물 대비 폴리이소시아네이트의 반응비율이 폴리이소시아네이트 내 이소시아네이트기 / 상기 혼합물내 수산기 비율이 당량비로 0.8~1.5가 되도록 중합반응에 사용되는 전량대비 55~65중량%의 폴리이소시아네이트를 투입하여 40~120℃에서 2~6시간 동안 중합반응하는 1차 중합반응 공정으로 실시하여 수평균분자량이 균일한 1차 중합물을 제조한 다음, (ⅱ) 상기 1차 중합반응 공정 후 상기 중합반응기에 중합반응에 사용되는 전량대비 50~80중량%의 나머지 쇄연장제와 불활성 유기용매를 상기 중합반응기에 투입하여 40~120℃에서 0.5~1시간 동안 반응시킨 다음, 계속해서 상기 중합반응기의 반응에 사용되는 전량대비 35~45중량%의 나머지 폴리이소시아네이트를 투입하여 40~120℃에서 2~5시간 동안 중합반응하는 2차 중합반응 공정으로 표면처리코팅용 친수성 폴리우레탄 수지를 제조한다.
본 발명에 따라 제조된 친수성 폴리우레탄 수지는 물에 희석되어 표면처리코팅액 배합시 유기용제 대신 물로 점도 조절이 가능하여 환경친화적인 효과가 있다.The present invention relates to a method for producing a hydrophilic polyurethane resin for surface treatment coatings, and more particularly, the present invention relates to (i) a total amount of polyester polyols used for polymerization, polyethylene polyols used for polymerization, and a polymerization reaction. 20 to 50% by weight of a chain extender and an inert organic solvent are added to the polymerization reactor and mixed with each other, and then the reaction of the polyisocyanate with respect to the mixture of polyester polyol, polyethylene polyol, and chain extender in the polymerization reactor. The ratio is 55 to 65% by weight of polyisocyanate relative to the total amount used in the polymerization reaction so that the ratio of isocyanate groups in the polyisocyanate / hydroxyl groups in the mixture is 0.8-1.5 in equivalent ratio. A primary polymerization product having a uniform number average molecular weight was prepared by the reaction of the first polymerization reaction. Next, (ii) 50 to 80% by weight of the remaining chain extender and the inert organic solvent relative to the total amount used in the polymerization reaction in the polymerization reactor after the first polymerization reaction step into the polymerization reactor 0.5 at 40 ~ 120 ℃ After the reaction for 1 hour, the remaining polyisocyanate of 35 to 45% by weight relative to the total amount used for the reaction of the polymerization reactor is subsequently polymerized at 40 to 120 ℃ for 2 to 5 hours To prepare a hydrophilic polyurethane resin for the surface treatment coating.
Hydrophilic polyurethane resin prepared according to the present invention is diluted in water, when the surface treatment coating liquid formulation can be adjusted to viscosity with water instead of the organic solvent has an environmentally friendly effect.
Description
본 발명은 표면처리코팅용 친수성 폴리우레탄 수지의 제조방법에 관한 것으로서, 구체적으로는 물에 희석될 수 있어 표면처리코팅액 배합시 유기용제 대신 물로 점도 조절이 가능한 표면처리코팅용 친수성 폴리우레탄 수지의 제조방법에 관한 것이다.The present invention relates to a method for producing a hydrophilic polyurethane resin for surface treatment coating, specifically, can be diluted in water to prepare a hydrophilic polyurethane resin for surface treatment coating that can be diluted with water instead of organic solvent when mixing the surface treatment coating liquid It is about a method.
