KR101943964B1 - An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound - Google Patents

An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound Download PDF

Info

Publication number
KR101943964B1
KR101943964B1 KR1020180043679A KR20180043679A KR101943964B1 KR 101943964 B1 KR101943964 B1 KR 101943964B1 KR 1020180043679 A KR1020180043679 A KR 1020180043679A KR 20180043679 A KR20180043679 A KR 20180043679A KR 101943964 B1 KR101943964 B1 KR 101943964B1
Authority
KR
South Korea
Prior art keywords
composition
amine group
elastomer
amine
compound
Prior art date
Application number
KR1020180043679A
Other languages
Korean (ko)
Inventor
윤정운
Original Assignee
윤정운
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 윤정운 filed Critical 윤정운
Priority to KR1020180043679A priority Critical patent/KR101943964B1/en
Priority to CN201810448953.2A priority patent/CN110386880A/en
Application granted granted Critical
Publication of KR101943964B1 publication Critical patent/KR101943964B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • C08G18/287—Imine compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

An imine compound containing an amine group is disclosed. The compound reacts to moisture in the air to be decomposed to amine and aldehyde, and has a urethane elastomer resin compound and a hardening agent of a urea elastomer resin compound. Moreover, a two-liquid type urethane/urea elastomer compound is provided to provide excellent physical characteristics as the decomposed amine group reacts to a main agent or/and a hardening agent having an isocyanate group in a dead end of the compound, and minimize an effect of material property as the aldehyde volatilizes.

Description

아민기를 함유한 이민계 조성물 및 그 제조방법, 아민기를 함유한 이민계 조성물을 포함하는 탄성체 수지 조성물{An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound}The present invention relates to an amine-based composition containing an amine group, a process for producing the same, and an elastomeric resin composition containing an amine group-containing imine compound containing an amine group, a process for producing the same, and an elastomer- imine compound}

본 발명은 새로운 아민기를 함유한 이민계 조성물 및 이의 제조방법, 상기 조성물을 포함하는 우레탄 탄성체 조성물, 우레아 탄성체 조성물에 관한 것이다.The present invention relates to an imine-based composition containing a novel amine group, a process for producing the same, a urethane elastomer composition comprising the composition, and a urea elastomer composition.

건축물의 방수 바닥재나 체육시설의 바닥재로는 우레탄 탄성체 조성물 또는 우레아 탄성체 조성물(이하 '탄성체 수지 조성물'이라 칭함)이 많이 사용된다.A urethane elastomer composition or a urea elastomer composition (hereinafter referred to as "elastomer resin composition") is often used as a waterproof flooring material of a building or a floor material of a sports facility.

폴리우레탄은 화학적으로 고분자 사슬 내에 우레탄 결합(~NH-COO~)을 갖는 고분자의 총칭으로 2가 이상의 이소시아네이트와 폴리올 등의 활성수소 화합물과의 결합에 의해 제조된다. 폴리우레탄수지는 사용되는 이소시아네이트와 폴리올의 선택범위가 넓어 연질에서 경질 까지, 엘라스토머에서 폼까지 다양한 제품설계가 가능하고 인장강도, 인열강도, 신율, 내마모성 등의 기계적 강도가 우수하며 가공성이 좋아 의류용, 신발용, 산업용 바퀴를 비롯하여 건축용도로서 옥상방수재, 실내체육관 바닥재, 육상트랙 등 산업용뿐 아니라 생활용품으로의 응용전개가 넓은 대표적인 고분자화합물이다.Polyurethanes are chemically synthesized polymers having a urethane bond (~NH-COO ~) in the polymer chain, and are produced by bonding an isocyanate having two or more hydroxyl groups with an active hydrogen compound such as a polyol. The polyurethane resin has a wide selection range of isocyanate and polyol to be used. It can design various products ranging from soft to hard, from elastomer to foam, and has excellent mechanical strength such as tensile strength, tear strength, elongation, abrasion resistance, It is a representative polymer compound that has wide application in industrial products such as rooftop waterproofing material, indoor gym flooring, land track, and industrial products as well as industrial products including industrial use, shoes, and industrial wheels.

폴리우레아수지는 말단에 1급 아민을 갖고 있는 폴리에테르아민(Polyetheramine)과 이소시아네이트와의 반응생성물로서,주제와 경화제를 작업현장에서 고압스프레이 장비를 사용하여 표면에 직접 분사하여 도막을 형성하는데, 기존의 방수, 바닥, 방식 코딩 시스템에 비해 극히 빠른 경화특성이 있으므로 작업의 효율성을 높일 수 있으며 수직면에도 흐름성 없이 연속적으로 요구하는 도막두께를 확보할 수 있다. 또한 경화특성상 주변 습기와의 반응보다 자체 반응성이 극히 빠르므로 타 코팅시스템에 비해 습기 및 온도 등에 거의 영향을 받지 않아 사용 환경의 범위가 넓다.Polyurea resin is a reaction product of isocyanate with polyetheramine having a primary amine at the terminal. It forms a film by spraying the main and hardener directly on the surface using high pressure spray equipment at the work site. Since it has extremely fast curing characteristics compared to the waterproof, floor and system coding systems of the present invention, it is possible to increase the efficiency of the work and ensure the required film thickness continuously without flow on the vertical surface. In addition, due to its curing properties, its reaction rate is extremely faster than the reaction with ambient moisture.

이러한 장점들로 인해 건축물의 방수재나 바닥재로서 우레탄 탄성체 수지 조성물, 우레아 탄성체 수지 조성물이 널리 사용되고 있다.Because of these advantages, a urethane elastomer resin composition and a urea elastomer resin composition are widely used as waterproofing materials and flooring materials for buildings.

이러한 탄성체 수지 조성물에는 경화제의 사용유무에 따라 1액형과 2액형(혹은 다액형)으로 분류할 수 있다. Such an elastomer resin composition can be classified into one-component type and two-component type (or multi-component type) depending on whether a curing agent is used or not.

