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KR20030018113A - Urethan compound and it's producing method - Google Patents

Urethan compound and it's producing method Download PDF

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Publication number
KR20030018113A
KR20030018113A KR1020010051676A KR20010051676A KR20030018113A KR 20030018113 A KR20030018113 A KR 20030018113A KR 1020010051676 A KR1020010051676 A KR 1020010051676A KR 20010051676 A KR20010051676 A KR 20010051676A KR 20030018113 A KR20030018113 A KR 20030018113A
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general formula
urethane
cnh
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compound
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손석호
이형달
정종국
남정윤
임정훈
김우식
박인준
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니카코리아 (주)
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/60Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms

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  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

본 발명은 접착력 및 내구성을 가지는 우레탄계 화합물 및 그 제조 방법에 관한 것으로, 셀룰로스계 섬유에 사용 가능한 표면 개질제 제조를 위해 내구성 모노머인 Vcl과 VDC를 대체하여,The present invention relates to a urethane-based compound having an adhesive force and durability, and to a method of manufacturing the same, replacing the durable monomers Vcl and VDC for the preparation of surface modifiers usable for cellulose fibers.

모노머의 공중합 과정에 참여할 수 있도록 2중 결합기를 부여하고 발수 처리와 열처리 공정을 거쳐 분리되는 우레탄 모노머를 제공하여 섬유 품질 향상과 인체 및 환경 친화적인 표면 개질제 제공을 이루기 위해 창출된 것으로,It was created to improve fiber quality and provide human and environment-friendly surface modifiers by providing a double bond group to participate in the copolymerization process of monomers and providing urethane monomers separated through water repellent treatment and heat treatment processes.

이러한 모노머는 -NCO말단기를 가지는 우레탄 모노머를 기본 성질로 하여 여기에 2중 결합을 가진 하이드록시 화합물과 옥심계 화합물을 부가 반응하여 생성되며 하기의 일반식(Ⅰ)로 표시되는 것을 특징으로 한다.Such monomers are produced by addition reaction of a hydroxy compound having a double bond and an oxime compound with a urethane monomer having a -NCO terminal group as a basic property, and are represented by the following general formula (I). .

일반식(Ⅰ)General formula (Ⅰ)

(Ⅰ) (Ⅰ)

R1은CnH2n, CnH2n-2O n=1∼10, R2는 탄소수 2 ∼ 14의 탄화수소기,R 1 is CnH 2 n, CnH 2 n- 2 O n = 1-10, R 2 is a C2-C14 hydrocarbon group,

R3은COO(CH2)n n=1∼4, (CH2)nn=0∼4, (CH2)nCOn=0∼4, R4는 H 또는 CnH2n+1n=1∼4R 3 is COO (CH 2 ) nn = 1-4, (CH 2 ) nn = 0-4, (CH 2 ) nCOn = 0-4, R 4 is H or CnH 2 n + 1 n = 1-4

Description

접착력 및 내구성을 가지는 우레탄계 화합물 및 그 제조 방법{Urethan compound and it's producing method}Urethane compound and it's producing method which have adhesive strength and durability

본 발명은 접착력 및 내구성을 가지는 우레탄계 화합물 및 그 제조 방법에 관한 것으로 더욱 상세하게는,The present invention relates to a urethane-based compound having an adhesive force and durability, and more particularly,

섬유를 비롯한 다양한 제품의 표면에 도포되어 발수, 발유등의 작용을 수행하는 표면 개질제에 첨가되어 표면 개질제의 접착력 및 내구성 부여를 위한 우레탄계 화합물 및 그 제조 방법에 관한 것이다.The present invention relates to a urethane-based compound applied to the surface of various products including fibers to perform water repellent, oil repellent, and the like, and to provide adhesion and durability of the surface modifier, and a method of manufacturing the same.

일반적으로 고분자 화학물은 단위 분자인 모노머(단량체)와 수 없이 많은 모노머가 상호 결합하여된 폴리머(중합체)의 구조를 가지며, 이러한 모노머 및 폴리머로 형성된 고분자 화학물은 다양한 형태와 적용 대상을 갖는다.In general, a polymer chemical has a structure of a polymer (polymer) in which a monomer (monomer) as a unit molecule and a number of monomers are bonded to each other, and the polymer chemical formed of such a monomer and a polymer has various forms and applications.

특히 프리 폴리머 타입의 우레탄계 화합물은 잉크, 접착제, 도료등에 첨가되어 대상물과 잉크, 접착제 및 도료등의 접착력 및 내구성 부여 작용을 하게 된다.In particular, the urethane-based compound of the prepolymer type is added to an ink, an adhesive, a paint, and the like to provide adhesion and durability to the object, ink, adhesive, and paint.

