KR20230080100A - Two-part reactive adhesive composition for cryogenic applications - Google Patents
Two-part reactive adhesive composition for cryogenic applications Download PDFInfo
- Publication number
- KR20230080100A KR20230080100A KR1020210167525A KR20210167525A KR20230080100A KR 20230080100 A KR20230080100 A KR 20230080100A KR 1020210167525 A KR1020210167525 A KR 1020210167525A KR 20210167525 A KR20210167525 A KR 20210167525A KR 20230080100 A KR20230080100 A KR 20230080100A
- Authority
- KR
- South Korea
- Prior art keywords
- isocyanate
- heptane
- isocyanatemethyl
- main part
- bicyclo
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000004823 Reactive adhesive Substances 0.000 title claims abstract description 65
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 230000001070 adhesive effect Effects 0.000 claims abstract description 52
- 239000000853 adhesive Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 45
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920000608 Polyaspartic Polymers 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 42
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000077 silane Inorganic materials 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims description 85
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 78
- 150000002513 isocyanates Chemical group 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- -1 lysine ester Chemical class 0.000 claims description 18
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 14
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007983 Tris buffer Substances 0.000 claims description 11
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QKOWXXDOHMJOMQ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)biuret Chemical compound O=C=NCCCCCCNC(=O)N(CCCCCCN=C=O)C(=O)NCCCCCCN=C=O QKOWXXDOHMJOMQ-UHFFFAOYSA-N 0.000 claims description 7
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004472 Lysine Substances 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 3
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 2
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- OADNRFNXACMWMJ-UHFFFAOYSA-N benzene;isocyanic acid Chemical compound N=C=O.C1=CC=CC=C1 OADNRFNXACMWMJ-UHFFFAOYSA-N 0.000 claims 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000007718 adhesive strength test Methods 0.000 description 8
- 239000003949 liquefied natural gas Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
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- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- WVWYODXLKONLEM-UHFFFAOYSA-N 1,2-diisocyanatobutane Chemical compound O=C=NC(CC)CN=C=O WVWYODXLKONLEM-UHFFFAOYSA-N 0.000 description 1
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- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
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- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
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- CCXLOQVMDTWRSP-UHFFFAOYSA-N 2-cyclohexylpropan-2-ylcyclohexane Chemical compound C1CCCCC1C(C)(C)C1CCCCC1 CCXLOQVMDTWRSP-UHFFFAOYSA-N 0.000 description 1
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
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- 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 1
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Images
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명의 일 예는 수산기가 변성된 폴리아스파틱 레진 및 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함하는 주제부; 및 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함하는 경화제부;로 구성되는 2액형 반응성 접착제 조성물을 제공한다. 또한, 본 발명의 바람직한 일 예는 수산기가 변성된 폴리아스파틱 레진, 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 및 이소시아네이트기를 포함하지 않는 실란계 커플링제를 포함하는 주제부; 및 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 및 이소시아네이트실란계 커플링제를 포함하는 경화제부;로 구성되는 2액형 반응성 접착제 조성물을 제공한다. 본 발명에 따른 2액형 반응성 접착제 조성물은 주제부와 경화제부의 경화 반응을 통해 -190℃ 이하의 극저온에서 6% 이상의 연신율과 함께 상온에서 10 MPa 이상의 겹치기전단 접착강도 및 2N/㎜ 이상의 T-박리 접착강도를 가지는 접착 도막을 형성할 수 있다.An example of the present invention includes a main part including a polyaspartic resin having a hydroxyl group modified and a polyisocyanate compound having two or more isocyanate functional groups; and a curing agent part comprising a polyisocyanate compound having three or more isocyanate functional groups. In addition, a preferred example of the present invention is a main part including a polyaspartic resin having a modified hydroxyl group, a polyisocyanate compound having two or more isocyanate functional groups, and a silane-based coupling agent not containing an isocyanate group; and a curing agent part including a polyisocyanate compound having three or more isocyanate functional groups and an isocyanatesilane-based coupling agent. The two-component reactive adhesive composition according to the present invention has an elongation of 6% or more at a cryogenic temperature of -190 ° C or less through a curing reaction of the main part and the curing agent part, lap shear adhesive strength of 10 MPa or more and T-peel adhesion of 2 N / mm or more at room temperature An adhesive coating film having strength can be formed.
Description
본 발명은 2액형 반응성 접착제 조성물에 관한 것으로서, 더 상세하게는 극저온 환경에서도 우수한 연신율과 함께 균형잡힌 전단 접착강도 및 박리 접착강도를 통해 열수축 응력 내지 열팽창 응력을 견딜 수 있는 극저온용 2액형 반응성 접착제 조성물에 관한 것이다.The present invention relates to a two-component reactive adhesive composition, and more particularly, to a cryogenic two-component reactive adhesive composition capable of withstanding heat shrinkage stress or thermal expansion stress through balanced shear adhesive strength and peel adhesive strength with excellent elongation even in a cryogenic environment. It is about.
액화천연가스(liquefied natural gas, LNG)와 액화가스 연료를 운반하는 운반선, 특히 LNG 운반선에는 LNG를 저장/보관하는 화물창이 구비되어 있다. LNG 운반선 화물창은 -163℃의 극저온 환경에서 액화한 천연가스가 수송 중 기화로 인해 손실되는 것을 방지하기 위해 도 1에서 보이는 바와 같이 1차 방벽/1차 단연재/2차 방벽/2차 단열재/선체의 순서로 적층되는 단열구조를 가지고 있다. 상기 LNG 운반선 화물창의 적층 단열구조 중 1차 단열재와 2차 방벽 사이의 부착 또는 2차 방벽과 2차 단열재 간의 연결은 소정의 접착제를 사용하는 접착 공법에 의해 이루어진다. LNG 운반선 화물창의 적층 단열구조를 형성하기 위해 사용되는 접착제는 극심한 온도차에 따른 열수축 및 열팽창 응력을 견뎌야 하기 때문에 극저온에서도 높은 연신율(elongation)을 유지하는 성능이 요구된다.Carriers carrying liquefied natural gas (LNG) and liquefied gas fuel, in particular, LNG carriers are provided with a cargo hold for storing/storing LNG. In order to prevent loss of natural gas liquefied in a cryogenic environment of -163 ° C due to vaporization during transportation, the cargo hold of an LNG carrier is a primary barrier / primary insulation material / secondary barrier / secondary insulation material / as shown in FIG. It has an insulation structure that is stacked in order of the hull. Attachment between the primary insulation and the secondary barrier or connection between the secondary barrier and the secondary insulation in the laminated insulation structure of the cargo hold of the LNG carrier is performed by an adhesive method using a predetermined adhesive. Since the adhesive used to form the laminated insulation structure of the cargo hold of an LNG carrier must withstand thermal contraction and thermal expansion stress due to extreme temperature differences, performance to maintain high elongation even at extremely low temperatures is required.
종래의 극저온용 접착제 중 1차 단열재과 2차 방벽을 접합하기 위해 주로 에폭시계 접착제가 사용되었고, 2차 방벽과 2차 단열재를 접합하기 위해 주로 폴리우레탄계 접착제사 사용되었다. 극저온용 에폭시계 접착제는 극저온용 폴리우레탄계 접착제에 비해 극저온 환경에서 신율이 작다는 단점이 있음에도 불구하고 극저온용 폴리우레탄계 접착제의 접착 특성이 에폭시계 접착제만큼 우수하지 않아 다른 형태의 접착제로 대체되지 못하고 있는 상황이다.Among conventional cryogenic adhesives, an epoxy-based adhesive is mainly used to bond a primary insulation material and a secondary barrier, and a polyurethane-based adhesive yarn is mainly used to bond a secondary barrier and a secondary insulation material. Epoxy-based adhesives for cryogenic use have the disadvantage of lower elongation in a cryogenic environment than polyurethane-based adhesives for cryogenic use, but the adhesive properties of polyurethane-based adhesives for cryogenic use are not as good as epoxy-based adhesives, so they are not replaced by other types of adhesives situation.
극저온에서 적용되는 접착제와 관련하여, 대한민국 등록특허공보 제10-2287124호에는 소정의 화학 구조식을 가지는 실릴화된 중합체 및 하나 이상의 필러를 포함하는 접착제 조성물이 개시되어 있다. 또한, 대한민국 등록특허공보 제10-1731124호에는 소정의 수지와 소정의 경화제의 반응에 의해 수득되는 폴리우레탄 접착제 조성물이 개시되어 있다. 상기 대한민국 등록특허공보 제10-1731124호의 접착제 조성물을 구성하는 소정의 수지는 폴리에테르 폴리올, 폴리에스테르 폴리올, 불포화 폴리올), 히드록실 말단을 갖는 열가소성 폴리우레탄 예비중합체로부터 선택되는 하나 이상의 폴리올; 1 차 또는 2 차 아민 또는 폴리아민의 군으로부터 선택되는 하나 이상의 역치 작용제(threshold agent), C2-C10 디올의 군으로부터 선택되는 사슬 연장제; 및 무기 충전제; 열-촉진화 가교 촉매 등을 포함하고, 소정의 경화제는 NCO 말단을 갖는 하나 이상의 폴리우레탄 예비중합체; 및 무기 충전제를 포함한다.Regarding an adhesive applied at a cryogenic temperature, Korean Patent Registration No. 10-2287124 discloses an adhesive composition including a silylated polymer having a predetermined chemical structure and one or more fillers. In addition, Korean Patent Registration No. 10-1731124 discloses a polyurethane adhesive composition obtained by reaction of a predetermined resin and a predetermined curing agent. The predetermined resin constituting the adhesive composition of Korean Patent Registration No. 10-1731124 is at least one polyol selected from polyether polyol, polyester polyol, unsaturated polyol), thermoplastic polyurethane prepolymer having a hydroxyl end; at least one threshold agent selected from the group of primary or secondary amines or polyamines, a chain extender selected from the group of C2-C10 diols; and inorganic fillers; heat-accelerated crosslinking catalysts; and inorganic fillers.