어떠한 탄성체 수지 조성물이건, 주제를 경화할 수 있는 경화제를 포함하고 있는데, 경화제로 일명 MOCA라고 불리는 4,4‘-Methylene bis(2-chloroaniline)(관용명:Bis(4-amino-3-chlorophenyl)methane)을 대부분 사용하고 있다. 그런데, 상기 MOCA는 유독물질로서 이를 0.1% 이상 함유한 혼합물질도 또한 유독물질로 분류할 정도로 인체 및 환경에 유해한 물질로 알려져 있다. 노동환경 건강연구소 발암물질 정보센터 자료에 따르면, 1급발암물질(암을일으키는 것이 사람 에대한연구 조사에서 이미 확증된 물질)로 분류되어 있고, The International Agency for Research on Cancer (IARC) 기준으로도 1급 발암물질로 분류되고 있다. 한국에서는 2020년이후부터는 건축용으로 사용이 제한된다.Any elastomeric resin composition contains a curing agent capable of curing the subject. It is also possible to use 4,4'-methylene bis (2-chloroaniline) (commonly known as MOCA, bis (4-amino-3-chlorophenyl) methane ) Are mostly used. However, the MOCA is known as a toxic substance, which is harmful to humans and the environment to such a degree that a mixed substance containing 0.1% or more thereof is also classified as a toxic substance. According to the Labor Environment Health Research Institute Carcinogen Information Center data, primary carcinogens (substances that cause cancer are already confirmed in research on humans), and the International Agency for Research on Cancer (IARC) Class 1 carcinogens are classified as. In Korea after 2020 it is limited to use for construction.

이에 경화된 탄성체의 물성 저하 없이 유해성이 적은 상기 Bis(4-amino-3-chlorophenyl)methane를 대체할 새로운 물질이 요구된다.Therefore, a novel material for replacing the above-mentioned bis (4-amino-3-chlorophenyl) methane is desired without deteriorating physical properties of the cured elastomer.

본 발명은 탄성체 수지 조성물의 필수 첨가제로서 상기 Bis(4-amino-3-chlorophenyl)methane를 대체할 아민기 함유 이민계 조성물을 제공하는 것이다. The present invention provides an amine group-containing imine-based composition which can replace the bis (4-amino-3-chlorophenyl) methane as an essential additive for an elastomer resin composition.

본 발명의 다른 목적은 상기 아민기 함유 이민계 조성물의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a process for producing the amine group-containing immiscible composition.

본 발명의 다른 목적은 상기 아민기 함유 이민계 조성물을 포함하는 2액형 우레탄 탄성체 수지 조성물을 제공하는 것이다.Another object of the present invention is to provide a two-pack type urethane elastomer resin composition comprising the amine group-containing imine-based composition.

본 발명의 다른 목적은 상기 아민기 함유 이민계 조성물을 포함하는 2액형 우레아 탄성체 수지 조성물을 제공하는 것이다.Another object of the present invention is to provide a two-pack type urea elastomer resin composition comprising the amine group-containing imine-based composition.

상기 목적을 달성하기 위한 본 발명은 하기 화학식 1로 표시되는 아민기를 함유한 이민계 조성물을 제공한다.In order to accomplish the above object, the present invention provides an imine-based composition containing an amine group represented by the following general formula (1).

Figure 112018106435529-pat00001

여기서, R1 은 프로필, 부틸, 이소부틸, 3-메틸부틸 또는 벤질이고,
R2는 폴리옥시프로필렌디아민유도체(
Figure 112018106435529-pat00008
), 이소포론디아민유도체(
Figure 112018106435529-pat00009
) 또는 디에틸톨루엔디아민 유도체(
Figure 112018106435529-pat00010
) 이고,
Figure 112018106435529-pat00001

Wherein R1 is propyl, butyl, isobutyl, 3-methylbutyl or benzyl,
R2 is a polyoxypropylene diamine derivative (
Figure 112018106435529-pat00008
), Isophorone diamine derivatives (
Figure 112018106435529-pat00009
) Or diethyltoluenediamine derivative (
Figure 112018106435529-pat00010
) ego,

삭제delete

삭제delete

몰비로 R1 : R2 = 1 : 0.5 ~ 1.5 이다. 0.5 미만이면 경화속도가 너무 늦어져 후공정에 영향을 주고 1.5를 초과하면 혼합후 초기경화속도가 빨라지고 점도가 급상승하여 작업이 어렵다.R1: R2 = 1: 0.5 to 1.5 in molar ratio. If it is less than 0.5, the curing rate becomes too slow to affect the post-process. If it exceeds 1.5, the initial curing speed after mixing is increased and the viscosity is increased so that the operation is difficult.

상기에서, 몰비로 R1 : R2 = 0.9 ~ 1.4 임이 바람직하다. In the above, the molar ratio of R1: R2 = 0.9 to 1.4 is preferable.

다른 관점에서, 본 발명은 상기 아민기를 함유한 이민계 조성물의 제조방법을 제공하는데, 플라스크에 Di-ethyltoluene diamine을 투입 교반하면서 Isobutyraldehyde을 분할 투입하여 60~70℃에서 4 - 8 시간 반응 후 Toluene을 투입하여 110 ~ 150℃에서 환류 중합하며 발생한 물을 제거하고 반응이 완료된 후에 감압하여 Tolene을 회수하는 것을 특징으로 한다.In another aspect, the present invention provides a method for preparing an amine-containing composition comprising the steps of: adding di-ethyltoluene diamine to a flask; adding isobutyraldehyde into the flask while stirring at 60 to 70 ° C for 4 to 8 hours; And the mixture is refluxed at 110 to 150 ° C to remove water. After completion of the reaction, depressurization is performed to recover the toluene.