섬유, 종이를 비롯한 각종 대상물은 표면 개질제로서 불소계 발수발유제를 표면에 도포하며, 이들 대상물과 표면 개질제의 접착성 및 내구성 부여를 위해 다양한 방법들이 시행되고 있다.Various objects such as fiber and paper apply a fluorine-based water and oil repellent agent to the surface as a surface modifier, and various methods have been implemented to impart the adhesion and durability of these objects and the surface modifier.

특히 섬유 가운데 셀룰로스(cellulose)계인 면, 레인온, 폴레에스테르/면(T/C), 폴리에스테르/레이온(T/R), 나일론/면(N/C), 나일론/레이온(N/R)등의 표면에 불소계 발수발유제를 도포하기 위해서는,In particular, cellulose-based cotton, rain-on, polyester / cotton (T / C), polyester / rayon (T / R), nylon / cotton (N / C), nylon / rayon (N / R) In order to apply a fluorine-based water / oil repellent agent to the surface of

불소계 발수발유제의 공중합 과정에서 내구성 부여 물질인 Vcl(Vinylchloride)이나 VDC(Vinylidine chloride)를 투입하여 폴리머 체인에 기능성을 부여하거나, 수지를 병용 처리하는 방법등이 시행되고 있다.In the process of copolymerizing a fluorine-based water and oil repellent, Vcl (Vinylchloride) or VDC (Vinylidine chloride), which is a durable substance, is added to impart functionality to the polymer chain, or a combination treatment of resins is being conducted.

Vcl과 VDC를 첨가하는 방법은 현재 가장 많이 사용되는 방법이나 두 물질의 취급이 어렵고 인체 및 환경에 치명적인 악영향을 초래하며,The addition of Vcl and VDC is currently the most commonly used method, but it is difficult to handle both materials and has a fatal adverse effect on the human body and the environment.

특히 셀룰로스계 섬유에 처리할 경우 섬유의 질감이 현저하게 저하되는 문제점을 안고 있었다.In particular, when treated to the cellulose-based fibers had a problem that the texture of the fiber is significantly reduced.

그리하여 상기한 문제점을 보완하기 위해 멜라민 수지를 병용 처리하는 방법이 이용되나, 이 역시 멜라민 수지의 작업 공정이 난이하여 원가 상승 요인으로 작용하여,Thus, in order to compensate for the above problems, a method of using a combination of melamine resins is used, but this also acts as a cost increase factor due to the difficulty of the work process of melamine resins,

대부분이 섬유의 질감과 환경 오염의 우려가 높은 Vcl과 VDC의 첨가물을 이용함으로 환경 파괴와 인체에 치명적인 병해를 야기하는 문제점으로 작용하였다.Most of them use the additives of Vcl and VDC, which are highly concerned about the texture of the fabric and environmental pollution, which causes problems of environmental destruction and fatal diseases.

이에 본 발명에서는 상기한 문제점을 해결하기 위해 창출된 것으로 셀룰로스계 섬유에 사용 가능한 표면 개질제 제조를 위해 내구성 모노머인 Vcl과 VDC를 대체하여,Accordingly, in the present invention, to solve the above problems, to replace the durable monomers Vcl and VDC for the production of surface modifiers usable for cellulose fibers,

모노머의 공중합 과정에 참여할 수 있도록 2중 결합기를 부여하고 발수 처리와 열처리 공정을 거쳐 분리되는 우레탄 모노머를 제공하여 섬유 품질 향상과 인체 및 환경 친화적인 표면 개질제 제공을 그 목적으로 한다.The purpose of the present invention is to provide a urethane monomer that is separated through a water-repellent treatment and a heat treatment process to provide a double bond group to participate in the copolymerization process of the monomer, and to improve fiber quality and provide a surface modifier that is human and environmentally friendly.

상기 목적을 달성하기 위한 본 발명인 접착력 및 내구성을 가지는 우레탄계 화합물 및 그 제조 방법은,Urethane-based compound having a bonding strength and durability of the present invention for achieving the above object and a method for producing the same,

표면 개질제의 일종인 불소계 발수발유제의 공중합 과정에서 접착력 및 내구성 부여를 위해 첨가되는 모노머인 Vcl과 VDC를 대체하여 불소계 발수발유제의 합성 공정에 우레탄계 모노머를 투입시켜,In the copolymerization process of the fluorine-based water and oil repellent, which is a type of surface modifier, a urethane-based monomer is added to the synthesis process of the fluorine-based water and oil repellent by replacing Vcl and VDC, which are monomers added to provide adhesion and durability.

반응 생성된 폴리머에 기능성을 부여하고 셀룰로스섬유에 처리할 경우 내구성 향상을 실현할 수 있다.Functionality can be imparted to the resulting polymer and treated with cellulose fibers to improve durability.