본 발명은 종래의 기술적 배경하에서 도출된 것으로서, 본 발명의 목적은 극저온 환경에서도 우수한 연신율과 함께 균형잡힌 전단 접착강도 및 박리 접착강도를 통해 열수축 응력 내지 열팽창 응력을 견딜 수 있는 극저온용 2액형 반응성 접착제 조성물을 제공하는 데에 있다.The present invention was derived under the conventional technical background, and an object of the present invention is a two-component reactive adhesive for cryogenic use that can withstand heat shrinkage stress or thermal expansion stress through balanced shear adhesive strength and peel adhesive strength with excellent elongation even in a cryogenic environment. It is to provide a composition.
상기 목적을 달성하기 위하여, 본 발명의 일 예는 수산기가 변성된 폴리아스파틱 레진 및 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함하는 주제부; 및 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함하는 경화제부;로 구성되고, 상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진은 수산기가 이소시아네이트기에 비활성인 관능기로 변성된 것이고, 상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진의 적어도 일부는 주제부의 다른 구성성분인 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물과의 어덕트화 반응(Adduct reaction)에 의해 점도가 10,000~200,000 센티포이즈(centipoises, cPs)의 범위를 갖는 어덕트화 변성 폴리아스파틱 레진으로 존재하는 것을 특징으로 하는 2액형 반응성 접착제 조성물을 제공한다.In order to achieve the above object, an example of the present invention is a main part including a polyisocyanate compound having a polyaspartic resin modified with a hydroxyl group and two or more isocyanate functional groups; and a curing agent part including a polyisocyanate compound having three or more isocyanate functional groups, wherein the polyaspartic resin in which the hydroxyl group, which is a component of the main part, is modified, is one in which the hydroxyl group is modified with a functional group inactive to the isocyanate group, and the main part is modified. At least a part of the polyaspartic resin in which the hydroxyl group, which is a component of the part, is modified, has a viscosity of 10,000 to 200,000 cm by an adduct reaction with a polyisocyanate compound having two or more isocyanate functional groups, which is another component of the main part. It provides a two-component reactive adhesive composition characterized in that it exists as an adduct modified polyaspartic resin having a range of centipoises (cPs).
상기 목적을 달성하기 위하여, 본 발명의 바람직한 일 예는 수산기가 변성된 폴리아스파틱 레진, 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 및 이소시아네이트기를 포함하지 않는 실란계 커플링제를 포함하는 주제부; 및 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 및 이소시아네이트실란계 커플링제를 포함하는 경화제부;로 구성되고, 상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진은 수산기가 이소시아네이트기에 비활성인 관능기로 변성된 것이고, 상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진의 적어도 일부는 주제부의 다른 구성성분인 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물과의 어덕트화 반응(Adduct reaction)에 의해 점도가 10,000~200,000 센티포이즈(centipoises, cPs)의 범위를 갖는 어덕트화 변성 폴리아스파틱 레진으로 존재하는 것을 특징으로 하는 2액형 반응성 접착제 조성물을 제공한다.In order to achieve the above object, a preferable example of the present invention is a main part comprising a polyaspartic resin having a modified hydroxyl group, a polyisocyanate compound having two or more isocyanate functional groups, and a silane-based coupling agent not containing an isocyanate group; and a curing agent part including a polyisocyanate compound having three or more isocyanate functional groups and an isocyanate silane-based coupling agent, wherein the polyaspartic resin in which the hydroxyl group, which is a component of the main part, is modified, is a functional group in which the hydroxyl group is inactive to the isocyanate group. At least a part of the polyaspartic resin having modified hydroxyl group, which is a component of the main part, is formed by an adduct reaction with a polyisocyanate compound having two or more isocyanate functional groups, which is another constituent of the main part. It provides a two-component reactive adhesive composition characterized in that it exists as an adduct modified polyaspartic resin having a viscosity in the range of 10,000 to 200,000 centipoise (cPs).
본 발명에 따른 2액형 반응성 접착제 조성물은 주제부와 경화제부의 경화 반응을 통해 -190℃ 이하의 극저온에서 6% 이상의 연신율과 함께 상온에서 10 MPa 이상의 겹치기전단 접착강도 및 2N/㎜ 이상의 T-박리 접착강도를 가지는 접착 도막을 형성할 수 있다.The two-component reactive adhesive composition according to the present invention has an elongation of 6% or more at a cryogenic temperature of -190 ° C or less through a curing reaction of the main part and the curing agent part, lap shear adhesive strength of 10 MPa or more and T-peel adhesion of 2 N / mm or more at room temperature An adhesive coating film having strength can be formed.
도 1은 일반적인 LNG 운반선 화물창의 단열 구조를 나타낸 것이다.
도 2는 본 발명의 실시예에서 제조한 극저온용 2액형 반응성 접착제 조성물의 이소시아네이트 지수(isocyanate index) 값에 따른 겹치기전단 접착강도 시험 결과를 나타낸 것이다.
도 3은 본 발명의 실시예에서 제조한 극저온용 2액형 반응성 접착제 조성물의 이소시아네이트 지수(isocyanate index) 값에 따른 T-박리 접착강도 시험 결과를 나타낸 것이다.
도 4는 본 발명의 실시예에서 제조한 극저온용 2액형 반응성 접착제 조성물의 이소시아네이트 지수(isocyanate index) 값에 따른 -190℃에서의 연신율(elongation) 측정 시험 결과를 나타낸 것이다.1 shows the insulation structure of a general LNG carrier cargo hold.
Figure 2 shows the results of the overlap shear adhesive strength test according to the isocyanate index (isocyanate index) value of the two-component reactive adhesive composition for cryogenic temperature prepared in Example of the present invention.
Figure 3 shows the T-peel adhesive strength test results according to the isocyanate index (isocyanate index) value of the two-component reactive adhesive composition for cryogenic temperature prepared in Example of the present invention.
Figure 4 shows the elongation measurement test results at -190 ℃ according to the isocyanate index (isocyanate index) value of the two-component reactive adhesive composition for cryogenic temperature prepared in Example of the present invention.
이하, 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 극저온 환경에서도 우수한 연신율과 함께 균형잡힌 전단 접착강도 및 박리 접착강도를 통해 열수축 응력 내지 열팽창 응력을 견딜 수 있는 극저온용 2액형 반응성 접착제 조성물에 관한 것이다.The present invention relates to a two-component reactive adhesive composition for cryogenic temperatures capable of withstanding thermal contraction stress or thermal expansion stress through balanced shear adhesive strength and peel adhesive strength with excellent elongation even in a cryogenic environment.
본 발명의 일 예에 따른 2액형 반응성 접착제 조성물은 주제부와 경화제부로 구성되고, 상기 주제부는 수산기가 변성된 폴리아스파틱 레진 및 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함하고, 상기 경화제부는 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함한다. 이하, 본 발명의 일 예에 따른 2액형 반응성 접착제 조성물을 주제부와 경화제부로 나누어 설명한다.A two-component reactive adhesive composition according to an embodiment of the present invention is composed of a main part and a curing agent part, wherein the main part includes a hydroxyl group-modified polyaspartic resin and a polyisocyanate compound having two or more isocyanate functional groups, and the curing agent part It includes polyisocyanate compounds having three or more isocyanate functional groups. Hereinafter, a two-component reactive adhesive composition according to an embodiment of the present invention will be described by dividing it into a main part and a curing agent part.
주제부subject part
주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진은 수산기가 이소시아네이트기에 비활성인 관능기로 변성된 것이다. 상기 이소시아네이트기에 비활성인 관능기는 이소시아네이트기와 반응하여 우레탄 결합 또는 우레아 결합을 형성하지 않는 관능기이다. 상기 이소시아네이트기에 비활성인 관능기의 예로는 n-프로필렌, n-부틸렌, n-헥실렌, n-헵틸렌, n-옥틸렌, n-노닐렌, n-데실렌, 시클로헥산-1,2-다이일, 시클로헥산-1,3-다이일, 시클로헥산-1,4-다이일, 시클로펜탄-1,3-다이일, 메틸렌비스(시클로헥산-1,4-다이일), 다이시클로헥실메탄, (다이메틸메틸렌)비스(시클로헥산-1,4-다이일), 다이메틸다이시클로헥실메탄, 1-아미노-3,3,5-트리메틸-5-아미노메틸시클로헥산, 글리시딜 등이 있다. 상기 수산기가 변성된 폴리아스파틱 레진은 바람직하게는 수산기가 적어도 1개 이상의 글리시딜기를 포함하는 관능기로 변성된 것이고, 더 바람직하게는 수산기가 적어도 2개 이상의 글리시딜기를 포함하는 관능기로 변성된 것이다. 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진은 상온(약 20℃)에서의 점도가 약 400~600 센티포이즈(centipoises, cPs)로서 접착제로 사용하기에는 너무 낮은 점도를 가진다. 본 발명의 일 예에 따른 2액형 반응성 접착제 조성물에서, 상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진의 적어도 일부는 주제부의 다른 구성성분인 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물과의 어덕트화 반응(Adduct reaction)에 의해 상온(약 20℃)에서의 점도가 10,000~200,000 센티포이즈(centipoises, cPs)의 범위를 갖는 어덕트화 변성 폴리아스파틱 레진으로 존재한다.The polyaspartic resin in which the hydroxyl group is modified, which is a component of the main part, is obtained by modifying the hydroxyl group with a functional group inactive to the isocyanate group. The functional group that is inactive to the isocyanate group is a functional group that does not form a urethane bond or a urea bond by reacting with the isocyanate group. Examples of the functional group inactive to the isocyanate group include n-propylene, n-butylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, cyclohexane-1,2- Diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, cyclopentane-1,3-diyl, methylenebis(cyclohexane-1,4-diyl), dicyclohexyl Methane, (dimethylmethylene)bis(cyclohexane-1,4-diyl), dimethyldicyclohexylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, glycidyl, etc. there is The hydroxyl group-modified polyaspartic resin is preferably one in which the hydroxyl group is modified with a functional group containing at least one glycidyl group, and more preferably the hydroxyl group is modified with a functional group containing at least two or more glycidyl groups. It became. Polyaspartic resin with modified hydroxyl group, which is a component of the main part, has a viscosity of about 400 to 600 centipoise (cPs) at room temperature (about 20° C.), which is too low to be used as an adhesive. In the two-component reactive adhesive composition according to one embodiment of the present invention, at least a part of the polyaspartic resin modified with a hydroxyl group, which is a constituent of the main part, is mixed with a polyisocyanate compound having two or more isocyanate functional groups, which is another constituent of the main part. It exists as an adduct modified polyaspartic resin having a viscosity in the range of 10,000 to 200,000 centipoise (cPs) at room temperature (about 20° C.) by an adduct reaction.