다른 관점에서, 본 발명은 상기 아민기를 함유한 이민계 조성물을 포함하는 2액형 폴리우레탄 탄성체 조성물을 제공한다.In another aspect, the present invention provides a two-pack type polyurethane elastomer composition comprising an amine-containing imine-based composition.

또한 다른 관점에서, 본 발명은 상기 아민기를 함유한 이민계 조성물을 포함하는 2액형 폴리우레아 탄성체 조성물을 제공한다.In another aspect, the present invention provides a two-pack type polyurea elastomer composition comprising an amine-containing imine-based composition.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

이하의 설명에서 편의상, 이액형 우레탄 탄성체 수지를 예를 들어 설명하나 본 발명이 이에 제한 되는 것은 아니다.For convenience, the liquid urethane elastomer resin will be described by way of example, but the present invention is not limited thereto.

본 발명자는 상기 문제점들을 해결하고자 인체에 무해하고, 우레탄 탄성체의 목적하는 물성에 영향이 거의 없는 물질을 찾고자 하는 연구 끝에, 대기중의 수분과 접촉시 아민과 알데하이드로 해리되는 이민계 조성물의 특성을 이용하면, 상기 해리된 아민기는 말단에 이소시아네이트기를 가진 주제 또는/및 경화제와 반응하여 우수한 물리적 물성을 갖는 우레탄(우레아) 결합을 형성하고 (말단의 이소시아네이트와 반응하여 가교결합을 형성하여 물성을 향상) 향수의 원료로도 사용되는 물질인 알데하이드는 휘발되어 물성의 영향을 최소화할 수 있는 2액형 우레탄 탄성체 수지 조성물을 완성할 수 있음을 발견하고 본 발명을 하게 되었다.(반응식 1 참조)In order to solve the above problems, the inventor of the present invention has conducted research to find a substance which is harmless to the human body and hardly influences the desired physical properties of the urethane elastomer. The inventors of the present invention have found that the properties of an imine- , The dissociated amine group reacts with a subject having an isocyanate group at the terminal and / or a curing agent to form a urethane (urea) bond having excellent physical properties (to improve physical properties by reacting with the terminal isocyanate to form crosslinking) The inventors of the present invention discovered that an aldehyde, which is also used as a raw material of perfume, can be volatilized to minimize the influence of physical properties, thereby completing a two-component urethane elastomer resin composition.

(반응식 1) (Scheme 1)

Figure 112018037295571-pat00002
Figure 112018037295571-pat00002

이액형 폴리우레탄 탄성체 수지 조성물이란, 이소시아네이트계 화합물(주제) 및 폴리올계 화합물(경화제)을 혼합하여 형성되는 폴리우레탄 탄성체 수지조성물을 말한다. The liquid type polyurethane elastomer resin composition refers to a polyurethane elastomer resin composition formed by mixing an isocyanate compound (a subject) and a polyol compound (a curing agent).

본 발명의 이액형 폴리우레탄 탄성체 수지 조성물에 사용할 수 있는 상기 이소시아네이트는 기존에 알려진 이소시아네이트을 모두 포함한다. 예를 들면, 1,6-헥사메틸렌 디이소시아네이트(1,6-hezamethylene diisocyanate, HDI), 메틸렌디페닐 디이소시아네이트(methylenediphenyl diisocyante, MDI), p-페닐렌 디이소시아네이트(p-phenylene diisocyanate, PPDI), 톨루엔 디이소시아네이트(toluene diisocyanate, TDI), 1,5-나프탈렌 디이소시아네이트(1,5-naphthalene diisocyanate, NDI), 이소포론 디이소시아네이트(isoporon diisocyanate, IPDI), 시클로헥실메탄 디이소시아네이트(cyclohexylmethane diisocyanate, H12MDI), 자이렌 디이소시아네이트( Xylene diisocyanate, XDI), 노보네인 디이소시아네이트(Norbornane diisocyanate, NBDI), 트리메틸 헥사메틸렌 디이소시아네이트(Trimethyl hexamethylene diisocyanate, TMDI) 및 이들로부터 선택된 혼합물 중 하나일 수 있다. The isocyanate which can be used in the liquid type polyurethane elastomer resin composition of the present invention includes all known isocyanates. For example, 1,6-hexamethylene diisocyanate (HDI), methylenediphenyl diisocyante (MDI), p-phenylene diisocyanate (PPDI), and the like. Toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), isoporon diisocyanate (IPDI), cyclohexylmethane diisocyanate (H12MDI) , Xylene diisocyanate (XDI), Norbornene diisocyanate (NBDI), Trimethyl hexamethylene diisocyanate (TMDI), and mixtures thereof .

또한 본 발명의 이액형 폴리우레탄 탄성체 수지 조성물에 사용할 수 있는 상기 폴리올로서는, 폴리부타디엔 디올, 폴리테트라메틸렌에테르 글리콜, 폴리프로필렌 옥사이드 클리콜(폴리옥시프로필렌글리콜), 폴리프로필렌 옥사이드 트리올, 폴리부틸렌 옥사이드 글리콜, 폴리부틸렌 옥사이드 트리온, 저분자 글리콜류 등이 사용될 수 있다.Examples of the polyols usable in the liquid type polyurethane elastomer resin composition of the present invention include polybutadiene diol, polytetramethylene ether glycol, polypropylene oxide glycol (polyoxypropylene glycol), polypropylene oxide triol, polybutylene Oxide glycols, polybutylene oxide trion, low molecular weight glycols and the like can be used.

또한 사슬확장제로서 부탄디올과 같은 저분자량 디올이나, 프로필렌카보네이트와 같은 저분자량 카보네이트류가 사용될 수 있으며, 기타 탄산칼슘 같은 충진제, 자외선 안정제, 경화촉진제 등을 포함할 수 있다.As the chain extender, low molecular weight diols such as butanediol and low molecular weight carbonates such as propylene carbonate may be used, and other fillers such as calcium carbonate, ultraviolet stabilizers, curing accelerators and the like may be included.