이러한 내구성 모노머는 불소계 발수발유제 뿐만 아니라 공중합을 통해 생성되는 모든 화합물의 제조 공정에 사용가능하다.Such durable monomers can be used in the manufacturing process of all compounds produced through copolymerization as well as fluorine-based water and oil repellents.

본 발명에서는 우레탄 모노머의 기본 골격을 -NCO기를 2개 가지는 디이소시아네이트계 우레탄 모노머로서,In the present invention, the basic skeleton of the urethane monomer is a diisocyanate-based urethane monomer having two -NCO groups,

이 우레탄 모노머는 기본 반응 물질로 이소시아네이트기와 하이드록시기와의 반응에 따라 다양한 물성을 가지는 물질로 변화될 수 있으며, 그 가운데 2중 결합기를 가지며 일정 온도 범위에서 분리 가능한 우레탄계 화합물을 합성하고자 함이다.The urethane monomer may be changed into a material having various physical properties according to the reaction of an isocyanate group with a hydroxyl group as a basic reaction material, and is intended to synthesize a urethane-based compound having a double bond group and separable at a predetermined temperature range.

그리하여 본 발명에서는 -NCO기를 가진 모노머와 그 외 이소시아네이트기와 하이드록시기 2가지 모노머간의 반응 몰비가 항상 일정하게 반응에 참여되며 디이소시아네이트의 일측에는 2중 결합기를 가지고 타측에는 고온에서 분리 가능한 기능성 기를 가지는 화합물을 합성하도록 한다.Thus, in the present invention, the reaction molar ratio between the monomer having -NCO group and the other two isocyanate groups and the hydroxy group always participates in the reaction constantly, and on one side of the diisocyanate has a double bond group and the other side has a functional group that can be separated at high temperature. Allow compounds to be synthesized.

상기와 같은 목적을 달성하기 위한 본 발명인 접착성 및 내구성을 지니는 우레탄계 화합물은,Urethane-based compound having an adhesive and durability of the present invention for achieving the above object,

일반식(Ⅰ)General formula (Ⅰ)

(Ⅰ) (Ⅰ)

여기서;here;

R1은CnH2n, CnH2n-2On=1∼10R 1 is CnH 2 n, CnH 2 n -2 On = 1 to 10

R2는 탄소수 2 ∼ 14의 탄화수소기R 2 is a hydrocarbon group having 2 to 14 carbon atoms

R3은COO(CH2)nn=1∼4R 3 is COO (CH 2 ) nn = 1 to 4

(CH2)nn=0∼4(CH 2 ) nn = 0 to 4

(CH2)nCOn=0∼4(CH 2 ) nCOn = 0 to 4

R4는 H 또는 CnH2n+1n=1∼4R 4 is H or CnH 2 n +1 n = 1 to 4

상기 일반식(Ⅰ)로 표시되는 우레탄계 화합물은,The urethane-based compound represented by the general formula (I),

하기의 일반식(Ⅱ),General formula (II) below,

OCN-R2-NCO(Ⅱ)OCN-R 2 -NCO (Ⅱ)

R2 : 탄소수 2∼14의 탄화수소기R2 is a hydrocarbon group having 2 to 14 carbon atoms

에,on,

하기 일반식(Ⅲ)General formula (III)

R1=NOH(Ⅲ)R 1 = NOH (III)

R1: CnH2n, CnH2n-2On=1∼10R 1 : CnH 2 n, CnH 2 n -2 On = 1 to 10

으로 표시되는 기능성 모노머와,A functional monomer represented by

하기 일반식(Ⅳ)General formula (IV)

CH2=CR4R3OH(Ⅳ)CH 2 = CR 4 R 3 OH (Ⅳ)

R3:COO(CH2)nn=1∼4R 3 : COO (CH 2 ) nn = 1 to 4

(CH2)nn=0∼4(CH 2 ) nn = 0 to 4

(CH2)nCOn=0∼4(CH 2 ) nCOn = 0 to 4

R4 :H 또는 CnH2n+1n=1∼4R4: H or CnH 2 n +1 n = 1 to 4

로 표시되는 2중 결합과 하이드록시기를 가진 모노머를 반응시켜 제조된다.It is prepared by reacting a monomer having a double bond and a hydroxyl group represented by.

상기 일반식(Ⅱ)로 표시되는 우레탄 모노머로는 -NCO기에 포함된 탄소를 제외한 탄소수가 2∼14인 디이소시아네이트류로 이루어진 군으로부터 선택된다.The urethane monomer represented by the general formula (II) is selected from the group consisting of diisocyanates having 2 to 14 carbon atoms except for carbon contained in the -NCO group.