주제부의 구성성분인 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물은 공지의 다양한 폴리이소시아네이트 화합물에서 선택될 수 있다. 예들 들어, 주제부의 구성성분인 폴리이소시아네이트 화합물은 트리메틸렌다이이소시아네이트, 테트라메틸렌다이이소시아네이트, 헥사메틸렌다이이소시아네이트, 펜타메틸렌다이이소시아네이트, 1,2-프로필렌다이이소시아네이트, 1,2-부틸렌다이이소시아네이트, 2,3-부틸렌다이이소시아네이트, 1,3-부틸렌다이이소시아네이트, 2,4,4- 또는 2,2,4-트리메틸헥사메틸렌다이이소시아네이트, 2,6-다이이소시아네이트메틸카프로에이트, 1,12-도데카메틸렌다이이소시아네이트 등의 지방족 다이이소시아네이트; 라이신에스테르트리이소시아네트, 1,4,8-트리이소시아네이트옥탄, 1,6,11-트리이소시아네이트운데칸, 1,8-다이이소시아네이트-4-이소시아네이트메틸옥탄, 1,3,6-트리이소시아네이트헥산, 2,5,7-트리메틸-1,8-다이이소시아네이트-5-이소시아네이트메틸옥탄 등의 지방족 트리이소시아네이트; 1,3-시클로펜텐다이이소시아네이트, 1,4-시클로헥산다이이소시아네이트, 1,3-시클로헥산다이이소시아네이트, 3-이소시아네이트메틸-3,5,5-트리메틸시클로헥실이소시아네이트(관용명: 이소포론다이이소시아네이트), 4,4'-메틸렌비스(시클로헥실이소시아네이트), 메틸-2,4-시클로헥산다이이소시아네이트, 메틸-2,6-시클로헥산다이이소시아네이트, 1,3- 또는1,4-비스(이소시아네이트메틸)시클로헥산(관용명: 수소첨가된 자일렌다이이소시아네이트) 또는 그 혼합물, 노르보르난다이이소시아네이트 등의 지환족 다이이소시아네이트; 1,3,5-트리이소시아네이트시클로헥산, 1,3,5-트리메틸이소시아네이트시클로헥산, 2-(3-이소시아네이트프로필)-2,5-다이(이소시아네이트메틸)-비시클로(2.2.1)헵탄, 2-(3-이소시아네이트프로필)-2,6-다이(이소시아네이트메틸)-비시클로(221)헵탄, 3-(3-이소시아네이트프로필)-2,5-다이(이소시아네이트메틸)-비시클로(221)헵탄, 5-(2-이소시아네이트에틸)-2-이소시아네트메틸-3-(3-이소시아네이트프로필)-비시클로(221)헵탄, 6-(2-이소시아네이트에틸)-2-이소시아네이트메틸-3-(3-이소시아네이트프로필)-비시클로(2.2.1)헵탄, 5-(2-이소시아네이트에틸)-2-이소시아네이트메틸-2-(3-이소시아네이트프로필)-비시클로(221)-헵탄, 6-(2-이소시아네이트에틸)-2-이소시아네이트메틸-2-(3-이소시아네이트프로필)-비시클로(2.2.1)헵탄 등의 지환족 트리이소시아네이트; 1,3- 또는 1,4-자일렌다이이소시아네이트 또는 그 혼합물, ω,ω'-다이이소시아네이트-1,4-디에틸벤젠, 1,3- 또는 1,4-비스(1-이소시아네이트-1-메틸에틸)벤젠(관용명: 테트라메틸자일렌다이이소시아네이트) 또는 그 혼합물 등의 방향지방족 다이이소시아네이트; 1,3,5-트리이소시아네이트메틸벤젠 등의 방향지방족 트리이소시아네이트; m-페닐렌다이이소시아네이트, p-페닐렌다이이소시아네이트, 4,4'-다이페닐다이이소시아네이트, 1,5-나프탈렌다이이소시아네이트, 2,4'- 또는 4,4'-다이페닐메탄다이이소시아네이트 또는 그 혼합물, 2,4- 또는 2,6-톨릴렌다이이소시아네이트 또는 그 혼합물, 4,4'톨루이딘다이이소시아네이트, 4,4'-다이페닐에테르다이이소시아네이트 등의 방향족 다이이소시아네이트; 트리페닐메탄-4,4',4"-트리이소시아네이트, 1,3,5-트리이소시아네이트벤젠, 2,4,6-트리이소시아네이트톨루엔 등의 방향족 트리이소시아네이트; 4,4'-다이페닐메탄-2,2',5,5'-테트라이소시아네이트 등의 방향족 테트라이소시아네이트 등이 있다. 본 발명의 일 예에 따른 2액형 반응성 접착제 조성물에서, 주제부의 구성성분인 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물은 수산기가 변성된 폴리아스파틱 레진과의 어덕트화 반응(Adduct reaction) 효율을 고려할 때 라이신에스테르트리이소시아네트, 1,4,8-트리이소시아네이트옥탄, 1,6,11-트리이소시아네이트운데칸, 1,8-다이이소시아네이트-4-이소시아네이트메틸옥탄, 1,3,6-트리이소시아네이트헥산, 2,5,7-트리메틸-1,8-다이이소시아네이트-5-이소시아네이트메틸옥탄, 1,3,5-트리이소시아네이트시클로헥산, 1,3,5-트리메틸이소시아네이트시클로헥산, 2-(3-이소시아네이트프로필)-2,5-다이(이소시아네이트메틸)-비시클로(221)헵탄, 2-(3-이소시아네이트프로필)-2,6-다이(이소시아네이트메틸)-비시클로(221)헵탄, 3-(3-이소시아네이트프로필)-2,5-다이(이소시아네이트메틸)-비시클로(221)헵탄, 5-(2-이소시아네이트에틸)-2-이소시아네트메틸-3-(3-이소시아네이트프로필)-비시클로(221)헵탄, 6-(2-이소시아네이트에틸)-2-이소시아네이트메틸-3-(3-이소시아네이트프로필)-비시클로(221)헵탄, 5-(2-이소시아네이트에틸)-2-이소시아네이트메틸-2-(3-이소시아네이트프로필)-비시클로(221)-헵탄, 6-(2-이소시아네이트에틸)-2-이소시아네이트메틸-2-(3-이소시아네이트프로필)-비시클로(221)헵탄, 1,3,5-트리이소시아네이트메틸벤젠, 트리페닐메탄-4,4',4"-트리이소시아네이트, 1,3,5-트리이소시아네이트벤젠, 2,4,6-트리이소시아네이트톨루엔, (2,4,6-트리옥소트리아진-1,3,5(2H,4H,6H)-트릴)트리스(헥사메틸렌)이소시아네이트, 1,3,5-트리스(6-이소시아네이토헥실)뷰렛, 4,4'-다이페닐메탄-2,2',5,5'-테트라이소시아네이트, 테트라이소시아네이트실란 및 4,4'-벤질리덴비스(6-메틸-m-페닐렌)테트라이소시아네이트로 이루어진 군에서 선택되는 1종 이상의 트리이소시아네이트 화합물 또는 테트라이소시아네이트 화합물로 구성되는 것이 바람직하다.The polyisocyanate compound having two or more isocyanate functional groups, which is a component of the main part, may be selected from various known polyisocyanate compounds. For example, the polyisocyanate compound, which is a component of the main part, is trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2 ,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, 1,12- aliphatic diisocyanates such as dodecamethylene diisocyanate; Lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, aliphatic triisocyanates such as 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane; 1,3-cyclopentene diisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate) , 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanate methyl) alicyclic diisocyanates such as cyclohexane (common name: hydrogenated xylene diisocyanate) or mixtures thereof and norbornanda diisocyanate; 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethylisocyanate cyclohexane, 2-(3-isocyanate propyl)-2,5-di(isocyanate methyl)-bicyclo(2.2.1)heptane, 2- (3-isocyanate propyl) -2,6-di (isocyanate methyl) -bicyclo (221) heptane, 3- (3-isocyanate propyl) -2,5-di (isocyanate methyl) -bicyclo (221) Heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo(221)heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-3- (3-Isocyanatepropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatepropyl)-bicyclo(221)-heptane, 6-( alicyclic triisocyanates such as 2-isocyanate ethyl)-2-isocyanate methyl-2-(3-isocyanate propyl)-bicyclo(2.2.1)heptane; 1,3- or 1,4-xylenediisocyanate or a mixture thereof, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanate-1- aromatic aliphatic diisocyanates such as methylethyl)benzene (common name: tetramethylxylene diisocyanate) or mixtures thereof; aromatic aliphatic triisocyanates such as 1,3,5-triisocyanate methylbenzene; m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, or aromatic diisocyanates such as mixtures, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4' toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate; Aromatic triisocyanates such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanate benzene, and 2,4,6-triisocyanate toluene; 4,4'-diphenylmethane-2 and aromatic tetraisocyanates such as ,2',5,5'-tetraisocyanate, etc. In the two-component reactive adhesive composition according to one embodiment of the present invention, the polyisocyanate compound having two or more isocyanate functional groups, which is a component of the main part, is Considering the efficiency of the adduct reaction with polyaspartic resin modified with hydroxyl group, lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1 ,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, 1,3,5-tri Isocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 2-(3-isocyanatepropyl)- 2,6-di(isocyanatemethyl)-bicyclo(221)heptane, 3-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 5-(2-isocyanateethyl )-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo(221)heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo (221) heptane, 5-(2-isocyanate ethyl)-2-isocyanate methyl-2-(3-isocyanate propyl)-bicyclo (221)-heptane, 6-(2-isocyanate ethyl)-2-isocyanate methyl- 2-(3-Isocyanate-propyl)-bicyclo(221)heptane, 1,3,5-triisocyanatemethylbenzene, triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanate Benzene, 2,4,6-triisocyanate toluene, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-tril)tris(hexamethylene)isocyanate, 1,3, 5-tris(6-isocyanatohexyl)biuret, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, tetraisocyanatesilane and 4,4'-benzylidenebis(6 It is preferably composed of at least one triisocyanate compound or tetraisocyanate compound selected from the group consisting of -methyl-m-phenylene)tetraisocyanate.