이액형 폴리우레아 탄성체 수지 조성물이란, 이소시아네이트계 화합물(주제) 및 아민계 화합물(경화제)을 혼합하여 형성되는 폴리우레아 탄성체 수지조성물을 말한다. The liquid type polyurea elastomer resin composition refers to a polyurea elastomer resin composition formed by mixing an isocyanate compound (a subject) and an amine compound (a curing agent).

본 발명의 이액형 폴리우레아 탄성체 수지 조성물에 사용할 수 있는 상기 이소시아네이트는 기존에 알려진 앞서 설명한 이소시아네이트를 모두 포함할 수 있다.The isocyanate that can be used in the liquid type polyurea elastomer resin composition of the present invention may include all of the isocyanates described above.

또한 본 발명의 이액형 폴리우레아 탄성체 수지 조성물에 사용할 수 있는 상기 아민계 화합물로는, 예를 들면 폴리에테르폴리아민류, 지방족 아민류, 지환식 아민류, 방향족 아민류 등일 수 있으며, 폴리에테르폴리아민류로서는, 트리에틸렌글리콜디아민, 테트라에틸렌글리콜디아민, 디에틸렌글리콜비스(프로필아민), 폴리옥시프로필렌디아민, 폴리옥시프로필렌트리아민류 및 이들로부터 선택된 혼합물 중 하나일 수 있다. 지방족 아민류로서는, 에틸렌디아민, 1,3-디아미노프로판, 1,4-디아미노프로판, 헥사메틸렌디아민, 2,5-디메틸헥사메틸렌디아민, 트리메틸헥사메틸렌디아민, 디에틸렌트리아민, 이미노비스프로필아민, 비스(헥사메틸렌)트리아민, 트리에틸렌테트라민, 테트라에틸렌펜타민, 펜타에틸렌헥사민, N-히드록시에틸에틸렌디아민, 테트라(히드록시에틸)에틸렌디아민 등을 들 수 있다. 지환식 아민류로서는, 이소포론디아민, 메타센디아민, N-아미노에틸피페라진, 비스(4-아미노-3-메틸디시클로헥실)메탄, 비스(아미노메틸)시클로헥산, 3,9-비스(3-아미노프로필)2,4,8,10-테트라옥사스피로(5,5)운데칸, 노르보르넨디아민 등을 들 수 있다. 방향족 아민류로서는, 테트라클로로-p-크실렌디아민, m-크실렌디아민, p-크실렌디아민, m-페닐렌디아민, o-페닐렌디아민, p-페닐렌디아민, 2,4-디아미노아니솔, 2,4-톨루엔디아민, 2,4-디아미노디페닐메탄, 4,4'-디아미노디페닐메탄, 4,4'-디아미노-1,2-디페닐에탄, 2,4-디아미노디페닐술폰, m-아미노페놀, m-아미노벤질아민, 벤질디메틸아민, 2-디메틸아미노메틸)페놀, 트리에탄올아민, 메틸벤질아민, α-(m-아미노페닐)에틸아민, α-(p-아미노페닐)에틸아민, 디아미노디에틸디메틸디페닐메탄, α,α'-비스(4-아미노페닐)-p-디이소프로필벤젠 및 이들로부터 선택된 혼합물 중 하나일 수 있다. Examples of the amine compound that can be used in the liquid type polyurea elastomer resin composition of the present invention include polyether polyamines, aliphatic amines, alicyclic amines, aromatic amines, and the like. As the polyether polyamines, Ethylene glycol diamine, ethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamine, and mixtures thereof. Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, Triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of the alicyclic amines include isophoronediamine, methadecenediamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9- -Aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine, and the like. Examples of the aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4- , 4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4- (M-aminophenyl) ethylamine, [alpha] - (p-amino) benzylamine, benzyldimethylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, Phenyl) ethylamine, diaminodiethyldimethyldiphenylmethane,?,? '- bis (4-aminophenyl) -p-diisopropylbenzene and mixtures thereof.

폴리우레아 탄성체 수지 조성물에도 사슬확장제, 안정제, 충진제 등의 첨가물이 혼합될 수 있음은 물론이다.Needless to say, the polyurea elastomer resin composition may also contain additives such as a chain extender, a stabilizer, and a filler.

본 발명에 따르면 기존 탄성체 수지조성물에 필수적으로 함유되었던 MOCA를 대체할 새로운 화합물(조성물)이 제공된다.According to the present invention, there is provided a novel compound (composition) which can be substituted for MOCA which is essentially contained in a conventional elastomer resin composition.

또한 물성을 저하함이 없이 친환경적인 폴리우레탄 탄성체 수지 조성물 및 폴리우레아 탄성체 수지 조성물이 제공된다.Also, an environmentally friendly polyurethane elastomer resin composition and a polyurea elastomer resin composition are provided without deteriorating physical properties.

도 1은 본 발명의 이민계 조성물의 IR 분광자료이고,
도 2는 본 발명의 이민계 조성물의 NMR 분광자료이다.1 is an IR spectroscopic data of the imine-based composition of the present invention,
2 is an NMR spectroscopic data of the imine-based composition of the present invention.

아민기를 함유한 이민계 조성물의 합성Synthesis of an amine group-containing imine-based composition

플라스크에 Di-ethyltoluene diamine(DETDA: Ethacureㄾ 100 Curative - Albemarle Corporation) 1,920g을 투입 교반하면서 Isobutyraldehyde(Tokyo Chemical Industry Co., Ltd.) 720g을 1시간에 걸쳐 3회 분할 투입하였다. 60~70℃에서 6시간 반응 후 Toluene을 100g 투입하여, 130℃에서 환류 중합하며 축합반응으로 발생한 물을 제거하고 반응이 완료된 후에 감압하여 Toluene을 회수하여 최종 아민기를 함유한 이민계 조성물 2,330g을 얻었다.(반응식 2 참조)1,920 g of Di-ethyltoluene diamine (DETDA: Ethacure 100 Curative - Albemarle Corporation) was added to the flask while stirring and 720 g of isobutyraldehyde (Tokyo Chemical Industry Co., Ltd.) was added in three times over 1 hour. After reacting at 60 to 70 ° C for 6 hours, 100 g of toluene was added and the mixture was refluxed at 130 ° C to remove water generated by the condensation reaction. After the completion of the reaction, the toluene was recovered under reduced pressure to obtain 2,330 g of the amine- (See Scheme 2).