상기 디이소시아네이트류로는 TDI(Tolylene-2, 4-diisocyanate), MDI(Diphenylmethane-4, 4-diisocyanate), HDI(Hexamethylene diisocyanate)등이 사용될 수 있다.As the diisocyanate, TDI (Tolylene-2, 4-diisocyanate), MDI (Diphenylmethane-4, 4-diisocyanate), HDI (Hexamethylene diisocyanate) and the like may be used.

상기 일반식(Ⅲ)으로 표시되는 옥심계의 화합물은 Biacetyl monoxime,Methylethylketone oxime등이 사용될 수 있다.As the oxime compound represented by the general formula (III), Biacetyl monoxime, Methylethylketone oxime, and the like may be used.

또한 상기 일반식(Ⅳ)로 표시되는 2중 결합기를 가진 화합물로는 2-Hydroxy ethylacrylate, 2-Hydroxypropylacrylate, 2-Hydroxyethylmethacrylate, 2-Hydroxypropylmethacrylate, Allylalcohol, Acrylic acid, methacrylic acid등이 사용될 수 있다.In addition, as the compound having a double bond group represented by the general formula (IV), 2-Hydroxy ethylacrylate, 2-Hydroxypropylacrylate, 2-Hydroxyethylmethacrylate, 2-Hydroxypropylmethacrylate, Allylalcohol, Acrylic acid, methacrylic acid and the like can be used.

상기 일반식(Ⅱ),(Ⅲ),(Ⅳ)의 부가반응은 상압하에서 40-80℃의 조건으로 2-5시간을 반응시키는 것이 바람직하며, 반응조 내에 포함된 공기의 영향을 최소화하기 위해 질소기류하에서 반응하도록 한다.The addition reaction of the general formula (II), (III), (IV) is preferably reacted for 2-5 hours under the condition of 40-80 ℃ under normal pressure, in order to minimize the effect of air contained in the reactor React under airflow.

이와 같이 일반식(Ⅱ),(Ⅲ),(Ⅳ)의 부가반응으로 생성된 일반식(Ⅰ)로 표시되는 화합물의 구체적인 예로,As a specific example of the compound represented by the general formula (I) generated by the addition reaction of the general formula (II), (III), (IV),

(Ⅰa) (Ⅰa)

(Ⅰb) (Ⅰb)

(Ⅰc) (Ic)

(Ⅰd) (Id)

가 나타나며 이러한 각 조성물들을 각 실시예를 통하여 좀 더 상세히 설명하면 다음과 같다.It appears and described in more detail through each of these compositions as follows.

아울러 일반식(Ⅰ)로 표시되는 화합물의 분석은,In addition, the analysis of the compound represented by general formula (I),

-적외선 흡수 스펙트럼; 브롬화 칼륨과 시료를 혼합하여 판상에서 FT-IR 분광광도계(Nicolet magma TM550)로 측정하고,Infrared absorption spectrum; Mix the sample with potassium bromide and measure on a plate by FT-IR spectrophotometer (Nicolet magma TM550),

-GPC; 시료는 용매로 THF를 사용하여 용액상태에서 측정하며,-GPC; Samples are measured in solution using THF as a solvent.

-양성자 핵자기 공명 스펙트럼; 시료는 용매로 Methanol을 사용하여 10중량%의 용액상태에서 H-NMR(Bruker Advance Digital 400㎒)로 측정하였다.Proton nuclear magnetic resonance spectra; Samples were measured by H-NMR (Bruker Advance Digital 400MHz) in a 10% by weight solution using Methanol as a solvent.

<실시예 1><Example 1>

완전히 건조된 냉각기 및 전동 교반기가 부착된 1ℓ 4구 반응조에 TDI(Tolylene-2, 4-diisocyanate) 174g을 넣고 질소가스를 공급한다.Into a 1 L four-necked reactor equipped with a completely dried cooler and an electric stirrer, 174 g of TDI (Tolylene-2, 4-diisocyanate) was added and nitrogen gas was supplied.

상기 반응조에 2-Hydroxyethylacrylate 116g을 적하 깔대기로 투입하고, 반응조의 온도가 60℃를 넘지 않게 유지하면서 1시간 동안 적하시킨다.116 g of 2-Hydroxyethylacrylate was added to the reactor with a dropping funnel, and the reactor was added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C.

이어 상기 반응조의 온도를 40-80℃로 유지시키며 교반 속도를 30-50rpm으로 약 30분에서 1시간동안 교반한다.The temperature of the reactor is then maintained at 40-80 ° C. and the stirring speed is stirred at 30-50 rpm for about 30 minutes to 1 hour.