본 발명의 일 예에 따른 2액형 반응성 접착제 조성물에서 상기 주제부는 주제부 전체 중량을 기준으로 수산기가 변성된 폴리아스파틱 레진 75~95 중량% 및 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 5~25 중량%를 포함하고, 바람직하게는 수산기가 변성된 폴리아스파틱 레진 82~92 중량% 및 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 9~18 중량%를 포함한다.In the two-component reactive adhesive composition according to an embodiment of the present invention, the main part contains 75 to 95% by weight of a hydroxyl-modified polyaspartic resin and 5 to 25 polyisocyanate compounds having two or more isocyanate functional groups based on the total weight of the main part. % by weight, preferably 82 to 92% by weight of a polyaspartic resin modified with a hydroxyl group and 9 to 18% by weight of a polyisocyanate compound having two or more isocyanate functional groups.
경화제부Curing agent part
본 발명의 일 예에 따른 2액형 반응성 접착제 조성물에서 경화제부는 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함한다. 상기 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물은 주제부의 어덕트화 변성 폴리아스파틱 레진과 반응하여 우레아 결합을 형성할 수 있는 것이라면 그 종류가 크게 제한되지 않으며 공지의 다양한 다관능성 폴리이소시아네이트 화합물에서 선택될 수 있다. 상기 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물은 라이신에스테르트리이소시아네트, 1,4,8-트리이소시아네이트옥탄, 1,6,11-트리이소시아네이트운데칸, 1,8-다이이소시아네이트-4-이소시아네이트메틸옥탄, 1,3,6-트리이소시아네이트헥산, 2,5,7-트리메틸-1,8-다이이소시아네이트-5-이소시아네이트메틸옥탄, 1,3,5-트리이소시아네이트시클로헥산, 1,3,5-트리메틸이소시아네이트시클로헥산, 2-(3-이소시아네이트프로필)-2,5-다이(이소시아네이트메틸)-비시클로(221)헵탄, 2-(3-이소시아네이트프로필)-2,6-다이(이소시아네이트메틸)-비시클로(221)헵탄, 3-(3-이소시아네이트프로필)-2,5-다이(이소시아네이트메틸)-비시클로(221)헵탄, 5-(2-이소시아네이트에틸)-2-이소시아네트메틸-3-(3-이소시아네이트프로필)-비시클로(221)헵탄, 6-(2-이소시아네이트에틸)-2-이소시아네이트메틸-3-(3-이소시아네이트프로필)-비시클로(221)헵탄, 5-(2-이소시아네이트에틸)-2-이소시아네이트메틸-2-(3-이소시아네이트프로필)-비시클로(221)-헵탄, 6-(2-이소시아네이트에틸)-2-이소시아네이트메틸-2-(3-이소시아네이트프로필)-비시클로(221)헵탄, 1,3,5-트리이소시아네이트메틸벤젠, 트리페닐메탄-4,4',4"-트리이소시아네이트, 1,3,5-트리이소시아네이트벤젠, 2,4,6-트리이소시아네이트톨루엔, (2,4,6-트리옥소트리아진-1,3,5(2H,4H,6H)-트릴)트리스(헥사메틸렌)이소시아네이트, 1,3,5-트리스(6-이소시아네이토헥실)뷰렛, 4,4'-다이페닐메탄-2,2',5,5'-테트라이소시아네이트, 테트라이소시아네이트실란 및 4,4'-벤질리덴비스(6-메틸-m-페닐렌)테트라이소시아네이트로 이루어진 군에서 선택되는 1종 이상의 트리이소시아네이트 화합물 또는 테트라이소시아네이트 화합물로 구성될 수 있고, 2액형 반응성 접착제 조성물에 형성된 접착 도막의 다양한 물성을 고려할 때 (2,4,6-트리옥소트리아진-1,3,5(2H,4H,6H)-트릴)트리스(헥사메틸렌)이소시아네이트, 1,3,5-트리스(6-이소시아네이토헥실)뷰렛, 테트라이소시아네이트실란 및 4,4'-벤질리덴비스(6-메틸-m-페닐렌)테트라이소시아네이트로 이루어진 군에서 선택되는 1종 이상의 트리이소시아네이트 화합물 또는 테트라이소시아네이트 화합물로 구성되는 것이 바람직하다.In the two-component reactive adhesive composition according to one embodiment of the present invention, the curing agent part includes a polyisocyanate compound having three or more isocyanate functional groups. The type of the polyisocyanate compound having three or more isocyanate functional groups is not particularly limited as long as it can form a urea bond by reacting with the adducted modified polyaspartic resin of the main part, and is selected from various known polyfunctional polyisocyanate compounds. It can be. The polyisocyanate compound having three or more isocyanate functional groups is lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl Octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, 1,3,5-triisocyanate cyclohexane, 1,3,5- Trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 2-(3-isocyanatepropyl)-2,6-di(isocyanatemethyl)- Bicyclo (221) heptane, 3- (3-isocyanate propyl) -2,5-di (isocyanate methyl) -bicyclo (221) heptane, 5- (2-isocyanate ethyl) -2-isocyanate methyl-3 -(3-Isocyanatepropyl)-bicyclo(221)heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo(221)heptane, 5-(2- Isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatepropyl)-bicyclo(221)-heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatepropyl)-b Cyclo(221)heptane, 1,3,5-triisocyanate methylbenzene, triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate Toluene, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-tril)tris(hexamethylene)isocyanate, 1,3,5-tris(6-isocyanato Hexyl) biuret, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, tetraisocyanatesilane and 4,4'-benzylidenebis(6-methyl-m-phenylene)tetraisocyanate It may be composed of one or more triisocyanate compounds or tetraisocyanate compounds selected from the group consisting of, and considering the various physical properties of the adhesive film formed on the two-component reactive adhesive composition (2,4,6-trioxotriazine-1 ,3,5(2H,4H,6H)-tril)tris(hexamethylene)isocyanate, 1,3,5-tris(6-isocyanatohexyl)biuret, tetraisocyanatesilane and 4,4'-benzylidene It is preferably composed of at least one triisocyanate compound or tetraisocyanate compound selected from the group consisting of bis(6-methyl-m-phenylene)tetraisocyanate.
본 발명의 바람직한 일 예에 따른 2액형 반응성 접착제 조성물은 주제부와 경화제부로 구성되고, 상기 주제부는 수산기가 변성된 폴리아스파틱 레진, 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 및 이소시아네이트기를 포함하지 않는 실란계 커플링제를 포함하고, 상기 경화제부는 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 및 이소시아네이트실란계 커플링제를 포함한다. 본 발명의 바람직한 일 예에 따른 2액형 반응성 접착제 조성물은 본 발명의 일 예에 따른 2액형 반응성 접착제 조성물과 비교할 때 주제부에 이소시아네이트기를 포함하지 않는 실란계 커플링제를 더 포함하고, 경화제부에 이소시아네이트실란계 커플링제를 더 포함한다. 따라서, 본 발명의 바람직한 일 예에 따른 2액형 반응성 접착제 조성물의 주제부 구성성분인 수산기가 변성된 폴리아스파틱 레진, 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물, 그리고 경화제부 구성성분인 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물은 본 발명의 일 예에 따른 2액형 반응성 접착제 조성물에서 설명한 내용을 참조하며, 구체적인 설명을 생략한다.A two-component reactive adhesive composition according to a preferred embodiment of the present invention is composed of a main part and a curing agent part, and the main part contains a hydroxyl group-modified polyaspartic resin, a polyisocyanate compound having two or more isocyanate functional groups, and an isocyanate group-free adhesive composition. A silane-based coupling agent is included, and the curing agent part includes a polyisocyanate compound having three or more isocyanate functional groups and an isocyanate-silane-based coupling agent. Compared to the two-component reactive adhesive composition according to one embodiment of the present invention, the two-component reactive adhesive composition according to a preferred embodiment of the present invention further includes a silane-based coupling agent not containing an isocyanate group in the main part, and isocyanate in the curing agent part. A silane-based coupling agent is further included. Therefore, the two-component reactive adhesive composition according to a preferred embodiment of the present invention includes a hydroxyl-modified polyaspartic resin, a polyisocyanate compound having two or more isocyanate functional groups, and three or more curing agent components. The polyisocyanate compound having an isocyanate functional group refers to the content described in the two-component reactive adhesive composition according to an embodiment of the present invention, and a detailed description thereof is omitted.