Figure 112018037295571-pat00003
Figure 112018037295571-pat00003

생성물의 구조를 확인하기 위해 NMR IR분광실험을 행하였다. 도1 및 2에 나타난 바와 같이, 반응식 2의 생성물의 구조를 확인할 수 있었다.NMR IR spectroscopy experiments were carried out to confirm the structure of the product. As shown in FIGS. 1 and 2, the structure of the product of Scheme 2 was confirmed.

실시예 1 ~ 5 및 비교예 1 ~ 2Examples 1 to 5 and Comparative Examples 1 to 2

위에서 합성한 본 발명 조성물을 포함하여 아래 표 1에서와 같은 조성으로 우레탄 탄성체 수지 조성물을 제조하였다. The urethane elastomer resin composition was prepared as shown in Table 1 below, including the composition of the present invention synthesized above.

주제부Topic section

주제부는 실시예 비교예 모두 NEODEX NEW TP-230(ECO) (강남화성)을 사용하였다.The subject part used NEODEX NEW TP-230 (ECO) (Kangnam Hwasung) in all of the example comparative examples.

경화제Hardener

비교예(MOCA 배합) Comparative Example (MOCA formulation)

온도조정이 가능한 별도의 용해조에 폴리옥시프로필렌글리콜(PP-3000)을 먼저 배합하고 4,4-메틸렌 비스(2-클로로아닐린)(일명 MOCA) 및 자외선안정제를 투 입하여 온도를 105℃까지 승온시켜 MOCA를 용해시켰다. 용해된 재료에 나머지 폴리옥시프로필렌글리콜, 탄산칼슘, 조색제, 프로필렌카보네이트, 디이아이소노닐프 탈레이트, 등을 배합하고 경화촉진제를 투입하여 가사시간 확인 후 제품을 제조하였다. Polyoxypropylene glycol (PP-3000) was first blended in a separate melting vessel capable of adjusting the temperature, and 4,4-methylene bis (2-chloroaniline) (aka MOCA) and ultraviolet stabilizer were charged. To dissolve MOCA. After dissolving the remaining polyoxypropylene glycol, calcium carbonate, colorant, propylene carbonate, diisononylphthalate, etc., the curing accelerator was added to the melted material to prepare a product.

실시예1 ~ 5 (본 발명 배합)Examples 1 to 5 (formulation of the present invention)

상기에서 제조한 본 발명의 이민계 조성물, 폴리옥시프로필렌글리콜, 탄산칼슘, 조색제, 프로필렌카보네이트, 디이아이소노닐프탈레이트 등을 배합하고 경화촉진제를 투입하여 가사시간 확인 후 제품을 제조하였다.The emulsion composition of the present invention, polyoxypropylene glycol, calcium carbonate, colorant, propylene carbonate, diisononylphthalate, and the like, which were prepared as described above, were added and a curing accelerator was added thereto to prepare a product after confirming the pot life.

탄성체 수지조성물의 경화Curing of the elastomer resin composition

주제 및 경화제를 1:3 중량비로 배합 및 교반 후 도막내부에 기포가 없도록 진공탈포공정을 시행하고 미리 준비한 이형처리된 유리판(50㎝ㅧ50㎝ㅧ2장)에 상기에서 제조한 우레탄 탄성체 수지조성물을 1.5~2.0㎜ 두께가 되도록 도포하였다. 도포한 유리판을 표준상태 [KS A0006의 20ㅁ2℃, 습도 60ㅁ20%]로 설정된 실험실에 24시간 이상 표준상태에서 보관하여 2주 후 물성을 측정하였다.(1: 3 weight ratio), and the mixture was stirred and then vacuum defoaming was carried out so that there was no air bubbles inside the coating film. The urethane elastomer resin composition Was applied so as to have a thickness of 1.5 to 2.0 mm. The coated glass plate was stored in a standard state (KS A0006 at 20 ° C and 2 ° C, humidity 60 ° C and 20% RH) for 24 hours or longer, and the properties were measured after 2 weeks.

구 분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 비교예1Comparative Example 1 비교예2Comparative Example 2 주제부 Topic section NEODEX?? NEW TP-230(ECO) (강남화성) NEODEX ?? NEW TP-230 (ECO) (Kangnam Hwaseong)
100
100 경화제Hardener 4,4-메틸렌 비스(2-클로로아닐린) (IHARA)4,4-methylenebis (2-chloroaniline) (IHARA) 2.62.6 2.82.8 본발명조성물The composition of the present invention 2.02.0 2.12.1 2.22.2 2.32.3 2.42.4 폴리옥시프로필렌글리콜
(KPX, PP-3000)Polyoxypropylene glycol
(KPX, PP-3000) 13.013.0 12.512.5 12.012.0 10.010.0 8.08.0 8.08.0 10.010.0 폴리옥시프로필렌글리콜
(KPX, GP-5000)Polyoxypropylene glycol
(KPX, GP-5000) 8.08.0 6.06.0 5.65.6 5.65.6 7.07.0 7.07.0 4.04.0 탄산칼슘
(OMYA korea)Calcium carbonate
(OMYA korea) 55.355.3 58.058.0 60.060.0 60.060.0 60.060.0 59.859.8 60.060.0 자외선 안정제
(송원산업)Ultraviolet stabilizer
(Songwon Industry) 0.40.4 0.40.4 0.40.4 0.40.4 0.40.4 0.40.4 0.40.4 조색제Colorant 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 프로필렌카보네이트
(Huntsman)Propylene carbonate
(Huntsman) 8.08.0 8.08.0 8.08.0 9.09.0 9.09.0 9.09.0 9.09.0 디이아이소노닐프탈레이트
(애경유화)Diisononyl phthalate
(Aekyung oil painting) 9.09.0 9.09.0 8.08.0 9.09.0 9.59.5 9.29.2 9.89.8 경화촉진제
(진양화성)Hardening accelerator
(Jinyang Hwaseong) 1.31.3 1.01.0 0.80.8 0.70.7 0.70.7 1.01.0 1.01.0 소 계sub Total 100100 100100 100100 100100 100100 100100 100100

