KR101609806B1 - Preparation of waterborne polyurethane resin using 2-methylcyclohexane-1,3,5-triamine and aterborne polyurethane resin - Google Patents
Preparation of waterborne polyurethane resin using 2-methylcyclohexane-1,3,5-triamine and aterborne polyurethane resin Download PDFInfo
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- KR101609806B1 KR101609806B1 KR1020140125529A KR20140125529A KR101609806B1 KR 101609806 B1 KR101609806 B1 KR 101609806B1 KR 1020140125529 A KR1020140125529 A KR 1020140125529A KR 20140125529 A KR20140125529 A KR 20140125529A KR 101609806 B1 KR101609806 B1 KR 101609806B1
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- water
- polyurethane resin
- prepolymer
- triamine
- isocyanate
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 41
- MHLXJPDUYGRIPL-UHFFFAOYSA-N 2-methylcyclohexane-1,3,5-triamine Chemical compound CC1C(N)CC(N)CC1N MHLXJPDUYGRIPL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000002009 diols Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 16
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 239000006085 branching agent Substances 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 20
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- -1 aliphatic isocyanate Chemical class 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- DFNLYRGDOWABDU-UHFFFAOYSA-N 1-methylcyclohexane-1,3,5-triamine Chemical compound CC1(N)CC(N)CC(N)C1 DFNLYRGDOWABDU-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 description 18
- 239000004814 polyurethane Substances 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000004072 triols Chemical class 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 description 1
- UOFSMFMNGAKHJO-UHFFFAOYSA-N 4-methyl-3-nitrobenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1[N+]([O-])=O UOFSMFMNGAKHJO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/83—Chemically modified polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
2-메틸사이클로헥산-1,3,5-트리아민을 이용한 수분산성 폴리우레탄 수지 제조방법 및 이를 이용하여 형성된 수분산성 폴리우레탄 수지에 관한 것으로서, 수분산형 폴리우레탄 수지는 하이드록시기를 갖는 폴리올, 카르복실기를 갖는 디올 및 지방족 디이소시아네이트를 혼합 반응시켜 이소시아네이트 말단형 폴리우레탄 예비중합체를 제조하는 단계와, 상기 이소시아네이트 말단형 폴리우레탄 예비중합체를 3급 아민으로 중화시켜 자기 유화형 예비중합체를 제조하는 단계와, 상기 자기 유화형 예비중합체에 물을 가하여 수 분산 시키는 단계와, 가지연장제로 2-메틸사이클로헥산-1,3,5-트리아민 이용하여 수 분산된 자기 유화형 예비중합체를 가교반응시켜 제조할 수 있다. The present invention relates to a process for producing a water-dispersible polyurethane resin using 2-methylcyclohexane-1,3,5-triamine and a water-dispersible polyurethane resin formed using the same, wherein the water-dispersible polyurethane resin is a polyol having a hydroxy group, Preparing an isocyanate-terminated polyurethane prepolymer by neutralizing the isocyanate-terminated polyurethane prepolymer with a tertiary amine to prepare a self-emulsifiable prepolymer; and mixing the diol with an aliphatic diisocyanate, Water-dispersing the self-emulsifiable prepolymer with water and dispersing the water-dispersed self-emulsifiable prepolymer using 2-methylcyclohexane-1,3,5-triamine as a branching agent. have.
Description
본 발명은 수분산성 폴리우레탄 수지의 제조방법 및 이를 이용하여 형성된 수분산성 폴리우레탄 수지에 관한 것으로서, 더욱 상세하게는 폐탄약인 TNT로부터 합성된 지방족 아민인 2-메틸사이클로헥산-1,3,5-트리아민을 이용한 수분산성 폴리우레탄 수지의 제조방법 및 이를 이용하여 형성된 수분산성 폴리우레탄 수지에 관한 것이다.The present invention relates to a process for producing a water-dispersible polyurethane resin and a water-dispersible polyurethane resin formed using the same, and more particularly to a process for producing a water-dispersible polyurethane resin comprising an aliphatic amine -Triamine and a water-dispersible polyurethane resin formed using the same.
폴리우레탄 수지는 일반적으로 섬유, 피혁, 플라스틱, 목재, 콘크리트, 유리, 금속재료 등의 코팅제나 접착제, 충진제 등으로 폭 넓게 사용되고 있으며, 폴리우레탄이 지니고 있는 여러 물성(내마모성, 인장강도, 유연성, 내구성, 강인성 등)들 때문에 사용범위가 점차 증가하는 추세에 있다. Polyurethane resins are widely used as coatings, adhesives and fillers for textile, leather, plastics, wood, concrete, glass and metal materials. They are widely used for various properties such as abrasion resistance, tensile strength, flexibility, durability , Toughness, etc.), the use range is gradually increasing.
이러한, 폴리우레탄 수지는 종래부터 유기용제를 사용하여 왔지만, 인체나 환경에 좋지 않은 영향을 미치고, 인화성도 있기 때문에 최근에는 유기용제의 사용에 따른 단점을 보완하고, 대기를 오염시키지 않은 범위 내에서 물을 용매로 사용하는 수분산 폴리우레탄 제조 방법이 널리 이용되고 있다. Such a polyurethane resin has conventionally used an organic solvent, but since it has a bad influence on the human body and the environment and has flammability, recently, the disadvantages of the use of the organic solvent have been supplemented, A water-dispersed polyurethane production method using water as a solvent is widely used.