주제부subject part
본 발명의 바람직한 일 예에 따른 2액형 반응성 접착제 조성물에서 상기 주제부의 구성성분인 실란계 커플링제는 이소시아네이트기를 포함하지 않는데, 그 이유눈 주제부와 경화제부가 혼합되기 전에 주제부의 구성성분인 어덕트화 변성 폴리아스파틱 레진과 실란계 커플링제간의 반응에 의해 주제부의 점도 등과 같이 물성이 변하는 것을 방지하기 위함이다. 이소시아네이트기를 포함하지 않는 실란계 커플링제는 공지의 다양한 실란계 커플링제에서 선택될 수 있다. 상기 주제부의 구성성분인 실란계 커플링제는 2-(3,4 에폭시 사이클로 헥실)-에틸트리메톡시실란, 3-글리시독시트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, N-2(아미노에틸)3-아미토프로필메틸디메톡시실란, N-2(아미노에틸)3-아미노프로필트리메톡시실란, N-2(아미노에틸)3-아미노프로필트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실리-N-(1,3-디메틸뷰틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, 3-머켑토프로필메틸디메톡시실란, 3-머켑토프로필트리에톡시실란, 비닐트리클로로실란, 비닐트리(2-메톡시에톡시)실란, 비닐트리에톡시실란, 비닐트리메톡시실란 및 3-메타크릴옥시프로필트리메톡시실란으로 이루어진 군에서 선택되는 1종 이상으로 구성될 수 있다. 또한, 상기 이소시아네이트기를 포함하지 않는 실란계 커플링제는 주제부와 경화제부가 혼합되었을 때 경화제부의 구성성분인 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물과 반응할 수 있는 아미노실란계 커플링제에서 선택되는 것이 바람직하고, 예를 들어, N-2(아미노에틸)3-아미토프로필메틸디메톡시실란, N-2(아미노에틸)3-아미노프로필트리메톡시실란, N-2(아미노에틸)3-아미노프로필트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실리-N-(1,3-디메틸뷰틸리덴)프로필아민 및 N-페닐-3-아미노프로필트리메톡시실란으로 이루어진 군에서 선택되는 1종 이상으로 구성될 수 있다. In the two-component reactive adhesive composition according to a preferred embodiment of the present invention, the silane-based coupling agent, which is a component of the main component, does not contain an isocyanate group, because the adduct, which is a component of the main component, is mixed before the main component and the curing agent are mixed. This is to prevent physical properties such as viscosity of the main part from being changed due to a reaction between the modified polyaspartic resin and the silane-based coupling agent. The silane-based coupling agent not containing an isocyanate group may be selected from various known silane-based coupling agents. The silane-based coupling agent, which is a component of the main part, is 2-(3,4 epoxy cyclohexyl)-ethyltrimethoxysilane, 3-glycidoxytrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, N-2 (aminoethyl) 3-amitopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysily-N-(1,3-dimethylbutylidene)propylamine, N -Phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrichlorosilane, vinyltri(2-methoxyethoxy)silane, vinyl It may be composed of at least one selected from the group consisting of triethoxysilane, vinyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. In addition, the silane-based coupling agent not containing an isocyanate group is selected from aminosilane-based coupling agents capable of reacting with a polyisocyanate compound having 3 or more isocyanate functional groups, which is a component of the curing agent part when the main part and the curing agent part are mixed. Preferred, for example, N-2 (aminoethyl) 3-amitopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-amino Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysily-N-(1,3-dimethylbutylidene)propylamine and N-phenyl- It may be composed of one or more selected from the group consisting of 3-aminopropyltrimethoxysilane.
본 발명의 바람직한 일 예에 따른 2액형 반응성 접착제 조성물에서 상기 주제부는 주제부 전체 중량을 기준으로 수산기가 변성된 폴리아스파틱 레진 75~95 중량%, 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 3~23 중량% 및 이소시아네이트기를 포함하지 않는 실란계 커플링제 0.1~2 중량%를 포함하고, 바람직하게는 수산기가 변성된 폴리아스파틱 레진 80~90 중량%, 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 6~20 중량% 및 이소시아네이트기를 포함하지 않는 실란계 커플링제 0.2~1 중량%를 포함한다.In the two-component reactive adhesive composition according to a preferred embodiment of the present invention, the main part contains 75 to 95% by weight of a hydroxyl-modified polyaspartic resin based on the total weight of the main part, and a polyisocyanate compound having two or more isocyanate functional groups. 23% by weight and 0.1 to 2% by weight of a silane-based coupling agent not containing an isocyanate group, preferably 80 to 90% by weight of a hydroxyl group-modified polyaspartic resin, polyisocyanate compound 6 having two or more isocyanate functional groups ~20% by weight and 0.2~1% by weight of a silane-based coupling agent not containing an isocyanate group.
경화제부Curing agent part
본 발명의 바람직한 일 예에 따른 2액형 반응성 접착제 조성물에서 상기 경화제부의 구성성분인 실란계 커플링제는 이소시아네이트기를 포함하는데, 그 이유는 이소시아네이트실란계 커플링제는 경화제부의 다른 구성성분과 반응하지 않고 주제부 성분과 혼합되었을 때 주제부 성분과 반응하여 접착 도막의 접착력을 강화시킬 수 있기 때문이다. 상기 이소시아네이트실란계 커플링제는 이소시아네이트기를 1개 이상 포함하는 공지의 다양한 실란계 커플링제에서 선택될 수 있다. 예를 들어, 상기 이소시아네이트실란계 커플링제는 3-이소시아네이토프로필트리메톡시실란 또는 3-이소시아네이토프로필트리에톡시실란에서 선택되는 1종 이상으로 구성될 수 있다.In the two-component reactive adhesive composition according to a preferred embodiment of the present invention, the silane-based coupling agent, which is a component of the curing agent part, includes an isocyanate group, because the isocyanate-silane-based coupling agent does not react with other components of the curing agent part and This is because when mixed with the component, it can react with the component of the main part to strengthen the adhesive strength of the adhesive coating film. The isocyanate silane-based coupling agent may be selected from various known silane-based coupling agents containing at least one isocyanate group. For example, the isocyanatesilane-based coupling agent may be composed of at least one selected from 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
본 발명의 바람직한 일 예에 따른 2액형 반응성 접착제 조성물에서 상기 경화제부는 경화제부 전체 중량을 기준으로 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 98~99.9 중량% 및 이소시아네이트실란계 커플링제 0.1~2 중량%를 포함하고, 바람직하게는 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 99~99.8 중량% 및 이소시아네이트실란계 커플링제 0.2~1 중량%를 포함한다.In the two-component reactive adhesive composition according to a preferred embodiment of the present invention, the curing agent part contains 98 to 99.9% by weight of a polyisocyanate compound having 3 or more isocyanate functional groups and 0.1 to 2% by weight of an isocyanate silane-based coupling agent based on the total weight of the curing agent part. It includes, preferably, 99 to 99.8% by weight of a polyisocyanate compound having three or more isocyanate functional groups and 0.2 to 1% by weight of an isocyanate silane-based coupling agent.
본 발명의 일 예 또는 바람직한 일 예에 따른 2액형 반응성 접착제 조성물은 주제부와 경화제부를 소정의 비율로 혼합한 후 경화 반응에 의해 접착 도막을 형성하는 방식으로 사용된다. 상기 경화 반응에 의해 생성되는 경화물은 폴리우레아 형태에 가까우므로 본 발명의 일 예 또는 바람직한 일 예에 따른 2액형 반응성 접착제 조성물은 폴리우레아계 접착제 조성물로 분류될 수 있다. 또한, 상기 주제부와 경화제부의 혼합 비율은 주제부 내 아민 관능기 몰수 대비 경화제부 내 이소시아네이트 관능기 몰수의 비로 정의되는 이소시아네이트 지수(isocyanate index)로 나타낼 수 있다. 본 발명의 일 예 또는 바람직한 일 예에 따른 2액형 반응성 접착제 조성물에서 주제부 및 경화제부는 2액형 반응성 접착제 조성물에 형성되는 접착 도막의 물성을 고려할 때 1~2의 이소시아네이트 지수(isocyanate index) 값 범위에서 혼합 사용되는 것이 바람직하고, 1.2~1.8의 이소시아네이트 지수(isocyanate index) 값 범위에서 혼합 사용되는 것이 더 바람직하다. 본 발명의 일 예 또는 바람직한 일 예에 따른 2액형 반응성 접착제 조성물에 의해 형성되는 접착 도막은 바람직하게는 -190℃ 이하의 극저온에서 6% 이상의 연신율과 함께 상온에서 10 MPa 이상의 겹치기전단 접착강도 및 2N/㎜ 이상의 T-박리 접착강도를 가진다.The two-component reactive adhesive composition according to one embodiment or a preferred embodiment of the present invention is used in such a way that an adhesive coating film is formed by a curing reaction after mixing a main part and a curing agent part in a predetermined ratio. Since the cured product produced by the curing reaction is close to the polyurea type, the two-component reactive adhesive composition according to one or a preferred embodiment of the present invention can be classified as a polyurea-based adhesive composition. In addition, the mixing ratio of the main part and the curing agent part may be represented by an isocyanate index defined as a ratio of the number of moles of isocyanate functional groups in the curing agent part to the number of moles of amine functional groups in the main part. In the two-component reactive adhesive composition according to an example or preferred embodiment of the present invention, the main part and the curing agent are in the isocyanate index value range of 1 to 2 when considering the physical properties of the adhesive film formed in the two-component reactive adhesive composition. It is preferable to use a mixture, and it is more preferable to use a mixture in the range of an isocyanate index value of 1.2 to 1.8. The adhesive coating film formed by the two-component reactive adhesive composition according to one embodiment or a preferred embodiment of the present invention preferably has an elongation of 6% or more at a cryogenic temperature of -190 ° C. or less and a lap shear adhesive strength of 10 MPa or more at room temperature and 2N /mm or more T-peel adhesive strength.
