WO2017160016A1 - Isocyanate bloqué réticulé à basse température et à double durcissement et composition le comprenant - Google Patents

Isocyanate bloqué réticulé à basse température et à double durcissement et composition le comprenant Download PDF

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WO2017160016A1
WO2017160016A1 PCT/KR2017/002465 KR2017002465W WO2017160016A1 WO 2017160016 A1 WO2017160016 A1 WO 2017160016A1 KR 2017002465 W KR2017002465 W KR 2017002465W WO 2017160016 A1 WO2017160016 A1 WO 2017160016A1
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diisocyanate
formula
isocyanate
bis
isocyanatomethyl
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PCT/KR2017/002465
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English (en)
Korean (ko)
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박영일
노승만
송영규
김범진
김진철
남준현
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한국화학연구원
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Publication of WO2017160016A1 publication Critical patent/WO2017160016A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • 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

Definitions

  • the present invention relates to a novel block isocyanate having a double cure reactive structure with different dissociation temperatures.
  • an aliphatic, aromatic, alicyclic or aromatic aliphatic compound containing two or more isocyanate groups in its molecular structure, and an isocyanate group of the compound containing an isocyanate group is caprolactam, methylethylketoxime block isocyanates in which isocyanate groups are blocked by at least one compound selected from the group of blocking compounds including methylethylketome, dimethylpyrazole, or diethylmaloate, or contain two or more isocyanate groups in a molecular structure Of a compound having at least one polyisocyanate or at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group selected from the group consisting of dimers, trimers, or oligomers of the compounds Double-curing low-temperature crosslinkable block isocyanate prepared by blocking an isocyanate group with a radical initiator capable of generating radicals by heat such as heat or ultraviolet rays, and having both unsaturated isocyan
  • Blocked isocyanate is a blocking of isocyanate groups to prevent chemical reaction between isocyanate group (-NCO) and hydroxyl group (-OH) or amine group (-NH 2 ).
  • Block isocyanates can be used in the production of liquid compositions, and block isocyanates can be used in organic solvents or aqueous systems, and crosslinking reactions of isocyanate groups and hydroxyl groups are widely used as paints, adhesives, coatings, and the like throughout the industry.
  • Laromer® LR 9000 developed by BASF, has a double bond of acrylate group and pre-isocyanate group at the same time, enabling dual curing through radical and urethane reactions to increase the degree of hardening and scratch resistance. A high coating film can be realized.
  • Laromer @ LR 9000 can be applied only as a two-component system due to pre-isocyanate, and requires the storage of a curing agent or a reaction initiator separately from the matrix resin, and has a disadvantage of poor storage stability.
  • Japanese Patent Publication JP4879557B which is a conventional technique for such a block isocyanate compound, discloses a method for producing a block isocyanate compound using a pyrazole compound, and in Korean Patent Application Publication No. KR2007-0064857A, a tire cord adhesive composition comprising a blocked isocyanate compound is disclosed.
  • US Patent No. 4,997,900 describes a powder coating composition using block diisocyanate using acetone oxime.
  • the existing isocyanate blocking group requires an excessive amount of high temperature energy due to its high chemical dissociation temperature, and the blocking group does not participate in the reaction when deblocked, becomes a volatile organic compound (VOC), and volatilizes to the atmosphere.
  • VOC volatile organic compound
  • the new double-curable block isocyanate system that can be cured at low temperatures, can compensate for the disadvantages of the conventional two-component system, and simultaneously reduce the harmful chemical VOC, saves energy and reduces carbon dioxide in the coating, paint, and adhesive technologies. It is expected to be of great help in emission reduction.
  • the present invention was developed to solve the above problems, and an object of the present invention is to provide a novel block isocyanate capable of curing at low temperature and reducing VOC, which is a hazardous chemical.
  • an aliphatic, aromatic, alicyclic, or aliphatic compound is a compound containing two or more isocyanate groups in its molecular structure, and an isocyanate group of the compound containing an isocyanate group is caprolactam, methylethylke Block isocyanates in which isocyanate groups are blocked by at least one compound selected from the group of isocyanate blocking compounds including methylethylketome, dimethylpyrazole, or diethylmaloate, or two or more isocyanates in a molecular structure
  • One or more polyisocyanates or one or more isocyanate-reactive groups and one or more free radically polymerizable impurities selected from the group consisting of dimers, trimers, or oligomers of compounds containing groups Group and an isocyanate group of a compound having an object to provide a low-temperature cross-linkable blocked isocyanate is produced by dual cure blocked radical initiator capable of generating a radical by light, such
  • a monomer or oligomer having an ethylenic or acrylic unsaturated double bond or hydroxyl group which can be mixed with the block isocyanate according to the present invention as a composition which can be crosslinked at low temperature, or a monomer having an unsaturated double bond and a hydroxyl group at the same time, or It is intended to provide a low temperature crosslinkable composition comprising an oligomer.
  • the compound of formula A and a polyisocyanate or at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group characterized in that it is prepared through the urea bond formation reaction It provides a low temperature crosslinkable block isocyanate capable of double curing.
  • R 1 , R 2 , R 3, R 4 in Formula A together with the carbon to which they are attached, form a normal alkyl, a cyclic ring, or a C 3 -C 12 cycloalkyl or aromatic.
  • the compound of Formula A may preferably be the following Formula 1 or Formula 2.
  • the polyisocyanate compound may contain two or more isocyanate groups in the molecular structure as aliphatic, aromatic, alicyclic, or aromatic, aliphatic compounds. More preferably, it may contain 2-6 isocyanate groups.