그와 같은 수분산성 폴리우레탄 수지로서, 예컨대, 일본국 특허 공개 (평)4-328187호 공보에서는 소수성인 폴리우레탄을 수성화 시키기 위하여, 폴리우레탄 골격중에 친수성기를 도입하여 자기 유화성 수지를 만든 후 수중에서 분산시키는 방법이 제안되어 있고, 일본국 특허 공개 (평)8-174429호 공보와 (평)8-193181호 공보에서는 수분산성 폴리우레탄 수지의 폴리올 성분으로서 디올과 트리올과의 혼합 폴리올을 이용하고, 이소시아네이트와 반응시킴으로써, 수분산성이 높은 예비 중합체를 얻는 것이 제안되어 있다.As such a water-dispersible polyurethane resin, for example, in JP-A-4-328187, a hydrophilic group is introduced into a polyurethane skeleton to make a hydrophilic polyurethane, And Japanese Unexamined Patent Publication Nos. 8-174429 and 8-193181 disclose a method of dispersing a mixed polyol of a diol and a triol as a polyol component of a water dispersible polyurethane resin, And reacting with isocyanate to obtain a prepolymer having high water dispersibility.
그러나, 기존의 수분산성 및 수지 제조방법으로는 용이한 수분산 과정을 거쳐서 우수한 기계적 물성 및 내화학성이 우수한 폴리우레탄 수지를 만들기가 어렵다. However, it is difficult to produce a polyurethane resin having excellent mechanical properties and chemical resistance through an easy water dispersion process in the conventional water dispersibility and resin production methods.
또한, 수분산성 폴리우레탄 수지를 제조하는 데 있어서 수분산 과정 이전에 우레탄 예비 중합체합성 하는 과정을 수행할 수 있다. 예비중합체를 합성하는 과정에서 최종적인 폴리우레탄 수지의 기계적 물성 및 내화학성 등을 높이고자 저분자량의 트리올을 사용하기도 하는데, 이러한 저분자량의 트리올을 사용하게 되면, 저분자량의 트리올과 이소시아네이트 화합물에의 반응에 의해, 트리올로 분지된 부분에 우레탄 결합이 집적되어 분자 내에 우레탄 결합의 밀도가 높은 부분이 발생된다. Further, in the production of the water-dispersible polyurethane resin, a urethane prepolymer synthesis process can be carried out before the water dispersion process. In order to increase the mechanical properties and chemical resistance of the final polyurethane resin during the synthesis of the prepolymer, low molecular weight triols may be used. When such low molecular weight triols are used, low molecular weight triols and isocyanates By reaction with the compound, a urethane bond is integrated in the triol-branched portion, and a portion having a high density of urethane bonds in the molecule is generated.
우레탄 결합의 밀도가 높은 부분이 발생한 우레탄 예비 중합체를 사용하여 얻어진 폴리우레탄 수지를 코팅제 등의 원료로서 사용한 경우, 우레탄 결합이 집적된 곳에서 수소 결합이 형성되는 점에서 경도는 발현되지만, 분자 전체의 패킹이 흐트러져 버리기 때문에 피막 형성능이 떨어져서 균일한 도막을 얻는 것이 곤란하거나, 얻어진 도막의 균열이 발생하기 쉽다는 문제가 있다.When a polyurethane resin obtained by using a urethane prepolymer in which a portion having a high density of urethane bonds is used is used as a raw material for a coating agent or the like, hardness is exhibited in that hydrogen bonding is formed at the place where urethane bonds are integrated, There is a problem that it is difficult to obtain a uniform coating film because the packing is disturbed and the film-forming ability deteriorates, and cracks of the obtained coating film are liable to occur.
또한, 가지연장 단계에서의 가교도를 높이는 방법으로는 수분산 후의 물과의 반응성을 고려할 경우 트리올 뿐만 아니라 모든 알코올을 사용할 수가 없기에 물보다 반응성이 빠른 아민을 사용하여야 한다. 하지만, 수분산성 폴리우레탄의 가지연장 단계의 제조 과정에서 주로 사용되는 아민은 디아민 들이며 가교도를 높이고자 사용할 수 있는 지방족 트리아민은 물에 잘 녹지 않는 선형 구조의 트리 아민들이 대부분이기에 가교도가 증가하여 수분산 과정에서의 높은 점도로 인하여 분산성이 떨어져서, 분산에 실패하거나 장시간의 분산과정이 필요로 하여 목표로 하는 물성의 폴리우레탄 수지를 제조하기가 어렵다.In addition, as a method of increasing the degree of crosslinking in the branch extension step, considering the reactivity with water after water dispersion, it is necessary to use amines which are more reactive than water because all alcohols can not be used as well as triols. However, amines which are mainly used in the process of preparing the water-dispersible polyurethane elongation step are diamines, and the aliphatic triamines which can be used for increasing the degree of crosslinking are triamines having a linear structure which is insoluble in water, It is difficult to produce a polyurethane resin having a desired physical property because dispersion is difficult due to a high viscosity in the dispersion process and dispersion is required or a long time dispersion process is required.
이에 본 발명의 기술적 과제는 종래와 같이 수분산성 폴리우레탄 수지의 제조에 있어 물성을 높이고자 트리올을 사용함으로 인해 나타나는 문제를 해결하고자 착안된 기술로서, TNT의 환원반응으로 합성이 가능한 새로운 지방족 트리아민인 2-메틸사이클로헥산-1,3,5-트리아민을 이용하여 수분산성 폴리우레탄 수지를 제조하는 방법을 제공하는데 있다. Accordingly, a technical object of the present invention is to provide a novel aliphatic tree which can be synthesized by the reduction reaction of TNT, as a technique which is aimed at solving the problem caused by using triol in order to enhance the physical properties in the production of the water dispersible polyurethane resin, And a method for producing a water-dispersible polyurethane resin using 2-methylcyclohexane-1,3,5-triamine, which is an amine.