상기 반응조에서 생성된 혼합물을 상온에서 냉각시킨 후 Methylethylketone oxime 92g을 적하 깔대기에 넣고 반응조의 온도가 60℃가 넘지 않도록 유지하면서1시간 동안 적하시킨다.(필요에 따라 촉매를 사용할 수 있슴)After the mixture produced in the reactor was cooled to room temperature, 92 g of Methylethylketone oxime was added to a dropping funnel and added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C. (A catalyst may be used if necessary.)

이와 같이 적하가 완료되면 반응조의 온도를 40-80℃로 유지하면서 1시간 동안 교반하며, 반응 완료 시점은 흡수 스펙트럼을 사용하여 -NCO기의 pick가 사라지면 반응을 종료하고 GPC와 NMR분석을 통하여 순도 80%인After the dropping is completed, the temperature of the reaction tank is maintained at 40-80 ° C for 1 hour, and the reaction is completed by using the absorption spectrum. When the pick of the -NCO group disappears, the reaction is terminated, and purity is obtained through GPC and NMR analysis. 80%

(Ⅰa)를 생성한다. (Ia) is produced.

<실시예 2><Example 2>

완전히 건조한 냉각기 및 전동 교반기가 부착된 1ℓ 4구 반응조에 TDI(Tolylene-2, 4-diisocyanate) 174g을 넣고 질소 가스를 봉입한다.174 g of TDI (Tolylene-2, 4-diisocyanate) was added to a 1 L four-necked reactor equipped with a completely dry cooler and an electric stirrer, and nitrogen gas was charged.

상기 반응조에 2-Hydroxyethylacrylate 116g을 적하 깔대기로 투입하고, 반응조의 온도가 60℃를 넘지 않게 유지하면서 1시간 동안 적하시킨다.116 g of 2-Hydroxyethylacrylate was added to the reactor with a dropping funnel, and the reactor was added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C.

이어 상기 반응조의 온도를 40-80℃로 유지시키며 교반 속도를 30-50rpm으로 약 30분에서 1시간동안 교반한다.The temperature of the reactor is then maintained at 40-80 ° C. and the stirring speed is stirred at 30-50 rpm for about 30 minutes to 1 hour.

상기 반응조에서 생성된 혼합물을 상온에서 냉각시킨 후 Biacetyl monoxime 121g을 적하 깔대기에 넣고 반응조의 온도가 60℃가 넘지 않도록 유지하면서 1시간 동안 적하시킨다.(필요에 따라 촉매를 사용할 수 있슴)After cooling the mixture produced in the reactor at room temperature, 121 g of Biacetyl monoxime was added to a dropping funnel and added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C. (A catalyst may be used if necessary.)

이와 같이 적하가 완료되면 반응조의 온도를 40-80℃로 유지하면서 1시간 동안 교반하며, 반응 완료 시점은 흡수 스펙트럼을 사용하여 -NCO기의 pick가 사라지면 반응을 종료하고 GPC와 NMR분석을 통하여 순도 78%인After the dropping is completed, the temperature of the reaction tank is maintained at 40-80 ° C for 1 hour, and the reaction is completed by using the absorption spectrum. When the pick of the -NCO group disappears, the reaction is terminated, and purity is obtained through GPC and NMR analysis. 78%

(Ⅰb)를 생성한다. (Ib) is produced.

<실시예 3><Example 3>

완전히 건조한 냉각기 및 전동 교반기가 부착된 1ℓ 4구 반응조에 MDI(Diphenylemethylene-4, 4-diisocyanate) 250g을 넣고 질소 가스를 봉입한다.250 g of MDI (Diphenylemethylene-4, 4-diisocyanate) was added to a 1 L four-neck reactor equipped with a completely dry cooler and an electric stirrer, and nitrogen gas was charged.

상기 반응조에 Acrylic acid 72g을 적하 깔대기로 투입하고, 반응조의 온도가 60℃를 넘지 않게 유지하면서 1시간 동안 적하시킨다.72 g of acrylic acid was added to the reactor by dropping funnel, and the reactor was added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C.

이어 상기 반응조의 온도를 40-80℃로 유지시키며 교반 속도를 30-50rpm으로 약 30분에서 1시간동안 교반한다.The temperature of the reactor is then maintained at 40-80 ° C. and the stirring speed is stirred at 30-50 rpm for about 30 minutes to 1 hour.

상기 반응조에서 생성된 혼합물을 상온에서 냉각시킨 후 Methylethylketone oxime 92g을 적하 깔대기에 넣고 반응조의 온도가 60℃가 넘지 않도록 유지하면서 1시간 동안 적하시킨다.(필요에 따라 촉매를 사용할 수 있슴)After the mixture produced in the reactor was cooled to room temperature, 92 g of Methylethylketone oxime was added to the dropping funnel and added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C. (A catalyst may be used if necessary.)