종래 원단 등의 기재상에 투습방수피막 등을 형성하는데 사용되는 표면처리코팅용 폴리우레탄 수지는 중합반응에 사용되는 전량의 폴리에스테르폴리올, 폴리에틸렌폴리올, 폴리이소시아네이트 및 쇄연장제를 중합반응기 내에 한번에 모두 투입하여 불활성 유기용매 중에서 반응시켜, 다시말해 1단계 중합반응공정을 거쳐 제조되어왔다.Polyurethane resins for surface treatment coatings used to form moisture-permeable waterproof coatings on substrates, such as conventional fabrics, contain all of polyester polyols, polyethylene polyols, polyisocyanates and chain extenders used in a polymerization reaction at once in a polymerization reactor. It was added and reacted in an inert organic solvent, that is, it was manufactured through the one-step polymerization reaction process.
이와같은 종래의 방법으로 제조된 표면처리코팅용 폴리우레탄 수지는 1단계 중합반응 공정만을 거쳐 제조되기 때문에 수평균분자량이 불균일한 문제가 있었다.The polyurethane resin for surface treatment coating prepared by such a conventional method has a problem in that the number average molecular weight is non-uniform because it is prepared only through a one-step polymerization reaction process.
그로인해 물에는 희석이 되지 않아 표면처리코팅액 배합시 톨루엔, 메틸에틸케톤, 디메틸포름아미드 등과 같은 유기용제를 사용하여 점도를 조절하야 하기 때문에, 코팅물의 건조시 상기 유기용제가 휘발되면서 대기를 오염시키는 문제가 발생되었다.As a result, water is not diluted, so the viscosity of the surface treatment coating solution must be adjusted using organic solvents such as toluene, methyl ethyl ketone, dimethylformamide, and the like. A problem has occurred.
이와같은 종래의 문제점들을 해결할 수 있도록 본 발명에서는 물에 희석되어 표면코팅처리액 배합시 유기용매 대신 물로 점도 조절이 가능하며 친환경적인 표면처리코팅용 친수성 폴리우레탄 수지를 제공하는 것을 과제로 한다.In order to solve the above problems, the present invention provides a hydrophilic polyurethane resin for surface treatment coating, which is diluted with water and is capable of viscosity control with water instead of an organic solvent when mixing the surface coating treatment solution.
이와같은 과제를 달성하기 위해서 본 발명에서는 (ⅰ) 중합반응에 사용되는 전량의 폴리에스테르폴리올, 중합반응에 사용되는 전량의 폴리에틸렌폴리올, 중합반응에 사용되는 전량대비 20~50중량%의 쇄연장제 및 불활성 유기용매를 중합반응기에 투입하여 혼합한 다음, 상기 중합반응기에 폴리에스테르폴리올, 폴리에틸렌폴리올 및 쇄연장제가 혼합된 혼합물 대비 폴리이소시아네이트의 반응비율이 폴리이소시아네이트 내 이소시아네이트기 / 상기 혼합물내 수산기 비율이 당량비로 0.8~1.5가 되도록 중합반응에 사용되는 전량대비 55~65중량%의 폴리이소시아네이트를 투입하여 40~120℃에서 2~6시간 동안 중합반응하는 1차 중합반응 공정으로 실시하여 수평균분자량이 균일한 1차 중합물을 제조한 다음, (ⅱ) 상기 1차 중합반응 공정 후 상기 중합반응기에 중합반응에 사용되는 전량대비 50~80중량%의 쇄연장제와 불활성 유기용매를 상기 중합반응기에 투입하여 40~120℃에서 0.5~1시간 동안 반응시킨 다음, 계속해서 상기 중합반응기의 반응에 사용되는 전량대비 35~45중량%의 나머지 폴리이소시아네이트를 투입하여 40~120℃에서 2~5시간 동안 중합반응하는 2차 중합반응 공정으로 표면처리코팅용 친수성 폴리우레탄 수지를 제조 한다.In order to achieve the above object, in the present invention, (i) the total amount of polyester polyol used in the polymerization reaction, the polyethylene polyol in the total amount used in the polymerization reaction, and the chain extender of 20 to 50% by weight relative to the total amount used in the polymerization reaction. And an inert organic solvent was added to the polymerization reactor, followed by mixing, and then the reaction ratio of polyisocyanate to the mixture of polyester polyol, polyethylene polyol, and chain extender in the polymerization reactor was higher than that of isocyanate group in the polyisocyanate / hydroxyl group in the mixture. 55 to 65% by weight of polyisocyanate is added to the total amount used in the polymerization reaction so as to be 0.8 to 1.5 in equivalent ratio, and the number average molecular weight is carried out by the first polymerization reaction process for polymerization for 2 to 6 hours at 40 to 120 ° C. After preparing a homogeneous primary polymer, (ii) after the primary polymerization step, 50 to 80% by weight of a chain extender and an inert organic solvent are added to the polymerization reactor and reacted for 0.5 to 1 hour at 40 to 120 ° C, followed by the reaction of the polymerization reactor. By adding the remaining polyisocyanate of 35 to 45% by weight relative to the total amount to prepare a hydrophilic polyurethane resin for the surface treatment coating by a second polymerization reaction process for a polymerization reaction at 40 ~ 120 ℃ for 2 to 5 hours.