본 발명의 다른 과제는 상술한 방법으로 제조되는 수분산성 폴리우레탄 수지를 제공하는데 있다. Another object of the present invention is to provide a water dispersible polyurethane resin produced by the above-mentioned method.
상기한 본 발명의 과제를 실현하기 위한 수분산형 폴리우레탄 수지를 제조하는 방법은 하이드록시기를 갖는 폴리올, 카르복실기를 갖는 디올 및 지방족 디이소시아네이트를 혼합 반응시켜 이소시아네이트 말단형 폴리우레탄 예비중합체를 제조하는 단계와, 상기 이소시아네이트 말단형 폴리우레탄 예비중합체를 3급 아민으로 중화시켜 자기 유화형 예비중합체를 제조하는 단계와, 상기 자기 유화형 예비중합체에 물을 가하여 수 분산 시키는 단계와, 가지연장제로 2-메틸사이클로헥산-1,3,5-트리아민 이용하여 수 분산된 자기 유화형 예비중합체를 수분산성 폴리우레탄으로 제조하는 단계를 포함한다. The method for producing the water-dispersible polyurethane resin for realizing the object of the present invention includes a step of mixing and reacting a polyol having a hydroxy group, a diol having a carboxyl group and an aliphatic diisocyanate to prepare an isocyanate-terminated polyurethane prepolymer , Neutralizing the isocyanate-terminated polyurethane prepolymer with a tertiary amine to prepare a self-emulsifiable prepolymer, water-dispersing the self-emulsifiable prepolymer with water and dispersing the dispersion in water with 2-methylcyclo Hexane-1,3,5-triamine to prepare a water-dispersible self-emulsifiable prepolymer as a water-dispersible polyurethane.
일 실시예에 있어서, 상기 이소시아네이트 말단형 폴리우레탄 예비중합체는 폴리올, 모노머 디올, 카르복실기를 갖는 디올과 및 지방족 이소시아네이트를 1.1 내지 2.5의 NCO/OH비를 갖도록 혼합 반응시켜 형성할 수 있다. In one embodiment, the isocyanate-terminated polyurethane prepolymer may be formed by mixing and reacting a polyol, a monomer diol, a diol having a carboxyl group, and an aliphatic isocyanate to have an NCO / OH ratio of 1.1 to 2.5.
일 실시예에 있어서, 상기 이소시아네이트 말단형 폴리우레탄 예비중합체는 폴리올 100 중량부에 대하여 카르복실기를 갖는 디올 5 내지 15중량부, 지방족 디이소시아네이트 40 내지 70중량부를 혼합 반응시켜 형성할 수 있다.In one embodiment, the isocyanate-terminated polyurethane prepolymer may be formed by mixing and reacting 5 to 15 parts by weight of a diol having a carboxyl group and 40 to 70 parts by weight of an aliphatic diisocyanate with respect to 100 parts by weight of the polyol.
일 실시예에 있어서, 상기 이소시아네이트 말단형 폴리우레탄 예비중합체 제조시 유기용제 및 모노머 디올을 부가하여 형성할 수 있다.In one embodiment, the isocyanate-terminated polyurethane prepolymer may be formed by adding an organic solvent and a monomeric diol.
일 실시예에 있어서, 상기 3급 아민은 우레탄 예비중합체 제조과정에서 사용된 카르복실산을 함유한 디올 1몰 기준으로 0.6 내지 1.0몰의 범위 내에서 사용하고, 상기 수분산성 폴리우레탄 제조시 2-메틸사이클로헥산-1,3,5-트리아민을 폴리올 100 중량부에 대하여 3 내지 12 중량부를 사용할 수 있다.In one embodiment, the tertiary amine is used in a range of 0.6 to 1.0 mole based on 1 mole of a diol containing a carboxylic acid used in the urethane prepolymer production process, and in the production of the water-dispersible polyurethane, Methylcyclohexane-1,3,5-triamine can be used in an amount of 3 to 12 parts by weight based on 100 parts by weight of the polyol.
일 실시예에 있어서, 상기 히드라진, 에틸렌디아민, 이소프로필아민 및 디에틸렌트리아민으로 이루어진 군에서 선택된 적어도 하나의 아민 화합물을 상기 2-메틸사이클로헥산-1,3,5-트리아민과 함께 혼합하여 사용할 수 있다. In one embodiment, at least one amine compound selected from the group consisting of hydrazine, ethylenediamine, isopropylamine and diethylenetriamine is mixed with the 2-methylcyclohexane-1,3,5-triamine Can be used.
상기한 본 발명의 과제를 실현하기 위한 수분산형 폴리우레탄 수지는 하이드록시기를 갖는 폴리올, 모노머 디올, 카르복실기를 갖는 디올 및 지방족 디이소시아네이트를 혼합 반응시켜 이소시아네이트 말단형 폴리우레탄 예비중합체를 제조하는 단계와, 상기 이소시아네이트 말단형 폴리우레탄 예비중합체를 3급 아민으로 중화시켜 자기 유화형 예비중합체를 제조하는 단계와, 상기 자기 유화형 예비중합체에 물을 가하여 수 분산 시키는 단계와, 가지연장제로 2-메틸사이클로헥산-1,3,5-트리아민 이용하여 수 분산된 자기 유화형 예비중합체를 수분산성 폴리우레탄 제조하는 단계를 수행함으로서 수득될 수 있다.The water-dispersible polyurethane resin for realizing the above object of the present invention comprises a step of mixing and reacting a polyol having a hydroxy group, a monomer diol, a diol having a carboxyl group and an aliphatic diisocyanate to prepare an isocyanate-terminated polyurethane prepolymer, Neutralizing the isocyanate-terminated polyurethane prepolymer with a tertiary amine to prepare a self-emulsifiable prepolymer; water-dispersing the self-emulsifiable prepolymer with water; and adding 2-methylcyclohexane -1,3,5-triamine to prepare a water-dispersed self-emulsifiable prepolymer by dispersing the water-dispersible polyurethane.