이하, 본 발명을 실시예를 통하여 보다 구체적으로 설명한다. 다만, 하기 실시예는 본 발명의 기술적 특징을 명확하게 예시하기 위한 것일 뿐, 본 발명의 보호 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for clearly illustrating the technical features of the present invention, but do not limit the protection scope of the present invention.
1. 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부 제조1. Preparation of main part and curing agent part of two-component reactive adhesive composition for cryogenic use
하기의 [화학식 1]로 표시되는 화학 구조를 가지고 상온(약 20℃) 점도가 약 476 센티포이즈(centipoises, cPs)인 수산기가 변성된 폴리아스파틱 레진(제품명 : AK Glue UM-5000; 공급사 : 애경화학, 한국) 87g, 하기의 [화학식 2]로 표시되는 화학 구조를 가지고 3개의 이소시아네이트 관능기를 가지는 (2,4,6-트리옥소트리아진-1,3,5(2H,4H,6H)-트릴)트리스(헥사메틸렌)이소시아네이트[(2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tris(hexamethylene) isocyanate; 제품명 : AK NATE AH-2100; 공급사 : 애경화학, 한국) 13g 및 아미노실란계 커플링제인 3-아미노프로필트리메톡시실란(3-aminopropyltrimethoxysilane) 0.3g을 균일하게 혼합하여 2액형 반응성 접착제 조성물의 주제부를 제조하였다. 상기 수산기가 변성된 폴리아스파틱 레진은 폴리아스파틱 레진(Polyaspartic resin)에 존재하는 수산기에 글리시딜기가 결합되어 수산기가 변성된 것이다. 상기 주제부를 구성하는 수산기가 변성된 폴리아스파틱 레진 대부분은 3개의 이소시아네이트 관능기를 가지는 (2,4,6-트리옥소트리아진-1,3,5(2H,4H,6H)-트릴)트리스(헥사메틸렌)이소시아네이트와의 어덕트화 반응(Adduct reaction)에 의해 상온(약 20℃) 점도가 약 10,000~200,000 센티포이즈(centipoises, cPs)인 어덕트화 변성 폴리아스파틱 레진으로 존재한다.A hydroxyl-modified polyaspartic resin having a chemical structure represented by the following [Formula 1] and a viscosity of about 476 centipoise (cPs) at room temperature (about 20 ° C) (product name: AK Glue UM-5000; supplier: Aekyung Chemical, Korea) 87g, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H) having a chemical structure represented by the following [Formula 2] and having three isocyanate functional groups -tris(hexamethylene) isocyanate [(2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tris(hexamethylene) isocyanate; Product Name: AK NATE AH-2100; 13 g of supplier: Aekyung Chemical, Korea) and 0.3 g of 3-aminopropyltrimethoxysilane, an aminosilane-based coupling agent, were uniformly mixed to prepare a main part of a two-component reactive adhesive composition. The hydroxyl group-modified polyaspartic resin is a hydroxyl group-modified resin obtained by binding a glycidyl group to a hydroxyl group present in the polyaspartic resin. Most of the polyaspartic resins in which the hydroxyl groups constituting the main part are modified have three isocyanate functional groups (2,4,6-trioxotriazine-1,3,5 (2H, 4H, 6H) -tris) tris ( It exists as an adduct modified polyaspartic resin having a viscosity of about 10,000 to 200,000 centipoise (cPs) at room temperature (about 20 ° C) by an adduct reaction with hexamethylene) isocyanate.
[화학식 1][Formula 1]
상기 화학식 1에서 R은 탄소수 6~30의 선형 또는 고리형 지방족 탄화수소기, 탄소수 6~30의 방향족 탄화수소기 등에서 선택된다.In Formula 1, R is selected from a linear or cyclic aliphatic hydrocarbon group having 6 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like.
[화학식 2][Formula 2]
또한, (2,4,6-트리옥소트리아진-1,3,5(2H,4H,6H)-트릴)트리스(헥사메틸렌)이소시아네이트[(2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tris(hexamethylene) isocyanate; 제품명 : AK NATE AH-2100; 공급사 : 애경화학, 한국) 100g 및 이소시아네이트실란계 커플링제인 3-이소시아네이토프로필트리에톡시실란(3-isocyanatopropyltriethoxysilane) 0.3g을 균일하게 혼합하여 2액형 반응성 접착제 조성물의 경화제부를 제조하였다.In addition, (2,4,6-trioxotriazine-1,3,5 (2H, 4H, 6H) -tril) tris (hexamethylene) isocyanate [(2,4,6-trioxotriazine-1,3,5 (2H,4H,6H)-triyl)tris(hexamethylene) isocyanate; Product Name: AK NATE AH-2100; 100 g of supplier: Aekyung Chemical, Korea) and 0.3 g of 3-isocyanatopropyltriethoxysilane, an isocyanatesilane-based coupling agent, were uniformly mixed to prepare a curing agent part of a two-component reactive adhesive composition.
2. 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부 혼합 비율에 따른 겹치기전단 접착강도, T-박리 접착강도, 연신율 측정2. Measurement of overlap shear adhesive strength, T-peel adhesive strength, and elongation according to the mixing ratio of the main part and the curing agent part of the two-component reactive adhesive composition for cryogenic use
위에서 제조한 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부를 이소시아네이트 지수(isocyanate index)가 0.5, 1.0, 1.5, 2.0, 2.5가 되게 혼합하여 극저온용 반응성 접착제 조성물을 제조하고, 주제부 및 경화제부의 혼합 비율에 따른 겹치기전단 접착강도, T-박리 접착강도 및 연신율을 측정하였다. 상기 이소시아네이트 지수(isocyanate index)는 폴리우레탄 제조 과정에서 사용되는 지수로, 주제부 내 수산화 관능기(-OH) 몰수 대비 경화제부 내 이소시아네이트 관능기(-NCO) 몰수의 비로 정의된다. 이소시아네이트 지수(isocyanate index) 값이 1이면 양쪽 관능기의 수가 같은 경우이고, 이소시아네이트 지수(isocyanate index) 값이 1보다 작으면 수산화 관능기(-OH)의 수가 이소시아네이트 관능기(-NCO)의 수보다 많은 경우이고, 이소시아네이트 지수(isocyanate index) 값이 1보다 크면 이소시아네이트 관능기(-NCO)의 수가 수산화 관능기(-OH)의 수보다 많은 경우이다. 이론적으로는 주제부 및 경화제부를 이소시아네이트 지수(isocyanate index)가 1이 되게 혼합하는 경우 미반응물이 잔류하지 않아 접착제로서의 성능이 가장 우수할 것으로 예측되나, 실제로는 다양한 원인에 의해 최적의 접착 성능이 얻어지는 이소시아네이트 지수(isocyanate index) 값은 접착제를 구성하는 성분들의 종류 및 조성비에 따라 달라지게 된다. 본 발명에 따른 극저온용 2액형 반응성 접착제 조성물은 주제부와 경화제부를 혼합하여 사용하는 경우 하기의 화학반응식 1에서 보이는 바와 같이 주제부 내의 아민 관능기와 경화제부 내의 이소시아네이트 관능기가 반응하여 폴리우레탄 형태가 아닌 폴리우레아 형태의 경화물을 형성하게 된다.The main part and the curing agent part of the two-component reactive adhesive composition for cryogenic temperature prepared above were mixed so that the isocyanate index was 0.5, 1.0, 1.5, 2.0, and 2.5 to prepare a reactive adhesive composition for cryogenic use, and the main part and the curing agent part Lap shear adhesive strength, T-peel adhesive strength and elongation were measured according to the mixing ratio. The isocyanate index is an index used in the polyurethane manufacturing process, and is defined as the ratio of the number of moles of isocyanate functional groups (-NCO) in the curing agent part to the number of moles of hydroxyl functional groups (-OH) in the main part. If the isocyanate index value is 1, the number of functional groups on both sides is the same, and if the isocyanate index value is less than 1, the number of hydroxyl functional groups (-OH) is greater than the number of isocyanate functional groups (-NCO), , If the isocyanate index value is greater than 1, the number of isocyanate functional groups (-NCO) is greater than the number of hydroxyl functional groups (-OH). Theoretically, when the main part and the curing agent part are mixed so that the isocyanate index is 1, it is predicted that the performance as an adhesive will be the best because no unreacted material remains, but in reality, optimal adhesive performance is obtained due to various reasons. The isocyanate index value varies depending on the type and composition ratio of components constituting the adhesive. When the two-component reactive adhesive composition for cryogenic use according to the present invention is used by mixing the main part and the curing agent part, as shown in Chemical Reaction 1 below, the amine functional group in the main part and the isocyanate functional group in the curing agent part react, so that it is not a polyurethane type. A cured product in the form of polyurea is formed.
[화학반응식 1][Chemical Reaction 1]
따라서, 본 발명에서는 이소시아네이트 지수(isocyanate index)를 주제부 내 아민 관능기 몰수 대비 경화제부 내 이소시아네이트 관능기 몰수의 비로 변형하여 사용하였다. 이소시아네이트 지수(isocyanate index) 값에 따른 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부 혼합 비율을 하기 표 1에 요약하였다.Therefore, in the present invention, the isocyanate index was used by modifying the ratio of the number of moles of isocyanate functional groups in the curing agent part to the number of moles of amine functional groups in the main part. The mixing ratio of the main part and the curing agent part of the two-component reactive adhesive composition for cryogenic use according to the isocyanate index value is summarized in Table 1 below.