본 발명에 따라 제조된 친수성 폴리우레탄 수지는 물에 희석되어 표면처리코팅액 배합시 유기용제 대신 물로 점도 조절이 가능하여 환경친화적인 효과가 있다.Hydrophilic polyurethane resin prepared according to the present invention is diluted in water, when the surface treatment coating liquid formulation can be adjusted to viscosity with water instead of the organic solvent has an environmentally friendly effect.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 먼저 중합반응에 사용되는 전량의 폴리에스테르폴리올, 중합반응에 사용되는 전량의 폴리에틸렌폴리올, 중합반응에 사용되는 전량대비 20~50중량%의 쇄연장제 및 불활성 유기용매를 중합반응기에 투입하여 혼합한 다음, 상기 중합반응기에 폴리에스테르폴리올, 폴리에틸렌폴리올 및 쇄연장제가 혼합된 혼합물 대비 폴리이소시아네이트의 반응비율이 폴리이소시아네이트 내 이소시아네이트기 / 상기 혼합물내 수산기 비율이 당량비로 0.8~1.5가 되도록 중합반응에 사용되는 전량대비 55~65중량%의 폴리이소시아네이트를 투입하여 40~120℃에서 2~6시간 동안 중합반응하는 1차 중합반응 공정을 거쳐 1차 중합물(예비중합물)을 제조한다.In the present invention, first, the total amount of polyester polyol used in the polymerization reaction, the polyethylene polyol used in the polymerization reaction, 20-50% by weight of a chain extender and an inert organic solvent are added to the polymerization reactor. And then mixed so that the reaction ratio of polyisocyanate to the mixture of polyester polyol, polyethylene polyol and chain extender in the polymerization reactor is 0.8 to 1.5 in equivalent ratio of isocyanate group / hydroxy group in the polyisocyanate. 55 to 65% by weight of polyisocyanate relative to the total amount used in the primary polymerization (preliminary polymerization) is prepared through a first polymerization reaction process for polymerization for 2 to 6 hours at 40 ~ 120 ℃.
이때, 상기 폴리에스테르폴리올 : 폴리에틸렌폴리올의 혼합비율을 질량비 기준으로 20~80 : 80~20으로 조절한다.At this time, the mixing ratio of the polyester polyol: polyethylene polyol is adjusted to 20 to 80:80 to 20 on a mass ratio basis.
보다 바람직하기로는 상기 혼합비율을 질량비 기준으로 40~60 : 60~40으로 조절한다.More preferably, the mixing ratio is adjusted to 40 to 60: 60 to 40 based on the mass ratio.