본 발명에 따른 수분산성 폴리우레탄 수지를 제조하는데 있어서 2-메틸사이클로헥산-1,3,5-트리아민을 수분산 과정 후 가지연장제, 가교제로 이용한다면 이전의 예비중합체 제조과정의 불균일한 우레탄 결합이나 높은 점도로 인한 분산과정에서의 어려움을 해결할 뿐만 아니라 기계적 물성 및 내화학성이 우수한 수분산성 폴리우레탄 수지를 제조할 수 있다.When 2-methylcyclohexane-1,3,5-triamine is used as a branching agent and a crosslinking agent after the water-dispersing process in the production of the water-dispersible polyurethane resin according to the present invention, uneven urethane It is possible to prepare a water-dispersible polyurethane resin which not only solves difficulties in the dispersion process due to bonding or high viscosity, but also has excellent mechanical properties and chemical resistance.
이하, 본 발명을 보다 상세하게 설명하고자 한다. 본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 본문에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. Hereinafter, the present invention will be described in more detail. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 성분, 단계, 공정, 조성물 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 성분, 단계, 공정, 조성물 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. In this application, the terms "comprises" or "having", etc. are intended to specify the presence of stated features, components, steps, processes, compositions, or combinations thereof in the specification, and not to limit the presence or addition of one or more other features or components, Steps, processes, compositions, or combinations thereof, which are not intended to be limiting.
또한, 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.
Also, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
수분산성 폴리우레탄 수지 및 이의 제조방법Water-dispersible polyurethane resin and method for producing the same
본 발명에 따른 수분산성 폴리우레탄 수지를 제조하기 위해서 하이드록시기를 갖는 폴리올, 카르복실기를 갖는 디올, 유기용제 및 지방족 디이소시아네이트를 혼합 반응시켜 카르복실기 작용기를 포함하는 이소시아네이트 말단형 폴리우레탄 예비중합체를 제조한다. (S110)In order to prepare the water-dispersible polyurethane resin according to the present invention, an isocyanate-terminated polyurethane prepolymer containing a carboxyl group functional group is prepared by mixing and reacting a polyol having a hydroxy group, a diol having a carboxyl group, an organic solvent and an aliphatic diisocyanate. (S110)
S110 단계에 있어서, 상기 우레탄 예비중합체의 제조에 사용되는 폴리올은 2개의 하이드록시기를 갖는 화합물로서 20℃에서 액체 상태 이거나 30℃ 이상의 녹는점을 가지는 결정성 폴리올을 사용할 수 있다. In step S110, the polyol used in the preparation of the urethane prepolymer may be a compound having two hydroxy groups, and may be a liquid state at 20 占 폚 or a crystalline polyol having a melting point of 30 占 폚 or higher.
상기 폴리올 폴리옥시알킬렌 폴리올, 폴리테트라메틸렌 글리콜 폴리올, 폴리에스테르 폴리올, 폴리카프락톤 폴리올, 폴리카보네이트 폴리올, 폴리부타디엔 폴리올 들 중에서 적어도 하나를 선택하여 사용할 수 있다. 분자량 1,000~4,000의 범위의 폴리올을 사용하는 것이 바람직하다. At least one of the polyol polyoxyalkylene polyol, polytetramethylene glycol polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, and polybutadiene polyol may be selected and used. It is preferable to use a polyol having a molecular weight in the range of 1,000 to 4,000.
상기 카르복실산을 함유하는 디올은 친수성기를 도입하기 위해 사용되며, 구체적으로는 2,2-디메틸올초산, 2,2-디메틸올젖산, 2,2-디메틸올프로피온산, 2,2-디메틸올부탄산, 2,2-디메틸올부티르산, 2,2-디메틸올발레르산 등의 디히드록시카복실산을 1종 또는 그 이상을 선택하여 사용할 수 있다. The diol containing carboxylic acid is used for introducing a hydrophilic group, and specific examples thereof include 2,2-dimethylol acetic acid, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2- One or more dihydroxycarboxylic acids such as carbonic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid can be selected and used.
상기 카르복실산을 함유하는 디올은 폴리올 100중량부에 대하여 5.0 내지 15.0중량부로 사용할 수 있다. 만일, 그 사용량이 5.0중량부 미만일 경우에는 수분산체의 안정성이 저하되며, 15.0중량부를 초과하면 내수성 및 접착력이 저하된다. The diol containing the carboxylic acid may be used in an amount of 5.0-15.0 parts by weight based on 100 parts by weight of the polyol. If the amount is less than 5.0 parts by weight, the stability of the aqueous dispersion is deteriorated. If the amount is more than 15.0 parts by weight, the water resistance and the adhesive strength are lowered.
일 예로서, 디히드록시카복실산을 사용함에 있어서 고체일 경우, 디히드록시카복실산 100중량부에 대하여 N-메틸-2-피롤리돈, 디메틸포름아마이드, 디메틸설폭사이드 중에서 선택된 유기용제를 100 ~200중량부 가하여 용해시킨 후 사용할 수 있다. As an example, when using a dihydroxycarboxylic acid, an organic solvent selected from N-methyl-2-pyrrolidone, dimethylformamide, and dimethylsulfoxide is added to 100 to 200 parts by weight of dihydroxycarboxylic acid By weight and dissolving it.