* 중량부 기준* By weight

표 1의 조성물을 경화시켜 도막을 제조하여 물성을 확인하여 표2에 기재하였다.The composition of Table 1 was cured to prepare a coating film, and its physical properties were confirmed.

구 분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 비교예1Comparative Example 1 비교예2Comparative Example 2 가사시간
(100,000cps
도달시간, 분)Housework time
(100,000 cps
Reaching time, minute) 8383 7575 6363 5858 4848 7878 7272 인장강도(N/㎟)Tensile strength (N / mm 2) 2.92.9 3.23.2 3.63.6 3.93.9 4.54.5 3.33.3 3.63.6 파단시 신장율(%)Elongation at break (%) 750750 763763 760760 780780 760760 780780 760760 인열강도(N/㎜)Tear strength (N / mm) 1717 1919 1919 2323 2626 1717 1919 경도(Shore A)Hardness (Shore A) 5454 5656 5858 5959 6262 5858 6060 열화처리 후의 인장성능(%)
(80℃ㅧ8주)Tensile Performance (%) after Degradation Treatment
(80 ° C ㅧ 8 weeks) 8383 8686 8585 8989 8282 2주 후
43%after 2 weeks
43% 2주 후
49%after 2 weeks
49%

표 2에서 확인할 수 있는 바와 같이, 본발명의 탄성체 조성물에 의한 도막은 기존 비교예의 도막과 대비시, 비교예의 도막과 동등하거나 더 우수한 물성을 보여주고 있다. 특히, 본발명의 탄성체 조성물에 의한 도막은 열화처리후의 인장성능이 비교예보다 월등히 우수함을 확인할 수 있었다.As can be seen from Table 2, the coating film of the elastomer composition of the present invention exhibits the same or better physical properties as the coating film of the comparative example when compared with the coating film of the conventional comparative example. Particularly, it was confirmed that the coating film of the elastomer composition of the present invention was much better in tensile performance after the deterioration treatment than the comparative example.

실시예 6 ~ 10 및 비교예 3 ~ 4Examples 6 to 10 and Comparative Examples 3 to 4

위에서 합성한 본 발명 조성물을 포함하여 아래 표 3에서와 같은 조성으로 우레아 탄성체 수지 조성물을 제조하였다. The urea elastomer resin composition was prepared as shown in Table 3 below, including the composition of the present invention synthesized above.

주제부Topic section

주제부는 실시예 비교예 모두 NEOFORCE KA-790(강남화성)을 사용하였다.The subject section is NEOFORCE KA-790 (Kangnam Hwaseong) was used.

경화제Hardener

비교예(MOCA 배합)Comparative Example (MOCA formulation)

상기 우레탄 탄성체 수지 조성물에서와 동일하다.Is the same as that of the urethane elastomer resin composition.

실시예6 ~ 10 (본 발명 배합)Examples 6 to 10 (compounding of the present invention)

본 발명의 이민계 조성물, 다이에틸톨루엔다이아민, 이소프론디아민, 폴리(옥시프로필렌)디아민, 폴리(옥시프로필렌)트리아민조색제, 자외선안정제 등을 배합하여 제품을 제조하였다.The product was prepared by blending the imine based composition of the present invention, diethyltoluenediamine, isophoronediamine, poly (oxypropylene) diamine, poly (oxypropylene) triamine coloring agent, ultraviolet stabilizer and the like.

탄성체 수지조성물의 경화Curing of the elastomer resin composition

우레아 탄성체는 건조속도가 수초에 불과하기 때문에 2액형 전용 우레아 스프레이 도장장비가 필요하며 스프레이 장비의 압력조건은 정지압 기준 최소 2,000Psi 이상이어야 하고 주제 및 경화제의 온도를 각각 60~70℃로 설정할 수 있어야 한다. 상기의 조건에 부합된 GRACO사 XP-2 장비를 사용하여 상기에서 제조한 우레아 탄성체 수지조성물을 미리 준비한 이형처리된 유리판(50㎝ㅧ50㎝)에 1.5~2.0㎜ 두께가 되도록 도포하였다. 도포한 유리판을 표준상태 [KS A0006의 20ㅁ2℃, 습도 60ㅁ20%]로 설정된 실험실에 24시간 이상 표준상태에서 보관하고 1주일 후 물성을 측정하였다.The urea elastomer requires only 2-pack type urea spray coating equipment because the drying speed is only a few seconds. The pressure condition of the spray equipment should be at least 2,000 psi of static pressure and the temperature of the main and hardener may be set at 60 ~ 70 ℃ . Using the GRACO XP-2 equipment conforming to the above conditions, the urea elastomer resin composition prepared above was applied to a release-treated glass plate (50 cm ㅧ 50 cm) prepared in advance to a thickness of 1.5-2.0 mm. The coated glass plate was stored in a standard state (KS A0006 at 20 ° C and 2 ° C, humidity 60 ° C and 20%) for 24 hours or longer and stored for one week.