한편, 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부를 이소시아네이트 지수(isocyanate index) 값이 2.5가 되게 혼합하는 경우 경화 반응이 거의 진행되지 않았고, 그로 인해 후술하는 겹치기전단 접착강도, T-박리 접착강도 및 연신율을 측정할 수 없었다.On the other hand, when the main part and the curing agent part of the two-component reactive adhesive composition for cryogenic use are mixed so that the isocyanate index value is 2.5, the curing reaction hardly proceeds, and as a result, the overlap shear adhesive strength and T-peel adhesion described later Strength and elongation could not be measured.
(1) 겹치기전단 접착강도(1) Adhesion strength before overlapping
겹치기전단 접착강도 시험은 ASTM D 1002(Single-lap shear test)에 의거하여 수행하였다. 겹치기전단 접착강도 시험 조건은 다음과 같다.The lap shear adhesive strength test was performed according to ASTM D 1002 (Single-lap shear test). Lap shear adhesive strength test conditions are as follows.
* 피착재 : 440GPa급 무도금 강판 1.4mm* Substrate: 440GPa class non-plated steel sheet 1.4mm
* 표면처리 : #800 폴리싱 후 아세톤 세척* Surface treatment: Acetone washing after #800 polishing
* 접착두께 : 0.2mm* Adhesion thickness: 0.2mm
* 인장속도 : 5 mm/min* Tensile speed : 5 mm/min
* 측정온도 : 상온(약 20℃)* Measurement temperature: room temperature (about 20℃)
도 2는 본 발명의 실시예에서 제조한 극저온용 2액형 반응성 접착제 조성물의 이소시아네이트 지수(isocyanate index) 값에 따른 겹치기전단 접착강도 시험 결과를 나타낸 것이다. 도 2에서 보이는 바와 같이 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부를 이소시아네이트 지수(isocyanate index) 값이 1.2 내지 1.8이 되게 혼합하는 경우 높은 겹치기전단 접착강도를 나타냈다.Figure 2 shows the results of the overlap shear adhesive strength test according to the isocyanate index (isocyanate index) value of the two-component reactive adhesive composition for cryogenic temperature prepared in Example of the present invention. As shown in FIG. 2, when the main part and the curing agent part of the two-component reactive adhesive composition for cryogenic temperature are mixed so that the isocyanate index value is 1.2 to 1.8, high overlap shear adhesive strength was exhibited.
(2) T-박리 접착강도(2) T-peel adhesive strength
T-박리 접착강도 시험은 ASTM 1876 (T-peel test)에 의거하여 수행하였다. T-박리 접착강도 시험 조건은 다음과 같다.The T-peel adhesive strength test was performed according to ASTM 1876 (T-peel test). The T-peel adhesive strength test conditions are as follows.
* 피착재 : 340GPa급 무도금 강판 0.7mm* Substrate: 340GPa class non-plated steel sheet 0.7mm
* 표면처리 : #800 폴리싱 후 아세톤 세척* Surface treatment: Acetone washing after #800 polishing
* 접착두께 : 0.2mm* Adhesion thickness: 0.2mm
* 인장속도 : 5 mm/min* Tensile speed : 5 mm/min
* 측정온도 : 상온(약 20℃)* Measurement temperature: room temperature (about 20℃)
도 3은 본 발명의 실시예에서 제조한 극저온용 2액형 반응성 접착제 조성물의 이소시아네이트 지수(isocyanate index) 값에 따른 T-박리 접착강도 시험 결과를 나타낸 것이다. 도 3에서 보이는 바와 같이 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부를 이소시아네이트 지수(isocyanate index) 값이 1.0 내지 1.8이 되게 혼합하는 경우 높은 T-박리 접착강도를 나타냈다.Figure 3 shows the T-peel adhesive strength test results according to the isocyanate index (isocyanate index) value of the two-component reactive adhesive composition for cryogenic temperature prepared in Example of the present invention. As shown in FIG. 3, high T-peel adhesive strength was exhibited when the main part and the curing agent part of the two-component reactive adhesive composition for cryogenic temperature were mixed so that the isocyanate index value was 1.0 to 1.8.
(3) 연신율(3) Elongation
극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부를 미리 설정한 이소시아네이트 지수(isocyanate index) 값이 되게 혼합하고, 혼합한 극저온용 반응성 접착제 조성물을 몰드에 채워넣고 경화 반응을 진행시켜 ISO 527-2 규격의 1BA 치수 시편을 제조하였다. 이후, 1.3 mm/min의 인장속도를 가하면서 -190℃에서의 연신율을 측정하였다.The main part and the curing agent part of the two-component reactive adhesive composition for cryogenic use are mixed to a preset isocyanate index value, the mixed reactive adhesive composition for cryogenic use is filled into a mold, and the curing reaction proceeds to meet the ISO 527-2 standard. of 1BA dimension specimens were prepared. Then, the elongation at -190 ° C. was measured while applying a tensile rate of 1.3 mm / min.
도 4는 본 발명의 실시예에서 제조한 극저온용 2액형 반응성 접착제 조성물의 이소시아네이트 지수(isocyanate index) 값에 따른 -190℃에서의 연신율(elongation) 측정 시험 결과를 나타낸 것이다. 도 4에서 보이는 바와 같이 극저온용 2액형 반응성 접착제 조성물의 주제부 및 경화제부를 이소시아네이트 지수(isocyanate index) 값이 1.2 내지 1.8이 되게 혼합하는 경우 -190℃에서 6% 이상의 연신율(elongation)을 나타냈고, 이를 -162℃에서의 연신율(elongation)로 환산하는 경우 9% 이상이다.Figure 4 shows the elongation measurement test results at -190 ℃ according to the isocyanate index (isocyanate index) value of the two-component reactive adhesive composition for cryogenic temperature prepared in Example of the present invention. As shown in FIG. 4, when the main part and the curing agent part of the two-component reactive adhesive composition for cryogenic use are mixed so that the isocyanate index value is 1.2 to 1.8, elongation of 6% or more is exhibited at -190 ° C, When converted to elongation at -162 ° C, it is 9% or more.
이상에서와 같이 본 발명을 상기의 실시예를 통해 설명하였지만 본 발명의 보호범위가 반드시 여기에만 한정되는 것은 아니며 본 발명의 범주와 사상을 벗어나지 않는 범위 내에서 다양한 변형실시가 가능함은 물론이다. 따라서, 본 발명의 보호범위는 본 발명에 첨부된 특허청구의 범위에 속하는 모든 실시 형태를 포함하는 것으로 해석되어야 한다.As described above, although the present invention has been described through the above embodiments, the protection scope of the present invention is not necessarily limited thereto, and various modifications are possible without departing from the scope and spirit of the present invention. Accordingly, the scope of protection of the present invention should be construed to include all embodiments falling within the scope of the claims appended hereto.
Claims (16)
3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물을 포함하는 경화제부;로 구성되고,
상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진은 수산기가 이소시아네이트기에 비활성인 관능기로 변성된 것이고,
상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진의 적어도 일부는 주제부의 다른 구성성분인 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물과의 어덕트화 반응(Adduct reaction)에 의해 점도가 10,000~200,000 센티포이즈(centipoises, cPs)의 범위를 갖는 어덕트화 변성 폴리아스파틱 레진으로 존재하는 것을 특징으로 하는 2액형 반응성 접착제 조성물.
a main part including a polyaspartic resin having a modified hydroxyl group and a polyisocyanate compound having two or more isocyanate functional groups; and
A curing agent part containing a polyisocyanate compound having three or more isocyanate functional groups;
The hydroxyl group-modified polyaspartic resin, which is a component of the main part, is a hydroxyl group modified with an isocyanate group-inactive functional group,
At least a part of the polyaspartic resin having a modified hydroxyl group, which is a component of the main part, has a viscosity of 10,000 to 10,000 by an adduct reaction with a polyisocyanate compound having two or more isocyanate functional groups, which is another constituent of the main part. A two-component reactive adhesive composition, characterized in that it is present as an adducted modified polyaspartic resin having a range of 200,000 centipoises (cPs).
The two-component reactive adhesive composition according to claim 1, wherein the hydroxyl group-modified polyaspartic resin, which is a component of the main part, has a hydroxyl group modified with a functional group containing at least one glycidyl group.
The method of claim 1, wherein the polyisocyanate compound having two or more isocyanate functional groups, which is a component of the main part, is lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, 1,3,5- Triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 2-(3-isocyanatepropyl) -2,6-di(isocyanatemethyl)-bicyclo(221)heptane, 3-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 5-(2-isocyanate Ethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo(221)heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-b Cyclo(221)heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatepropyl)-bicyclo(221)-heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl -2-(3-isocyanate-propyl)-bicyclo(221)heptane, 1,3,5-triisocyanatemethylbenzene, triphenylmethane-4,4',4"-triisocyanate, 1,3,5-tri Isocyanate benzene, 2,4,6-triisocyanate toluene, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-tril)tris(hexamethylene)isocyanate, 1,3 ,5-tris(6-isocyanatohexyl)biuret, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, tetraisocyanatesilane and 4,4'-benzylidenebis( A two-component reactive adhesive composition, characterized in that it is at least one selected from the group consisting of 6-methyl-m-phenylene) tetraisocyanate.
The method of claim 1, wherein the polyisocyanate compound having three or more isocyanate functional groups, which is a component of the curing agent part, is lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, 1,3,5- Triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 2-(3-isocyanatepropyl) -2,6-di(isocyanatemethyl)-bicyclo(221)heptane, 3-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 5-(2-isocyanate Ethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo(221)heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bi Cyclo(221)heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatepropyl)-bicyclo(221)-heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl -2-(3-isocyanate-propyl)-bicyclo(221)heptane, 1,3,5-triisocyanatemethylbenzene, triphenylmethane-4,4',4"-triisocyanate, 1,3,5-tri Isocyanate benzene, 2,4,6-triisocyanate toluene, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-tril)tris(hexamethylene)isocyanate, 1,3 ,5-tris(6-isocyanatohexyl)biuret, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, tetraisocyanatesilane and 4,4'-benzylidenebis( A two-component reactive adhesive composition, characterized in that it is at least one selected from the group consisting of 6-methyl-m-phenylene) tetraisocyanate.