그리고 상기 지방족 이소시아네이트는 1,6-헥산 디이소시아네이트(HDI), 이소포론 디이소시아네이트(IPDI), 메틸렌 비스(p-사이클로헥실 이소시아네이트((H12MDI) 등으로부터 1종 또는 그 이상을 선택하여 사용할 수 있다.And the aliphatic isocyanates are 1,6-hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene bis (cyclohexyl isocyanate p- ((H 12 MDI) by selecting one or more available, such as from have.
상기 카르복실기 작용기를 포함하는 이소시아네이트 말단형 우레탄 예비중합체는 통상의 폴리우레탄 제조방법에 따라 폴리올, 카르복실기를 갖는 디올(ex-디메틸폴리올 프로피온산) 및 지방족 이소시아네이트 혼합물을 NCO/OH 몰비가 1.1 내지 2.5로 반응시켜 제조할 수 있다. 이때 NCO/OH 몰비가 1.1보다 작으면 물성이 약해지며, 2.5를 초과하면 저장안정성이 저하된다.The isocyanate-terminated urethane prepolymer containing a carboxyl group functional group may be prepared by reacting a polyol, a diol having a carboxyl group (ex-dimethylpolyol propionic acid) and an aliphatic isocyanate mixture at an NCO / OH molar ratio of 1.1 to 2.5 according to a conventional polyurethane production method Can be manufactured. If the molar ratio of NCO / OH is less than 1.1, the physical properties are weakened. If it exceeds 2.5, storage stability is deteriorated.
일 예로서, 카르복실기 작용기를 포함하는 이소시아네이트 말단형 폴리우레탄 예비중합체 제조시 모노머 디올을 추가적으로 사용할 수 있다. 상기 모노머 디올은 에틸렌글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,3-부탄디올, 1,2-부탄디올, 1,5-펜탄디올, 1,4-펜탄디올, 1,3-펜탄디올, 1,6-헥산디올, 1,7-헵탄디올, 디에틸렌글리콜, 트리에틸렌글리콜 등으로부터 1종 또는 그 이상을 선택하여 사용할 수 있다. As an example, a monomer diol may additionally be used in preparing an isocyanate-terminated polyurethane prepolymer containing a carboxyl group functionality. The monomer diol may be selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, Pentanediol, 1,6-hexanediol, 1,7-heptanediol, diethylene glycol, triethylene glycol, and the like.
이어서, 상기 카르복실기 작용기를 포함하는 이소시아네이트 말단형 우레탄 예비중합체를 3급 아민으로 중화시켜 자기 유화형 예비중합체를 제조한다.(S120)Subsequently, the isocyanate-terminated urethane prepolymer containing the carboxyl group functional group is neutralized with a tertiary amine to prepare a self-emulsifiable prepolymer (S120)
S120 단계에 있어서, 상기 본 발명의 중화과정에서 사용되는 3급 아민은 제조된 우레탄 예비중합체를 중화시키기 위해 사용되며, 상기 3차아민은 트리에틸아민, N-메틸모르포린, 디메틸아미노에탄올, 암모니아수 등으로부터 1종 또는 그 이상을 선택하여 사용할 수 있다.In the step S120, the tertiary amine used in the neutralization process of the present invention is used for neutralizing the urethane prepolymer. The tertiary amine may be triethylamine, N-methylmorpholine, dimethylaminoethanol, And the like can be selected and used.
상기 우레탄 예비중합체 제조과정에서 사용된 카르복실산을 함유한 디올 1몰 기준으로 0.6 내지 1.0몰 만큼 사용하는 것이 바람직하다. 상기 3급 아민의 사용량이 0.6몰 이하이면 중화가 잘 이루어지지 않으며, 1.0몰을 초과하면 카르복실산과 반응 후 잔존하는 3급 아민에 의하여 수분산 후의 점도가 상승하는 결과를 초래한다. It is preferable to use 0.6 to 1.0 mol based on 1 mol of the diol containing the carboxylic acid used in the urethane prepolymer production process. When the amount of the tertiary amine used is less than 0.6 mol, neutralization is not achieved. If the amount of the tertiary amine is more than 1.0 mol, the viscosity after the water dispersion is increased by the tertiary amine remaining after the reaction with the carboxylic acid.
이어서, 상기 자기 유화형 예비중합체에 물을 가하여 수 분산 시킨다. (S130)Next, water is added to the self-emulsifiable prepolymer and water-dispersed. (S130)
S130 단계에 있어서, 상기 물은 폴리올 100 중량부에 대하여 250 내지 350 중량부를 사용할 수 있다. In step S130, the water may be used in an amount of 250 to 350 parts by weight based on 100 parts by weight of the polyol.
이어서, 가지연장제로 2-메틸사이클로헥산-1,3,5-트리아민 이용하여 수 분산된 자기 유화형 예비중합체를 수분산성 폴리우레탄 수지로 제조한다. (S140)Next, a self-emulsifiable prepolymer water-dispersed using 2-methylcyclohexane-1,3,5-triamine as an elongation agent is prepared as a water-dispersible polyurethane resin. (S140)
S140 단계에 있어서, 상기 2-메틸사이클로헥산-1,3,5-트리아민은 하기 구조식1과 같이 TNT의 환원반응으로 합성되며, 우레탄 예비중합체를 수분산성 폴리우레탄을 제조하기 위한 가지연장제와 가교제로 폴리올 100 중량부에 대하여 3.5 내지 12 중량부의 범위 내에서 사용될 수 있다.In step S140, the 2-methylcyclohexane-1,3,5-triamine is synthesized by a reduction reaction of TNT as shown in the following structural formula 1, and the urethane prepolymer is reacted with an extender for producing a water- May be used as a crosslinking agent in a range of 3.5 to 12 parts by weight based on 100 parts by weight of the polyol.