폴리에스테르폴리올의 혼합비율이 상기 범위보다 적으면 얻어지는 폴리우레탄 수지의 투습도와 내구성이 충분하지 못하게되고, 폴리에틸렌폴리올의 혼합비율이 상기 범위보다 적으면 얻어지는 폴리우레탄 수지의 세탁내구성 및 유연성이 저하된다.If the blending ratio of the polyester polyol is less than the above range, the moisture permeability and durability of the resulting polyurethane resin will not be sufficient, and if the blending ratio of the polyethylene polyol is less than the above range, the laundry durability and flexibility of the resulting polyurethane resin will be lowered.
본 발명에서는 폴리에스테르폴리올과 폴리에틸렌폴리올의 혼합비율을 상기 범위로 조절함으로서, 투습방수피막 제조시 투습도, 내수성, 유연성 및 세탁내구성(접착력)이 모두 동시에 향상시킬 수 있도록 한다.In the present invention, by adjusting the mixing ratio of the polyester polyol and polyethylene polyol in the above range, the moisture permeability, water resistance, flexibility and durability of the laundry (adhesiveness) at the time of manufacturing the moisture-permeable waterproof film can be improved at the same time.
또한, 본 발명에서는 폴리에스테르폴리올, 폴리에틸렌폴리올 및 쇄연장제가 혼합된 혼합물 대비 폴리이소시아네이트의 반응비율을 폴리이소시아네이트내 이소시아네이트기 / 상기 혼합물내 수산기 비율이 당량비로 0.8~1.5, 보다 바람직하기로는 0.9~1.12가 되도록 조정하는 것을 특징으로 한다.In addition, in the present invention, the reaction ratio of the polyisocyanate to the mixture of the polyester polyol, the polyethylene polyol, and the chain extender is 0.8 to 1.5, more preferably 0.9 to 1.12, in the equivalence ratio of the isocyanate group in the polyisocyanate / hydroxyl group in the mixture. It characterized in that the adjustment to be.
상기 1차 중합반응 공정은 1차 중합물의 수평균분자량이 5,000~10,000이 될때까지 실시하는 것이 최종 중합물의 수평균분자량을 균일하게 하는데 바람직하다.The first polymerization step is preferably carried out until the number average molecular weight of the primary polymer is 5,000 to 10,000 to uniformize the number average molecular weight of the final polymer.
다음으로, 상기 1차 중합반응 공정 후 상기 중합반응기에 중합반응에 사용되는 전량대비 50~80중량%의 나머지 쇄연장제와 불활성 유기용매를 상기 중합반응기에 투입하여 40~120℃에서 0.5~1시간 동안 반응시킨 다음, 계속해서 상기 중합반응기의 반응에 사용되는 전량대비 35~45중량%의 나머지 폴리이소시아네이트를 투입하여 40~120℃에서 2~5시간 동안 중합반응하는 2차 중합반응 공정을 거쳐 표면처리코팅용 친수성 폴리우레탄수지를 제조한다.Next, after the first polymerization step, 50 to 80% by weight of the remaining chain extender and an inert organic solvent are added to the polymerization reactor in the polymerization reactor to 0.5 to 1 at 40 to 120 ° C. After the reaction for a period of time, the remaining polyisocyanate of 35 to 45% by weight relative to the total amount used for the reaction of the polymerization reactor is continuously added to undergo a second polymerization process for polymerization at 40 to 120 ℃ for 2 to 5 hours. Hydrophilic polyurethane resin for surface treatment coating is prepared.
본 발명에서는 상기 폴리에스테르폴리올과 폴리에틸렌폴리올의 혼합물 1몰을 기준으로 0.5~10몰, 보다 바람직하기로는 1~4몰의 쇄연장제를 사용함을 특징으로 한다.In the present invention, 0.5 to 10 moles, more preferably 1 to 4 moles of a chain extender, is used based on 1 mole of the mixture of the polyester polyol and polyethylene polyol.