The method of claim 1, wherein the main part comprises 75 to 95% by weight of a hydroxyl-modified polyaspartic resin and 5 to 25% by weight of a polyisocyanate compound having two or more isocyanate functional groups based on the total weight of the main part. A liquid-type reactive adhesive composition.
상기 이소시아네이트 지수(isocyanate index)는 주제부 내 아민 관능기 몰수 대비 경화제부 내 이소시아네이트 관능기 몰수의 비로 정의되는 것을 특징으로 하는 2액형 반응성 접착제 조성물.
The method of any one of claims 1 to 5, wherein the main part and the curing agent part are mixed and used in the isocyanate index value range of 1 to 2,
The isocyanate index is a two-component reactive adhesive composition, characterized in that defined as the ratio of the number of moles of isocyanate functional groups in the curing agent to the number of moles of amine functional groups in the main part.
The method of claim 6, wherein the adhesive coating film formed after the curing reaction by mixing the main part and the curing agent part has an elongation of 6% or more at a cryogenic temperature of -190 ° C or less and an overlapping shear adhesive strength of 10 MPa or more at room temperature (20 ° C) and a T-peel adhesive strength of 2 N/mm or more.
3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 및 이소시아네이트실란계 커플링제를 포함하는 경화제부;로 구성되고,
상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진은 수산기가 이소시아네이트기에 비활성인 관능기로 변성된 것이고,
상기 주제부의 구성성분인 수산기가 변성된 폴리아스파틱 레진의 적어도 일부는 주제부의 다른 구성성분인 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물과의 어덕트화 반응(Adduct reaction)에 의해 점도가 10,000~200,000 센티포이즈(centipoises, cPs)의 범위를 갖는 어덕트화 변성 폴리아스파틱 레진으로 존재하는 것을 특징으로 하는 2액형 반응성 접착제 조성물.
a main part including a polyaspartic resin modified with a hydroxyl group, a polyisocyanate compound having two or more isocyanate functional groups, and a silane-based coupling agent not containing an isocyanate group; and
A curing agent unit comprising a polyisocyanate compound having three or more isocyanate functional groups and an isocyanate silane-based coupling agent;
The hydroxyl group-modified polyaspartic resin, which is a component of the main part, is a hydroxyl group modified with an isocyanate group-inactive functional group,
At least a part of the polyaspartic resin having a modified hydroxyl group, which is a component of the main part, has a viscosity of 10,000 to 10,000 by an adduct reaction with a polyisocyanate compound having two or more isocyanate functional groups, which is another constituent of the main part. A two-component reactive adhesive composition, characterized in that it is present as an adducted modified polyaspartic resin having a range of 200,000 centipoises (cPs).
The two-component reactive adhesive composition according to claim 8, wherein the hydroxyl group-modified polyaspartic resin, which is a component of the main part, has a hydroxyl group modified with a functional group containing at least one glycidyl group.
The method of claim 8, wherein the polyisocyanate compound having two or more isocyanate functional groups, which is a component of the main part, is lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, 1,3,5- Triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 2-(3-isocyanatepropyl) -2,6-di(isocyanatemethyl)-bicyclo(221)heptane, 3-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 5-(2-isocyanate Ethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo(221)heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-b Cyclo(221)heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatepropyl)-bicyclo(221)-heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl -2-(3-isocyanate-propyl)-bicyclo(221)heptane, 1,3,5-triisocyanatemethylbenzene, triphenylmethane-4,4',4"-triisocyanate, 1,3,5-tri Isocyanate benzene, 2,4,6-triisocyanate toluene, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-tril)tris(hexamethylene)isocyanate, 1,3 ,5-tris(6-isocyanatohexyl)biuret, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, tetraisocyanatesilane and 4,4'-benzylidenebis( A two-component reactive adhesive composition, characterized in that it is at least one selected from the group consisting of 6-methyl-m-phenylene) tetraisocyanate.
The method of claim 8, wherein the polyisocyanate compound having three or more isocyanate functional groups, which is a component of the curing agent part, is lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, 1,3,5- Triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 2-(3-isocyanatepropyl) -2,6-di(isocyanatemethyl)-bicyclo(221)heptane, 3-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo(221)heptane, 5-(2-isocyanate Ethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo(221)heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bi Cyclo(221)heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatepropyl)-bicyclo(221)-heptane, 6-(2-isocyanateethyl)-2-isocyanatemethyl -2-(3-isocyanate-propyl)-bicyclo(221)heptane, 1,3,5-triisocyanatemethylbenzene, triphenylmethane-4,4',4"-triisocyanate, 1,3,5-tri Isocyanate benzene, 2,4,6-triisocyanate toluene, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-tril)tris(hexamethylene)isocyanate, 1,3 ,5-tris(6-isocyanatohexyl)biuret, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, tetraisocyanatesilane and 4,4'-benzylidenebis( A two-component reactive adhesive composition, characterized in that it is at least one selected from the group consisting of 6-methyl-m-phenylene) tetraisocyanate.
The method of claim 8, wherein the silane-based coupling agent that does not contain an isocyanate group, which is a component of the main part, is 2-(3,4 epoxy cyclohexyl)-ethyltrimethoxysilane, 3-glycidoxytrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2(aminoethyl)3-amitopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltri Methoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysily-N-(1, 3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrichlorosilane, vinyltri (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane, characterized in that at least one member selected from the group consisting of two-component reactive adhesive composition .
The method of claim 8, wherein the isocyanate silane-based coupling agent, which is a component of the curing agent part, is characterized in that at least one selected from 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. A two-component reactive adhesive composition.
상기 주제부는 주제부 전체 중량을 기준으로 수산기가 변성된 폴리아스파틱 레진 75~95 중량%, 2개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 3~23 중량% 및 이소시아네이트기를 포함하지 않는 실란계 커플링제 0.1~2 중량%를 포함하고,
상기 경화제부는 경화제부 전체 중량을 기준으로 3개 이상의 이소시아네이트 관능기를 가지는 폴리이소시아네이트 화합물 98~99.9 중량% 및 이소시아네이트실란계 커플링제 0.1~2 중량%를 포함하는 것을 특징으로 하는 액형 반응성 접착제 조성물.
According to claim 8,
The main part includes 75 to 95% by weight of a hydroxyl-modified polyaspartic resin, 3 to 23% by weight of a polyisocyanate compound having two or more isocyanate functional groups, and 0.1% by weight of a silane-based coupling agent not containing an isocyanate group, based on the total weight of the main part. ~ 2% by weight;
The curing agent part comprises 98 to 99.9% by weight of a polyisocyanate compound having 3 or more isocyanate functional groups and 0.1 to 2% by weight of an isocyanate silane-based coupling agent based on the total weight of the curing agent part Liquid reactive adhesive composition.
상기 이소시아네이트 지수(isocyanate index)는 주제부 내 아민 관능기 몰수 대비 경화제부 내 이소시아네이트 관능기 몰수의 비로 정의되는 것을 특징으로 하는 2액형 반응성 접착제 조성물.
The method of any one of claims 8 to 14, wherein the main part and the curing agent part are mixed and used in the isocyanate index value range of 1 to 2,
The isocyanate index is a two-component reactive adhesive composition, characterized in that defined as the ratio of the number of moles of isocyanate functional groups in the curing agent to the number of moles of amine functional groups in the main part.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010090502A (en) * | 2000-03-17 | 2001-10-18 | 스타르크, 카르크 | High Functionality Polyisocyanates |
| JP3890179B2 (en) * | 2000-02-01 | 2007-03-07 | 大日精化工業株式会社 | Solvent-free adhesive |
| JP3976359B2 (en) * | 1995-05-18 | 2007-09-19 | バイエル・コーポレーシヨン | Aspartate-functional polyhydantoin prepolymer and its use in paints |
| KR20100028580A (en) * | 2007-07-03 | 2010-03-12 | 바이엘 머티리얼사이언스 아게 | Medical adhesives for surgery |
| JP2019089897A (en) * | 2017-11-13 | 2019-06-13 | 三井化学株式会社 | Use of modified polyaspartic acid-based polymer, and agent and material containing the same |
| JP6808491B2 (en) * | 2014-10-21 | 2021-01-06 | 株式会社カネカ | Curable resin composition and cured product |
-
2021
- 2021-11-29 KR KR1020210167525A patent/KR102619234B1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3976359B2 (en) * | 1995-05-18 | 2007-09-19 | バイエル・コーポレーシヨン | Aspartate-functional polyhydantoin prepolymer and its use in paints |
| JP3890179B2 (en) * | 2000-02-01 | 2007-03-07 | 大日精化工業株式会社 | Solvent-free adhesive |
| KR20010090502A (en) * | 2000-03-17 | 2001-10-18 | 스타르크, 카르크 | High Functionality Polyisocyanates |
| KR20100028580A (en) * | 2007-07-03 | 2010-03-12 | 바이엘 머티리얼사이언스 아게 | Medical adhesives for surgery |
| JP6808491B2 (en) * | 2014-10-21 | 2021-01-06 | 株式会社カネカ | Curable resin composition and cured product |
| JP2019089897A (en) * | 2017-11-13 | 2019-06-13 | 三井化学株式会社 | Use of modified polyaspartic acid-based polymer, and agent and material containing the same |
Non-Patent Citations (2)
| Title |
|---|
| 대한조선학회 VOL. 58 NO. 2 PP. 66_72 * |
| 접착 및 계면 제15권 제3호 2014년 * |
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