구조식 1. 디아미노니트로톨루엔의 제조법Structure 1. Preparation of diaminonitrotoluene
상기 2-메틸사이클로헥산-1,3,5-트리아민은 구조식 1에서 보는 바와 같이 지방족 구조를 가지면서 물에 녹는 트리아민으로서 수분산성 폴리우레탄 가지연장 단계에서 단독으로 사용되거나 다른 아민들과 혼합되어져 사용될 수 있다.The 2-methylcyclohexane-1,3,5-triamine can be used alone in the water-dispersible polyurethane branch elongation step as a water-soluble triamine having an aliphatic structure as shown in the structural formula 1 or mixed with other amines Can be used.
상기 다른 아민의 예로서는 1급 또는 2급 아미노기를 2개 이상 함유하는 히드라진, 에틸렌디아민, 이소프로필아민, 디에틸렌트리아민 등을 들 수 있다. Examples of the other amine include hydrazine, ethylenediamine, isopropylamine, and diethylenetriamine, which contain two or more primary or secondary amino groups.
본 발명의 폴리우레탄 수지 제조시 가지연장 단계에서의 가교도를 높이는 방법으로는 수분산 후의 물과의 반응성을 고려할 경우 트리올 뿐만 아니라 모든 알코올을 사용할 수가 없기에 물보다 반응성이 빠른 아민(2-메틸사이클로헥산-1,3,5-트리아민)을 사용하여야 한다. As a method for increasing the degree of crosslinking in the step of elongating the polyurethane resin of the present invention, considering the reactivity with water after water dispersion, all alcohols as well as triols can not be used. Therefore, amines (2-methylcyclo Hexane-1,3,5-triamine) should be used.
또한, 상기 메틸사이클로헥산-1,3,5-트리아민 이용하여 수분산성 폴리우레탄 수지 제조시 수분산과 가지연장, 가교가 끝난 후의 수분산성 폴리우레탄의 고형분의 농도는 10 내지 45%로 조정될 수 있다.Further, the concentration of the solid content of the water-dispersible polyurethane after water dispersion, branch extension and crosslinking in the production of the water-dispersible polyurethane resin using the methylcyclohexane-1,3,5-triamine can be adjusted to 10 to 45% .
그리고 본 발명의 수분산성 폴리우레탄 수지의 제조시 필요에 따라 점도 조절제, 경화제, 산화방지제 및 노화방지제, 소포제, 레벨링제 등의 첨가제를 첨가할 수 있다.In the production of the water-dispersible polyurethane resin of the present invention, additives such as viscosity adjusting agents, curing agents, antioxidants and antioxidants, antifoaming agents and leveling agents may be added.
상술한 방법으로 제조되는 수분산성 폴리우레탄 수지는 2-메틸사이클로헥산-1,3,5-트리아민을 수분산 과정 후 가지연장제, 가교제로 이용하여 형성됨으로 인해 이전의 예비중합체 제조과정의 불균일한 우레탄 결합이나 높은 점도로 인한 분산과정에서의 어려움이 발생하지 않을 뿐만 아니라 기계적 물성 및 내화학성이 우수한 특성을 갖는다.The water-dispersible polyurethane resin prepared by the above-mentioned method is formed by using 2-methylcyclohexane-1,3,5-triamine as a branching agent and a crosslinking agent after the water dispersion process, It does not cause difficulties in the dispersion process due to a urethane bond or a high viscosity, and has properties of excellent mechanical properties and chemical resistance.
이하, 본 발명의 바람직한 실시예와 비교예의 설명을 통해 본 발명을 보다 상세하게 설명하고자 한다. 그러나 하기 실시예는 본 발명의 이해를 돕기 위한 일 예에 불과한 것으로 이에 의해 본 발명의 권리범위가 축소되거나 한정되어서는 안 된다.
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments and comparative examples of the present invention. However, the following examples are merely examples for helping understanding of the present invention, and thus the scope of the present invention should not be limited or limited.
[실시예 1][Example 1]
수평균 분자량이 2000인 폴리카보네이트디올 204.69g, 디메틸올프로피온산 21.77g, N-메틸-2-피롤리돈 32.49g, 이소포론 디이소시아네이트 105.82g을 가한 후 온도를 80~85℃로 조정하여 210분 동안 반응하여 이소시아네이트 말단 우레탄 예비중합체를 제조하였다.204.69 g of a polycarbonate diol having a number average molecular weight of 2000, 21.77 g of dimethylolpropionic acid, 32.49 g of N-methyl-2-pyrrolidone and 105.82 g of isophorone diisocyanate were added and the temperature was adjusted to 80 to 85 캜, To prepare an isocyanate-terminated urethane prepolymer.
제도된 예비중합체의 온도를 70℃로 냉각시킨 후 빠르게 교반하면서 트리에틸아민 13.64g을 가하여 중화하였다. 중화된 예비중합체에 물 592.47을 첨가하여 10여분 동안 분산 시켰다. 여기에 2-메틸사이클로헥산-1,3,5-트리아민 16.17g을 물에 용해시켜 정량적으로 투입한 후 추가적으로 60분동안 가지연장, 가교반응을 실시하여 고형분 35%의 수분산성 폴리우레탄을 얻었다.
The temperature of the prepared prepolymer was cooled to 70 캜 and neutralized by adding 13.64 g of triethylamine with rapid stirring. To the neutralized prepolymer was added water 592.47 and dispersed for 10 minutes. 16.17 g of 2-methylcyclohexane-1,3,5-triamine was dissolved in water and the mixture was quantitatively added. The mixture was further subjected to a branch extension and crosslinking reaction for 60 minutes to obtain a water-dispersible polyurethane having a solid content of 35% .