쇄연장제의 사용량이 상기 범위를 벗어나면 얻어지는 폴리우레탄 수지의 투습도, 내수성, 접착력 및 유연성이 동시에 우수하게 되지 않는다.When the amount of the chain extender used is out of the above range, the moisture permeability, water resistance, adhesion, and flexibility of the resulting polyurethane resin do not become excellent at the same time.
상기 쇄연장제는 에틸렌글리콜, 1,4-부틸렌글리콜, 네오펜틸글리콜, 디에틸렌글리콜 또는 트리에틸렌글리콜 등이다.The chain extender is ethylene glycol, 1,4-butylene glycol, neopentyl glycol, diethylene glycol or triethylene glycol and the like.
본 발명에는 불활성 유기용제, 즉 폴리이소시아네이트 등의 폴리우레탄 수지 원료와 반응하지 않는 유기용제를 사용한다.In the present invention, an inert organic solvent, that is, an organic solvent which does not react with a polyurethane resin raw material such as polyisocyanate is used.
습식법으로 투습방수피막을 제조하는 경우에는 불활성 유기용매로 수혼화성 유기용제를 사용하고, 건식법으로 투습방수피막을 제조하는 경우에는 휘발성이 높은 유기용제를 사용하는 것이 바람직하다.It is preferable to use a water miscible organic solvent as an inert organic solvent when preparing a moisture-permeable waterproof coating by a wet method, and to use a highly volatile organic solvent when producing a moisture-permeable waterproof coating by a dry method.
상기 불활성 유기용제의 구체적인 예로는 디메틸포름아미드, 디메틸아세트아미드, 톨루엔, 메틸에틸케톤, 이소프로판올 또는 이들중에서 선택된 2종 이상의 혼합물 등이다.Specific examples of the inert organic solvent include dimethylformamide, dimethylacetamide, toluene, methyl ethyl ketone, isopropanol or a mixture of two or more selected from these.
상기 1차 중합반응 공정에 투입되는 불활성 유기용매 : 상기 2차 중합반응 공정에 투입되는 불활성 유기용매의 중량비율이 1:3 ~ 1:5인 것이 바람직하다.It is preferable that the weight ratio of the inert organic solvent to be added to the primary polymerization reaction: the inert organic solvent to be introduced into the secondary polymerization reaction is 1: 3 to 1: 5.
상기 쇄연장제는 에틸렌글리콜, 1,4-부틸렌글리콜, 네오펜틸글리콜, 디에틸렌글리콜 또는 트리에틸렌글리콜 등이다.The chain extender is ethylene glycol, 1,4-butylene glycol, neopentyl glycol, diethylene glycol or triethylene glycol and the like.
다음으로, 본 발명에 따라 제조된 친수성 폴리우레탄 수지로 기재상에 투습방수피막을 제조하는 방법에 대해 살펴본다.Next, look at a method for producing a moisture-permeable waterproof film on a substrate with a hydrophilic polyurethane resin prepared according to the present invention.
본 발명의 방법으로 제조된 친수성 폴리우레탄 수지를 물에 희석시켜 점도를 조절하여 표면처리코팅액을 제조한 후, 이를 원단 등의 기재위에 코팅(도포)후 건조하면 투습방수피막이 기재상에 형성된다.The hydrophilic polyurethane resin prepared by the method of the present invention is diluted with water to prepare a surface treatment coating liquid by adjusting the viscosity, and then coated (coated) on a substrate such as fabric and dried to form a moisture-permeable waterproof film on the substrate.
상기 기재로는 합성섬유나 천연섬유 등으로 이루어진 직물, 편물 또는 부직포 등이 주로 사용된다.As the base material, a woven fabric, a knitted fabric or a nonwoven fabric made of synthetic fibers or natural fibers is mainly used.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 살펴본다.Hereinafter, the present invention will be described in more detail with reference to Examples.
그러나 본 발명은 하기 실시예에 의해 보호범위가 한정되는 것은 아니다.However, the present invention is not limited to the scope of protection by the following examples.