이와 같이 적하가 완료되면 반응조의 온도를 40-80℃로 유지하면서 1시간 동안 교반하며, 반응 완료 시점은 흡수 스펙트럼을 사용하여 -NCO기의 pick가 사라지면 반응을 종료하고 GPC와 NMR분석을 통하여 순도 55%인After the dropping is completed, the temperature of the reaction tank is maintained at 40-80 ° C for 1 hour, and the reaction is completed by using the absorption spectrum. When the pick of the -NCO group disappears, the reaction is terminated, and purity is obtained through GPC and NMR analysis. 55%

(Ⅰc)를 생성한다. (Ic) is produced.

<실시예 4><Example 4>

완전히 건조한 냉각기 및 전동 교반기가 부착된 1ℓ 4구 반응조에HDI(Hexamethylene diisocyanate) 168g을 넣고 질소 가스를 봉입한다.168 g of HDI (Hexamethylene diisocyanate) was added to a 1 L four-necked reactor equipped with a completely dry cooler and an electric stirrer, and nitrogen gas was charged.

상기 반응조에 Allyl alcohol 58g을 적하 깔대기로 투입하고, 반응조의 온도가 60℃를 넘지 않게 유지하면서 1시간 동안 적하시킨다.58 g of Allyl alcohol was added to the reaction vessel by dropping funnel, and the reaction vessel was added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C.

이어 상기 반응조의 온도를 40-80℃로 유지시키며 교반 속도를 30-50rpm으로 약 30분에서 1시간동안 교반한다.The temperature of the reactor is then maintained at 40-80 ° C. and the stirring speed is stirred at 30-50 rpm for about 30 minutes to 1 hour.

상기 반응조에서 생성된 혼합물을 상온에서 냉각시킨 후 Methylethylketone oxime 92g을 적하 깔대기에 넣고 반응조의 온도가 60℃가 넘지 않도록 유지하면서 1시간 동안 적하시킨다.(필요에 따라 촉매를 사용할 수 있슴)After the mixture produced in the reactor was cooled to room temperature, 92 g of Methylethylketone oxime was added to the dropping funnel and added dropwise for 1 hour while maintaining the temperature of the reactor not to exceed 60 ° C. (A catalyst may be used if necessary.)

이와 같이 적하가 완료되면 반응조의 온도를 40-80℃로 유지하면서 1시간 동안 교반하며, 반응 완료 시점은 흡수 스펙트럼을 사용하여 -NCO기의 pick가 사라지면 반응을 종료하고 GPC와 NMR분석을 통하여 순도 58%인After the dropping is completed, the temperature of the reaction tank is maintained at 40-80 ° C for 1 hour, and the reaction is completed by using the absorption spectrum. When the pick of the -NCO group disappears, the reaction is terminated, and purity is obtained through GPC and NMR analysis. 58%

(Ⅰd)를 생성한다. (Id) is generated.

상기와 같이 실시예 1에서 실시예 4까지 제조한 우레탄계 화합물을 사용하여 불소계 발수발유제를 공중합한 후 섬유에 처리하여 내세탁성 시험을 실시하였으며,As described above, the urethane-based compounds prepared in Example 1 to Example 4 were copolymerized with a fluorine-based water and oil repellent, and then treated to fibers to perform a laundry resistance test.

불소계 발수발유제를 폴리에스터(polyester)에 처리하여 초기 발수성과 10회 세탁 후의 발수성을 점검하여 그 결과를 표 1에서와 같이 도시하였다.The fluorine-based water and oil repellent agent was treated with polyester to check initial water repellency and water repellency after 10 washes, and the results are shown in Table 1 below.

이 때 사용한 불소계 발수발유제의 사용량은 1%soln.이며 내세탁성시험은 KSK 0114기계 세탁법에 준수하며, 발수성은 JIS L 1092 Water spray에 의하여 실시하였다.The amount of fluorine-based water and oil repellent used at this time was 1% soln. The washing resistance test was in accordance with KSK 0114 machine washing method. Water repellency was carried out by JIS L 1092 Water spray.

표 1)Table 1

표2)는 불소계 발수발유제를 나일론(Nylon)에 처리하여 초기 발수성과 10회 세탁 후 발수성을 점검하였으며, 시험 조건은 표 1에서와 같이 동일하다.Table 2) treated the fluorine-based water and oil repellent with nylon to check the initial water repellency and the water repellency after 10 washes. The test conditions are the same as in Table 1.