[실시예 2][Example 2]
수평균 분자량이 2000인 폴리카보네이트디올 204.69g, 디메틸올프로피온산 21.77g, N-메틸-2-피롤리돈 32.49g, 이소포론 디이소시아네이트 105.82g을 가한 후 온도를 80~85℃로 조정하여 210분 동안 반응하여 이소시아네이트 말단 우레탄 예비중합체를 제조하였다.204.69 g of a polycarbonate diol having a number average molecular weight of 2000, 21.77 g of dimethylolpropionic acid, 32.49 g of N-methyl-2-pyrrolidone and 105.82 g of isophorone diisocyanate were added and the temperature was adjusted to 80 to 85 캜, To prepare an isocyanate-terminated urethane prepolymer.
제도된 예비중합체의 온도를 70℃로 냉각시킨 후 빠르게 교반하면서 트리에틸아민 13.64g을 가하여 중화하였다. 중화된 예비중합체에 물 597.98을 첨가하여 10여분 동안 분산 시켰다. 여기에 2-메틸사이클로헥산-1,3,5-트리아민 8.09g, 에틸렌디아민 5.08g을 물에 용해시켜 정량적으로 투입한 후 추가적으로 60분동안 가지연장, 가교반응을 실시하여 고형분 35%의 수분산성 폴리우레탄을 얻었다.The temperature of the prepared prepolymer was cooled to 70 캜 and neutralized by adding 13.64 g of triethylamine with rapid stirring. To the neutralized prepolymer was added 597.98 of water and dispersed for 10 minutes. 8.09 g of 2-methylcyclohexane-1,3,5-triamine and 5.08 g of ethylenediamine were dissolved in water and quantitatively added. The mixture was further subjected to crosslinking reaction for 60 minutes to obtain 35% To obtain an acidic polyurethane.
실시예 1과 같이 얻어진 수분산성 폴리우레탄 기계적 물성을 측정하기 위하여
To measure the water-dispersible polyurethane mechanical properties obtained as in Example 1
[비교예 1][Comparative Example 1]
수평균 분자량이 2000인 폴리카보네이트디올 204.69g, 디메틸올프로피온산 21.77g, N-메틸-2-피롤리돈 32.49g, 트리메틸올프로판 16.17g, 이소포론 디이소시아네이트 178.14g을 가한 후 온도를 80~85℃로 조정하여 210분 동안 반응하여 이소시아네이트 말단 우레탄 예비중합체를 제조하였다.After adding 204.69 g of polycarbonate diol having a number average molecular weight of 2000, 21.77 g of dimethylolpropionic acid, 32.49 g of N-methyl-2-pyrrolidone, 16.17 g of trimethylolpropane and 178.14 g of isophorone diisocyanate, Lt; 0 > C and reacted for 210 minutes to prepare an isocyanate-terminated urethane prepolymer.
제도된 예비중합체의 온도를 70℃로 냉각시킨 후 빠르게 교반하면서 트리에틸아민 13.64g을 가하여 중화하였다. 중화된 예비중합체에 물 757.28을 첨가하여 10여분 동안 분산 시켰다. 여기에 에틸렌디아민 17.12g을 물에 용해시켜 정량적으로 투입한 후 추가적으로 60분동안 가지연장, 가교반응을 실시하여 고형분 35%의 수분산성 폴리우레탄을 얻었다.
The temperature of the prepared prepolymer was cooled to 70 캜 and neutralized by adding 13.64 g of triethylamine with rapid stirring. To the neutralized prepolymer was added water 757.28 and dispersed for 10 minutes. 17.12 g of ethylenediamine was dissolved in water and the mixture was quantitatively added thereto. Thereafter, an extension and crosslinking reaction were further carried out for 60 minutes to obtain a water-dispersible polyurethane having a solid content of 35%.
[비교예 2][Comparative Example 2]
수평균 분자량이 2000인 폴리카보네이트디올 204.69g, 디메틸올프로피온산 21.77g, N-메틸-2-피롤리돈 32.49g, 트리메틸올프로판 4.47g, 이소포론 디이소시아네이트 125.8g을 가한 후 온도를 80~85℃로 조정하여 210분 동안 반응하여 이소시아네이트 말단 우레탄 예비중합체를 제조하였다.After adding 204.69 g of polycarbonate diol having a number average molecular weight of 2000, 21.77 g of dimethylolpropionic acid, 32.49 g of N-methyl-2-pyrrolidone, 4.47 g of trimethylolpropane and 125.8 g of isophorone diisocyanate, Lt; 0 > C and reacted for 210 minutes to prepare an isocyanate-terminated urethane prepolymer.
제도된 예비중합체의 온도를 70℃로 냉각시킨 후 빠르게 교반하면서 트리에틸아민 13.64g을 가하여 중화하였다. 중화된 예비중합체에 물 635.89을 첨가하여 10여분 동안 분산 시켰다. 여기에 에틸렌디아민 12.09g을 물에 용해시켜 정량적으로 투입한 후 추가적으로 60분동안 가지연장, 가교반응을 실시하여 고형분 35%의 수분산성 폴리우레탄을 얻었다.
The temperature of the prepared prepolymer was cooled to 70 캜 and neutralized by adding 13.64 g of triethylamine with rapid stirring. 635.89 of water was added to the neutralized prepolymer and dispersed for 10 minutes. 12.09 g of ethylenediamine was dissolved in water and metered in. The mixture was further subjected to an elongation and crosslinking reaction for 60 minutes to obtain a water-dispersible polyurethane having a solid content of 35%.