실시예 1Example 1
중합반응용기에 폴리에스테르폴리올 130㎏, 폴리에틸렌폴리올 130㎏, 쇄연장제인 1,4-부탄디올 3.4㎏, 점도조절제인 아크릴모노머 10㎏, 최종 생성 폴리우레탄 수지 대비 50ppm에 상당하는 촉매인 비스무스 카복실레이트(KAT 348, KING Industries 제조)을 투입하여 혼합한 다음, 상기 중합반응용기에 디페닐메탄디이소시아네이트 60㎏(이소시아네트기/수산기 비율이 1.02에 상응함)을 투입하여 70℃에서 3.5시간동안 1차 중합반응시켜 수평균분자량 8,000인 1차 중합물을 제조하였다.In the polymerization vessel, 130 kg of polyester polyol, 130 kg of polyethylene polyol, 3.4 kg of 1,4-butanediol as a chain extender, 10 kg of acryl monomer as a viscosity modifier, and bismuth carboxylate as a catalyst equivalent to 50 ppm compared to the final polyurethane resin ( KAT 348, manufactured by KING Industries) was added to the mixture, and then 60 kg of diphenylmethane diisocyanate (the isocyanate group / hydroxy group ratio corresponds to 1.02) was added to the polymerization reactor for 1 hour at 70 ° C. for 3.5 hours. The primary polymerization was a primary polymer having a number average molecular weight of 8,000.
다음으로, 상기 중합반응용기에 쇄연장제인 1,4-부탄디올 6.0㎏과 메틸에틸케톤 550㎏ 및 N-메틸피롤리돈 50㎏을 첨가한 후, 질소분위기 하에서 70℃로 1시간동안 반응시킨 다음, 계속해서 상기 중합반응기에 디페닐메탄디이소시아네이트 40㎏(이소시아네이트기/수산기 비율이 0.9에 상응함)을 투입하여 70℃에서 3.5시간동안 반응시켜 친수성 폴리우레탄 수지를 제조하였다.Next, 6.0 kg of 1,4-butanediol as a chain extender, 550 kg of methyl ethyl ketone and 50 kg of N-methylpyrrolidone were added to the polymerization reaction vessel, and then reacted at 70 ° C. for 1 hour under a nitrogen atmosphere. Subsequently, 40 kg of diphenylmethane diisocyanate (isocyanate group / hydroxyl group ratio corresponds to 0.9) was added to the polymerization reactor and reacted at 70 ° C. for 3.5 hours to prepare a hydrophilic polyurethane resin.
상기와 같이 제조된 친수성 폴리우레탄 수지를 물에 희석시켜 표면처리코팅액을 배합한 후, 상기 표면처리코팅액을 폴리에스테르 원단 위에 나이프 오버롤 방식으로 코팅하여 두께가 20㎛인 투습방수피막을 제조하였다.The hydrophilic polyurethane resin prepared as described above was diluted with water to mix a surface treatment coating solution, and then the surface treatment coating solution was coated on a polyester fabric by a knife over roll method to prepare a moisture-permeable waterproof film having a thickness of 20 μm.
제조된 친수성 폴리우레탄 수지의 물에 대한 희석성능(이하"희석성능"이라 함) 투습방수피막의 각종물성을 평가한 결과는 표 2와 같았다.The dilution performance (hereinafter referred to as "dilution performance") on the water of the prepared hydrophilic polyurethane resin was evaluated for the various physical properties of the moisture-permeable waterproof film is shown in Table 2.
실시예 2 내지 실시예 4Examples 2-4
중합반응시 투입되는 원료의 종류 및 투입량을 표 1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 조건으로 친수성 폴리우레탄 수지 및 투습방수피막을 제조하였다.A hydrophilic polyurethane resin and a moisture-permeable waterproof film were prepared under the same conditions as in Example 1 except that the type and amount of the raw materials to be added during the polymerization reaction were changed as shown in Table 1.