구 분division 실시예6Example 6 실시예7Example 7 실시예8Example 8 실시예9Example 9 실시예10Example 10 비교예3Comparative Example 3 비교예4Comparative Example 4 주제부  Topic section NEOFORCE?? KA-790 (강남화성)NEOFORCE ?? KA-790 (Kangnam Hwaseong) 100100 경화제Hardener 다이에틸톨루엔다이아민
(Lonza)Diethyltoluenediamine
(Lonza) 18.018.0 19.019.0 본발명조성물The composition of the present invention 18.018.0 19.019.0 20.020.0 21.021.0 22.022.0 이소프론디아민
(BASF)Isoflondiamine
(BASF) 4.04.0 5.05.0 4.04.0 3.03.0 2.02.0 폴리(옥시프로필렌)디아민
Huntsman D-2000Poly (oxypropylene) diamine
Huntsman D-2000 74.074.0 72.072.0 71.071.0 71.071.0 71.071.0 76.076.0 72.072.0 폴리(옥시프로필렌)트리아민
Huntsman
T-5000Poly (oxypropylene) triamine
Huntsman
T-5000 1.01.0 1.01.0 1.01.0 5.05.0 8.08.0 자외선 안정제
(송원산업)Ultraviolet stabilizer
(Songwon Industry) 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 조색제Colorant 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 소 계sub Total 100.0100.0 100.0100.0 100.0100.0 100.0100.0 100100 100.0100.0 100.0100.0

* 중량부 기준* By weight

구 분division 실시예6Example 6 실시예7Example 7 실시예8Example 8 실시예9Example 9 실시예10Example 10 비교예3Comparative Example 3 비교예4Comparative Example 4 지촉건조시간
(분)Touch dry time
(minute) 3232 2929 2828 2323 2020 1818 1717 인장강도(N/㎟)Tensile strength (N / mm 2) 19.519.5 20.120.1 파단시 신장율(%)Elongation at break (%) 440440 415415 395395 340340 332332 340340 335335 인열강도(N/㎜)Tear strength (N / mm) 5858 5959 6262 6666 7171 6565 6868 경도(Shore A)Hardness (Shore A) 8383 8484 8686 8888 9090 8888 9090

표 4에서 확인할 수 있는 바와 같이, 본발명의 탄성체 조성물에 의한 도막은 기존 비교예의 도막과 대비시, 비교예의 도막과 동등하거나 더 우수한 물성을 보여주고 있다. 특히, 본발명의 탄성체 조성물에 의한 도막은 파단시의 신장성능이 비교예보다 우수함을 확인할 수 있었다.As can be seen from Table 4, the coating film of the elastomer composition of the present invention exhibits the same or better physical properties as the coating film of the comparative example in comparison with the coating film of the conventional comparative example. In particular, it was confirmed that the coating film of the elastomer composition of the present invention had better stretching performance at break than the comparative example.

Claims (5)

하기 화학식 1로 표시되는 아민기를 함유한 이민계 조성물
Figure 112018106435529-pat00011

여기서, R1 은 프로필, 부틸, 이소부틸, 3-메틸부틸 또는 벤질이고,
R2는 폴리옥시프로필렌디아민유도체(
Figure 112018106435529-pat00012
), 이소포론디아민유도체(
Figure 112018106435529-pat00013
) 또는 디에틸톨루엔디아민 유도체(
Figure 112018106435529-pat00014
) 이고,
몰비로 R1 : R2 = 1 : 0.5 ~ 1.5 이다.An amine-containing composition comprising an amine group represented by the following formula
Figure 112018106435529-pat00011

Wherein R1 is propyl, butyl, isobutyl, 3-methylbutyl or benzyl,
R2 is a polyoxypropylene diamine derivative (
Figure 112018106435529-pat00012
), Isophorone diamine derivatives (
Figure 112018106435529-pat00013
) Or diethyltoluenediamine derivative (
Figure 112018106435529-pat00014
) ego,
R1: R2 = 1: 0.5 to 1.5 in molar ratio. 1항에 있어서, 몰비로 R1 : R2 = 1 : 0.9 ~ 1.4 임을 특징으로 하는 아민기를 함유한 이민계 조성물.The amine-containing composition according to claim 1, wherein R1: R2 = 1: 0.9 to 1.4 in terms of molar ratio. 플라스크에 Di-ethyltoluene diamine을 투입 교반하면서 Isobutyraldehyde을 분할 투입하여 60~70℃에서 4 - 8 시간 반응후 Toluene을 투입하여 110 ~ 150℃에서 환류 중합하며 발생한 물을 제거하고 반응이 완료된 후에 감압하여 Tolene을 회수하는 것을 특징으로 하는 하기 화학식 1로 표시되는 아민기를 함유한 이민계 조성물의 제조방법.
Figure 112018106435529-pat00005

여기서, R1 은 프로필, 부틸, 이소부틸, 3-메틸부틸 또는 벤질이고,
R2는 폴리옥시프로필렌디아민유도체(
Figure 112018106435529-pat00015
), 이소포론디아민유도체(
Figure 112018106435529-pat00016
) 또는 디에틸톨루엔디아민 유도체(
Figure 112018106435529-pat00017
) 이고,
몰비로 R1 : R2 = 1 : 0.5 ~ 1.5 이다.Di-ethyltoluene diamine was added to the flask. Isobutyraldehyde was added dropwise to the flask. The mixture was reacted at 60 ~ 70 ℃ for 4 - 8 hours, then toluene was added and the mixture was refluxed at 110 ~ 150 ℃. Water was removed, And recovering the amine group represented by the following formula (1).
Figure 112018106435529-pat00005

Wherein R1 is propyl, butyl, isobutyl, 3-methylbutyl or benzyl,
R2 is a polyoxypropylene diamine derivative (
Figure 112018106435529-pat00015
), Isophorone diamine derivatives (
Figure 112018106435529-pat00016
) Or diethyltoluenediamine derivative (
Figure 112018106435529-pat00017
) ego,
R1: R2 = 1: 0.5 to 1.5 in molar ratio. 1항 또는 2항의 조성물을 포함하는 2액형 폴리우레탄 탄성체 조성물.A two-pack type polyurethane elastomer composition comprising the composition of claims 1 or 2. 1항 또는 2항의 조성물을 포함하는 2액형 폴리우레아 탄성체 조성물.