수분산 폴리우레탄 수지의 안정성 평가Evaluation of stability of water-dispersed polyurethane resin
각 실시예 및 각 비교예에서 제조과정중의 안정성 및 제조된 수분산 폴리우레탄 수지를 50℃에서 7일간 저장한 후, 눈으로 확인하여 분산성을 관찰하였다. 표 1에서 제조과정중의 안정성이 문제가 된 경우에는 XX, 제조한 후 수분산 폴리우레탄의 수지의 저장성 평가에서 균일하게 분산되어 있지 않으면 X, 균일한 상태면 O로 나타내었다.
Stability during the manufacturing process and the water-dispersed polyurethane resin prepared in each of the Examples and Comparative Examples were stored at 50 ° C for 7 days, and visually observed for dispersibility. In Table 1, when the stability during the manufacturing process was a problem, X was expressed as X if the resin was not uniformly dispersed in the storage stability evaluation of the resin of the water-dispersed polyurethane after the preparation, and as O in the homogeneous state.
폴리우레탄 필름의 제조Production of polyurethane film
실시예 1,2와 비교예 1,2를 통해 합성 한 수분산성 폴리우레탄 수지를 이형판에 약 0.5mm 두께로 균일하게 도포하였다. 이어서, 120℃로 6시간 건조 한 후, 이형판에서 박리하여 필름의 물성을 평가하였다.
The water-dispersible polyurethane resin synthesized through Examples 1 and 2 and Comparative Examples 1 and 2 was uniformly applied to a release plate at a thickness of about 0.5 mm. Subsequently, the film was dried at 120 DEG C for 6 hours and then peeled off from the release plate to evaluate the physical properties of the film.
필름의 기계적 물성 평가Evaluation of Mechanical Properties of Film
상기 폴리우레탄 필름의 기계적 물성을 알아보기 위하여 만능시험측정기(UTM)를 이용하여 인장강도, 신장율 등을 측정하였으며, 표1에 나타내었다. 내화학성을 평가하기 알코올 러빙테스트를 위하여 표 1에 나타내었다.
The tensile strength, elongation and the like of the polyurethane film were measured using a universal testing machine (UTM) to determine the mechanical properties of the polyurethane film. Evaluation of chemical resistance Table 1 shows an alcohol rubbing test.
필름의 내용제성 및 내알콜성 평가Evaluation of solvent resistance and alcohol resistance of film
건조된 폴리우레탄 필름에 대한 내화학적 성질을 알아보기 위하여 메틸에틸케톤과 메탄올을 면장갑에 묻혀서 50회 이상의 러빙테스트(rubbing test)을 실시하여 내용제성 및 내알콜성을 확인하였다. 내용제성 및 내알콜성이 우수한 경우에는 O, 보통의 경우에는 △, 떨어지는 경우에는 X로 결과를 표 1에 나타내었다.[In order to investigate the chemical properties of dried polyurethane film, solvent resistance and alcohol resistance were examined by rubbing test of methyl ethyl ketone and methanol in cotton gloves 50 times or more. When the solvent resistance and alcohol resistance were excellent, the results are shown in Table 1 as O, in the normal case,?, And in the case of falling, X. [
[표 1][Table 1]
실시예 1, 2는 수분산성 폴리우레탄 제조 과정에서 전혀 문제가 발생하지 않았지만, 특히, 비교예 1의 경우에서는 예비중합체 제조시 저분자 트리올을 사용하여 가교도를 높인 결과 수분산 과정에서 높은 점도로 인하여 원활한 분산이 이루어지지 않았으며, 이로 인하여 가지연장 후 수분산성 폴리우레탄의 안정성이 저하되어 겔화 현상이 발생하였다.In Examples 1 and 2, no problem occurred during the production of the water-dispersible polyurethane. However, in Comparative Example 1, in the preparation of the prepolymer, low molecular weight triols were used to increase the degree of crosslinking. As a result, And the dispersion of water dispersible polyurethane after the elongation of the branches deteriorated to cause gelation phenomenon.
실시예 1, 2와 비교예 1, 2의 결과를 통하여 2-메틸사이클로헥산-1,3,5-트리아민을 가지연장제, 가교제로 사용할 경우 인장강도 및 인열강도 등의 기계적 물성이 매우 우수하였으며, 높은 가교도로 인하여 내화학성 평가에서 우수한 결과를 얻을 수 있는 것이 확인되었다.
The results of Examples 1 and 2 and Comparative Examples 1 and 2 show that when 2-methylcyclohexane-1,3,5-triamine is used as a branching and crosslinking agent, mechanical properties such as tensile strength and tear strength are very high And it was confirmed that excellent results were obtained in chemical resistance evaluation due to high degree of crosslinking.
Claims (6)
상기 이소시아네이트 말단형 폴리우레탄 예비중합체를 3급 아민으로 중화시켜 자기 유화형 예비중합체를 제조하는 단계;
상기 자기 유화형 예비중합체에 물을 가하여 수 분산 시키는 단계; 및
가지연장제로 2-메틸사이클로헥산-1,3,5-트리아민 이용하여 수 분산된 자기 유화형 예비중합체를 수분산성 폴리우레탄 제조하는 단계를 포함하는 것을 특징으로 하는 수분산성 폴리우레탄 수지의 제조방법.A polyol having a hydroxyl group, a diol having a carboxyl group and an aliphatic diisocyanate to prepare an isocyanate-terminated polyurethane prepolymer;
Neutralizing the isocyanate-terminated polyurethane prepolymer with a tertiary amine to prepare a self-emulsifiable prepolymer;
Water-dispersing the self-emulsifiable prepolymer by water; And
Dispersing the self-emulsifiable prepolymer with water by using 2-methylcyclohexane-1,3,5-triamine as a branching agent to prepare a water-dispersible polyurethane resin .
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