표 2)Table 2

표3)은 불소계 발수발유제를 면(Cotton)에 처리하여 초기 발수성과 10회 세탁 후 발수성을 점검하였으며, 이 때 사용한 불소계 발수발유제의 사용량은 3%soln.이며 내세탁성 시험은 KSK 0114 기계 세탁법에 준수하며, 발수성은 JIS L 1092 Water spray에 의하여 실시하였다.Table 3) shows the initial water repellency and water repellency after washing 10 times by treating fluorine-based water and oil repellent on cotton. The amount of fluorine-based water and oil repellent used at this time is 3% soln and the washing resistance test is KSK 0114. Comply with the machine washing method, water repellency was carried out by JIS L 1092 Water spray.

표 3)Table 3

상기와 같이 일반식(Ⅰ)의 구체적 화합물인 Ⅰa - Ⅰd까지의 우레탄 화합물은 기존에 사용되는 내구성 모노머인 Vcl과 VDC에 비하여 섬유 표면에 대한 내구성이 거의 동일한 수치 결과를 나타낸다.As described above, the urethane compounds up to Ia to Id, which are specific compounds of the general formula (I), show numerical results of almost the same durability on the fiber surface as compared to the conventionally used durable monomers Vcl and VDC.

또한 표1 - 표3에서 알 수 있듯이 우레탄 화합물을 사용한 불소계 발수발유제는 모든 섬유에 사용 가능하며, 종래 Vcl과 VDC를 사용한 불소계 발수발유제가 셀룰로스섬유에서의 촉감 저하와 같은 문제점을 해결할 수 있다.In addition, as shown in Table 1 to Table 3, fluorine-based water and oil repellents using urethane compounds can be used for all fibers, and conventional fluorine-based water and oil repellents using Vcl and VDC can solve problems such as deterioration of touch in cellulose fibers. .

이상과 같은 본 발명인 접착력 및 내구성을 가지는 우레탄계 화합물 및 그 제조 방법은 향상된 내구성으로 인해 이를 첨가한 표면 개질제인 불소계 발수발유제의 접착력 및 내구성 증대를 꾀할 수 있으며,Urethane-based compound having a bonding strength and durability and a method of manufacturing the present invention as described above can improve the adhesion and durability of the fluorine-based water and oil repellent agent is a surface modifier added thereto due to improved durability,

특히 내세탁성에 탁월한 효과를 나타내어 섬유를 비롯한 목재, 종이등의 셀룰로스계 물질의 방수처리에 적용이 가능하고, 잉크, 접착제, 도료등에도 우레탄 화합물을 첨가하여 접착력 강화를 이룰 수 있는 유용한 발명이다.In particular, it shows an excellent effect on the washing resistance is applicable to the waterproofing treatment of cellulose-based materials such as wood, paper, such as fibers, and is a useful invention that can enhance the adhesion by adding a urethane compound to ink, adhesives, paints and the like.

Claims (5)