제조된 친수성 폴리우레탄 수지의 물에 대한 희석성능(이하"희석성능"이라 함) 투습방수피막의 각종물성을 평가한 결과는 표 2와 같았다.The dilution performance (hereinafter referred to as "dilution performance") on the water of the prepared hydrophilic polyurethane resin was evaluated for the various physical properties of the moisture-permeable waterproof film is shown in Table 2.
(g/d)The tensile strength
(g / d)
표 2의 인장강도 및 100% 신장시 모듈러스는 ASTM E252 방법으로 측정하였고, 희석석능은 전문가 10명중 8명 이상이 좋다고 판단하면 우수로 판정하였다.Tensile strength and modulus at 100% elongation of Table 2 were measured by ASTM E252 method, dilution ability was determined to be excellent when judged that 8 or more of 10 experts is good.
Claims (6)
(ⅱ) 상기 1차 중합반응 공정 후 상기 중합반응기에 중합반응에 사용되는 전량대비 50~80중량%의 나머지 쇄연장제와 불활성 유기용매를 상기 중합반응기에 투입하여 40~120℃에서 0.5~1시간 동안 반응시킨 다음, 계속해서 상기 중합반응기의 반응에 사용되는 전량대비 35~45중량%의 나머지 폴리이소시아네이트를 투입하여 40~120℃에서 2~5시간 동안 중합반응하는 2차 중합반응 공정 : 들을 포함하는 것을 특징으로 하는 표면처리코팅용 친수성 폴리우레탄 수지의 제조방법.(Iii) A total amount of polyester polyol used in the polymerization reaction, a polyethylene polyol used in the polymerization reaction, 20-50% by weight of a chain extender and an inert organic solvent are added to the polymerization reactor. After mixing, the reaction ratio of polyisocyanate to the mixture of polyester polyol, polyethylene polyol and chain extender in the polymerization reactor is 0.8 to 1.5 in equivalent ratio of isocyanate group / hydroxy group in polyisocyanate. Primary polymerization reaction step of polymerization reaction for 2 to 6 hours at 40 ~ 120 ℃ by adding 55 to 65% by weight of polyisocyanate relative to the total amount used:
(Ii) 50 to 80% by weight of the remaining chain extender and an inert organic solvent are added to the polymerization reactor to the polymerization reactor in the polymerization reactor to 0.5 to 1 at 40 to 120 ° C. After the reaction for 2 hours, the second polypolymerization process of the polymerization reaction for 2 to 5 hours at 40 ~ 120 ℃ by continuously adding 35 ~ 45% by weight of the remaining polyisocyanate to the total amount used for the reaction of the polymerization reactor: Method for producing a hydrophilic polyurethane resin for surface treatment coating comprising a.
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| JPH09157409A (en) * | 1995-12-01 | 1997-06-17 | Nippon Miractran Kk | Moisture-permeable film or sheet and its production |
| KR20020032354A (en) * | 2000-10-25 | 2002-05-03 | 다이니뽄 잉끼 가가꾸 고오교오 가부시끼가이샤 | Aqueous dispersion of polyurethane resins and aqueous adhesives |
| JP2008518058A (en) * | 2004-10-25 | 2008-05-29 | ダウ グローバル テクノロジーズ インコーポレイティド | Prepolymers made from hydroxymethyl-containing polyester polyols derived from fatty acids |
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| KR20020032354A (en) * | 2000-10-25 | 2002-05-03 | 다이니뽄 잉끼 가가꾸 고오교오 가부시끼가이샤 | Aqueous dispersion of polyurethane resins and aqueous adhesives |
| JP2008518058A (en) * | 2004-10-25 | 2008-05-29 | ダウ グローバル テクノロジーズ インコーポレイティド | Prepolymers made from hydroxymethyl-containing polyester polyols derived from fatty acids |
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