A two-pack type polyurea elastomer composition comprising the composition of claims 1 or 2.









KR1020180043679A 2018-04-16 2018-04-16 An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound KR101943964B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020180043679A KR101943964B1 (en) 2018-04-16 2018-04-16 An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound
CN201810448953.2A CN110386880A (en) 2018-04-16 2018-05-11 Imine compound of amino-contained and preparation method thereof, elastomer resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020180043679A KR101943964B1 (en) 2018-04-16 2018-04-16 An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound

Publications (1)

Publication Number Publication Date
KR101943964B1 true KR101943964B1 (en) 2019-01-30

Family

ID=65277077

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020180043679A KR101943964B1 (en) 2018-04-16 2018-04-16 An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound

Country Status (2)

Country Link
KR (1) KR101943964B1 (en)
CN (1) CN110386880A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102123893B1 (en) * 2020-03-31 2020-06-17 한국석유공업 주식회사 Imine chain extender composition containing amine functionality monoaspartic ester group and elastomer composition including the same
KR102123894B1 (en) * 2020-03-31 2020-06-17 한국석유공업 주식회사 Imine crosslinking agent composition containing amine functionality monoaspartic ester group and elastomer composition including the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6828405B1 (en) * 1995-05-23 2004-12-07 The Sherwin-Williams Company Polyimine/polyisocyanate coating composition
US20070060733A1 (en) * 2005-09-15 2007-03-15 Jozef Verborgt Polyenureas and method of making the same
US20140275464A1 (en) * 2005-09-15 2014-09-18 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Polyenureas and method of making the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070100112A1 (en) * 2005-10-27 2007-05-03 Bayer Materialscience Llc Polyurethane-urea elastomers
EP1876196A1 (en) * 2006-06-30 2008-01-09 Sika Technology AG VOC free or low VOC polyurethane coating
EP2072550A1 (en) * 2007-12-21 2009-06-24 Sika Technology AG Hardening compounds with reduced gas emission
EP2189484B1 (en) * 2008-10-31 2011-05-18 Sika Technology AG Polyurethane composition comprising organomethoxysilane having anisostropic material properties
CN104884494B (en) * 2013-01-22 2018-07-20 Sika技术股份公司 The liquid comprising two kinds of different aldimines for roof applies waterproof membrane
US11214706B2 (en) * 2015-12-21 2022-01-04 Sika Technology Ag Polyurethane composition with low plasticiser migration
JP6880061B2 (en) * 2015-12-21 2021-06-02 シーカ テクノロジー アクチェンゲゼルシャフト Polyardimine and curable polyurethane composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6828405B1 (en) * 1995-05-23 2004-12-07 The Sherwin-Williams Company Polyimine/polyisocyanate coating composition
US20070060733A1 (en) * 2005-09-15 2007-03-15 Jozef Verborgt Polyenureas and method of making the same
US20140275464A1 (en) * 2005-09-15 2014-09-18 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Polyenureas and method of making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102123893B1 (en) * 2020-03-31 2020-06-17 한국석유공업 주식회사 Imine chain extender composition containing amine functionality monoaspartic ester group and elastomer composition including the same
KR102123894B1 (en) * 2020-03-31 2020-06-17 한국석유공업 주식회사 Imine crosslinking agent composition containing amine functionality monoaspartic ester group and elastomer composition including the same

Also Published As

Publication number Publication date
CN110386880A (en) 2019-10-29

Similar Documents

Publication Publication Date Title
CN1307224C (en) Polyurethane composition
KR101310615B1 (en) Polyurethane membranous waterproof composition and spray type coating method using the same
JP6455426B2 (en) One-component moisture-curing polyurethane composition
KR101141511B1 (en) Environment friendly polyurea paint composition having high elasticity and method using the same
JP5039328B2 (en) One-part moisture-curable polyurethane composition
KR101943964B1 (en) An imine compound containing an amine group, a process for producing the same, and an elastomer-resin-composition containing the imine compound
JP4475090B2 (en) Two-component curable polyurethane resin composition
JP6171330B2 (en) Adhesive composition
JP6069576B2 (en) Process for producing spray polyurethane elastomer and elastomer produced by the process
JP5106801B2 (en) One-part room temperature and moisture-curing shoe repair agent and shoe repair method
JP4736438B2 (en) Two-component room temperature curable liquid urethane composition
JP2017066335A (en) Urethane adhesive composition
JP6172056B2 (en) Urethane adhesive composition
KR100879980B1 (en) One -liquid type curable polyurethane resin composition for key-pad and its making method
JP4581195B2 (en) Two-component polyurethane waterproof membrane
KR20150025992A (en) Urethane waterproofing material using slag
JP6442638B1 (en) Two-component mixed room temperature curing pavement and elastic pavement method
JP7020449B2 (en) Resin composition for coating, hardened film, concrete coating structure, and surface coating method for concrete structure
ES2297229T3 (en) SYSTEMS OF TWO COMPONENTS FOR THE PREPARATION OF ELASTIC COATINGS.
JP2000226424A (en) Urethane prepolymer composition
KR101448349B1 (en) Environment―friendly Hybrid Polyurea Composition
JP2000007989A (en) Cold curable composition for forming waterproof coating film
JP2006111805A (en) Two-pack curable polyurethane resin composition
KR100927870B1 (en) Water based adhesive composition for styrene ethylene butadiene styrene type impact absorbing material
KR20060079552A (en) Two-component type room temperature curable polyurethane composition

Legal Events

Date Code Title Description
E701 Decision to grant or registration of patent right
GRNT Written decision to grant