접착성 및 내구성을 지니는 우레탄계 화합물 및 그 제조 방법에 있어서;In the urethane-based compound having the adhesion and durability and a method for producing the same; 일반식(Ⅱ),General formula (II), OCN-R2-NCO(Ⅱ)OCN-R 2 -NCO (Ⅱ) R2 : 탄소수 2∼14의 탄화수소기R2 is a hydrocarbon group having 2 to 14 carbon atoms 와,Wow, 하기 일반식(Ⅲ)General formula (III) R1=NOH(Ⅲ)R 1 = NOH (III) R1: CnH2n, CnH2n-2On=1∼10R 1 : CnH 2 n, CnH 2 n -2 On = 1 to 10 으로 표시되는 기능성 모노머와,A functional monomer represented by 하기 일반식(Ⅳ)General formula (IV) CH2=CR4R3OH(Ⅳ)CH 2 = CR 4 R 3 OH (Ⅳ) R3:COO(CH2)nn=1∼4R 3 : COO (CH 2 ) nn = 1 to 4 (CH2)nn=0∼4(CH 2 ) nn = 0 to 4 (CH2)nCOn=0∼4(CH 2 ) nCOn = 0 to 4 R4 :H 또는 CnH2n+1n=1∼4R4: H or CnH 2 n +1 n = 1 to 4 로 표시되는 2중 결합과 하이드록시기를 가진 모노머를 반응시켜 하기 일반식(Ⅰ)로 표시되는 것을 특징으로 하는 접착성 및 내구성을 지니는 우레탄계 화합물.A urethane-based compound having adhesiveness and durability, which is represented by the following general formula (I) by reacting a monomer having a double bond with a hydroxyl group. 일반식(Ⅰ)General formula (Ⅰ) (Ⅰ) (Ⅰ) 여기서;here; R1은CnH2n, CnH2n-2On=1∼10R 1 is CnH 2 n, CnH 2 n -2 On = 1 to 10 R2는 탄소수 2 ∼ 14의 탄화수소기R 2 is a hydrocarbon group having 2 to 14 carbon atoms R3은COO(CH2)nn=1∼4R 3 is COO (CH 2 ) nn = 1 to 4 (CH2)nn=0∼4(CH 2 ) nn = 0 to 4 (CH2)nCOn=0∼4(CH 2 ) nCOn = 0 to 4 R4는 H 또는 CnH2n+1n=1∼4R 4 is H or CnH 2 n +1 n = 1 to 4 제 1 항에 있어서;The method of claim 1; 상기 일반식(Ⅱ)로 표시되는 -NCO기를 가진 우레탄 화합물은 TDI(Tolylene-2, 4-diisocyanate), MDI(Diphenylmethane-4, 4-diisocyanate), HDI(Hexamethylene diisocyanate)등의 탄소수가 2∼14로 구성된 군으로부터 선택되는 것을 특징으로 하는 접착성 및 내구성을 지니는 우레탄계 화합물.The urethane compound having an -NCO group represented by the general formula (II) includes 2 to 14 carbon atoms such as TDI (Tolylene-2, 4-diisocyanate), MDI (Diphenylmethane-4, 4-diisocyanate), and HDI (Hexamethylene diisocyanate). Adhesive and durable urethane-based compound, characterized in that selected from the group consisting of. 제 1 항에 있어서;The method of claim 1; 상기 일반식(Ⅲ)으로 표시되는 옥심계의 화합물은 Biacetyl monoxime, Methylethylketone oxime으로 구성된 군으로부터 선택된 것을 특징으로 하는 접착성 및 내구성을 지니는 우레탄계 화합물.The compound of the oxime system represented by the general formula (III) is a urethane compound having adhesion and durability, characterized in that selected from the group consisting of Biacetyl monoxime, Methylethylketone oxime. 제 1 항에 있어서;The method of claim 1; 상기 일반식(Ⅳ)로 표시되는 2중 결합기를 가진 화합물은 2-Hydroxy ethylacrylate, 2-Hydroxypropylacrylate, 2-Hydroxyethylmethacrylate, 2-Hydroxypropylnethacrylate, Allylalcohol, Acrylic acid, methacrylic acid로 구성된 군으로부터 선택되는 것을 특징으로 하는 접착성 및 내구성을 지니는 우레탄계 화합물.Compound having a double bond group represented by the general formula (IV) is selected from the group consisting of 2-Hydroxy ethylacrylate, 2-Hydroxypropylacrylate, 2-Hydroxyethylmethacrylate, 2-Hydroxypropylnethacrylate, Allylalcohol, Acrylic acid, methacrylic acid Urethane-based compound having adhesiveness and durability. 상기 일반식(Ⅱ),(Ⅲ),(Ⅳ)의 화합물을,Compounds of the general formula (II), (III), (IV), 상압하에서 40-80℃의 조건으로 2-5시간동안 질소 기류가 충진된 반응조에서 반응시켜 일반식(Ⅰ)을 생성하는 것을 특징으로 하는 접착성 및 내구성을 지니는 우레탄계 화합물의 제조 방법.A process for producing a urethane-based compound having adhesiveness and durability, characterized in that the reaction is carried out in a reactor filled with a nitrogen stream for 2-5 hours under normal pressure at 40-80 ° C. to produce general formula (I).
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100663267B1 (en) * 2004-07-13 2007-01-02 김종한 Underground pipe laying
KR100688617B1 (en) * 2006-05-25 2007-03-02 (주) 부경종합기술단 Flat sewer pipe

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60127317A (en) * 1983-12-13 1985-07-08 Toagosei Chem Ind Co Ltd Manufacture of curable composition
US4647646A (en) * 1983-12-22 1987-03-03 Usm Corporation Heat curable compositions
JPH0995655A (en) * 1995-09-30 1997-04-08 Toppan Printing Co Ltd Electron beam curable monofunctional urethane (meth) acrylate oligomer and electron beam curable adhesive composition containing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60127317A (en) * 1983-12-13 1985-07-08 Toagosei Chem Ind Co Ltd Manufacture of curable composition
US4647646A (en) * 1983-12-22 1987-03-03 Usm Corporation Heat curable compositions
JPH0995655A (en) * 1995-09-30 1997-04-08 Toppan Printing Co Ltd Electron beam curable monofunctional urethane (meth) acrylate oligomer and electron beam curable adhesive composition containing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100663267B1 (en) * 2004-07-13 2007-01-02 김종한 Underground pipe laying
KR100688617B1 (en) * 2006-05-25 2007-03-02 (주) 부경종합기술단 Flat sewer pipe

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