  • the present invention provides a low-temperature crosslinkable block isocyanate capable of double curing having a chemical structure of formula (B).
  • R 1 , R 2 , R 3 , R 4 independently forms a normal alkyl, a cyclic ring, or a cycloalkyl of C 3 -C 12 with the carbon to which it is attached or aromatic, n is an integer of 1 or more, X is an aliphatic, aromatic, alicyclic of C 2 -C 30 Or C2-C40 aliphatic, aromatic, cycloaliphatic, or aliphatic aliphatic or which contains one or more free radically polymerizable unsaturated groups.
  • the compound of formula B is an aliphatic, aromatic, cycloaliphatic, or aliphatic polyisocyanate of C2-C30 or at least one isocyanate reactive group and at least one free radical polymerization. It may be prepared through a urea bond formation reaction between a compound having a unsaturated unsaturated group and a compound of Formula (A).
  • X is C2-C40 aliphatic, aromatic, cycloaliphatic, or aliphatic polyisocyanate or C2-C40 aliphatic, aromatic containing at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group, It may be derived from an alicyclic or aromatic aliphatic compound.
  • the compound having a polyisocyanate or at least one free radical polymerizable unsaturated group includes an isocyanate group with caprolactam, methylethylketome, dimethylpyrazole, or diethylmaloate. It may be a block isocyanate in which isocyanate group is blocked by at least one compound selected from the group of isocyanate blocking compounds.
  • the polyisocyanate may be at least one selected from the group consisting of dimers, trimers, or oligomers of compounds containing two or more isocyanate groups in a molecular structure.
  • the low-temperature crosslinkable composition capable of double curing in the present invention is the double-curable low-temperature crosslinkable block isocyanate according to the present invention; And it may include a monomer or oligomer having an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time.
  • the low-temperature crosslinkable composition is a low-crosslinkable block isocyanate capable of double curing according to the present invention; And monomers or oligomers containing only one of unsaturated double bonds or hydroxyl groups.
  • the new block isocyanate of the double-curing reactive structure having different dissociation temperatures has a fast coating process by first forming a curing reaction at the coating surface and the interface as the blocking group dissociable at low temperature dissociates. Since the crosslinking in the interior gradually increases in temperature, the diblocked pre-isocyanate proceeds, so it is very useful in coating, coating, and adhesion technology requiring rapid surface hardening in automobile mass production process. There is this.
  • the new block isocyanate having a double curing reaction type structure having different dissociation temperatures is mixed with monomers or oligomers having an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time to form a crosslinking reaction with both the unsaturated double bond and the hydroxyl group. It is possible to double cure. In addition, since it can be cured even when mixed with monomers or oligomers containing only one of unsaturated double bonds or hydroxyl groups, it can be utilized in various coatings, coatings, and adhesion techniques.
  • Figure 1 shows the FT-IR spectrum of the block isocyanate through the reaction of the radical initiator and the diisocyanate compound according to an embodiment of the present invention.
  • Figure 2 shows the FT-IR spectrum of the block isocyanate through the reaction of the diisocyanate compound containing a radical initiator and an acrylic ester group according to an embodiment of the present invention.
  • Figure 3 schematically shows a rheology analysis system for the preparation of low-temperature cross-linkable composition pre-mixture according to an embodiment of the present invention and the curing behavior analysis using the same.
  • FIG. 5 schematically illustrates a preparation example of a low-temperature crosslinkable composition pre-mixture according to an embodiment of the present invention, and a rheology analysis system for analyzing hardening behavior using the same.
  • polyisocyanate means an isocyanate having at least two isocyanate groups in its molecular structure. More specifically, an aliphatic, aromatic, alicyclic or aromatic aliphatic compound means containing two to six isocyanate groups in the molecular structure.
  • the isocyanate group is blocked by at least one compound selected from the group of isocyanate blocking compounds including caprolactam, methylethylketome, dimethylpyrazole, or diethylmaloate. May be blocked isocyanate.
  • I mean. It is also meant to include compounds containing 2 to 6 isocyanate groups in the molecular structure as dimers, symmetric or asymmetric trimers, or oligomers of aliphatic diisocyanates. In particular, in the case of a trimer, it may decompose
  • Compounds having at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group include at least one isocyanate reactive group, vinyl group, acryl group, meta group in the molecular structure of C2-C40 aliphatic, aromatic, cycloaliphatic, or aliphatic compound.
  • It is a monomer or oligomer which has 1 or more of free radically polymerizable unsaturated groups, such as a vinyl group, an acryl group, and methacryl group. More preferably, it is a urethane acrylate or urethane methacrylate oligomer which has an isocyanate group in a sock end, and has an acryl group or a methacrylate group in the side chain of a molecular chain.
  • a linking chemical bond in the isocyanate group is blocked by the reaction of the isocyanate group and the radical initiator of the compound having the corresponding polyisocyanate or at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group. It refers to the molecular structure of the compound having the corresponding polyisocyanate or at least one free radical polymerizable unsaturated group except for the urea group.
  • the radical initiator includes both a thermal initiator which generates radicals by heat and a photo initiator which generates radicals by light such as ultraviolet rays.
  • a thermal initiator is more preferable, you may mix and use a thermal initiator and a photoinitiator as a radical initiator as needed.
  • TRI thermal radical initiator
  • the compound of Formula A and a polyisocyanate or at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group can be prepared through a urea bond formation reaction.
  • R 1 , R 2 , R 3, R 4 in Formula A together with the carbon to which they are attached, form a normal alkyl, a cyclic ring, or a C 3 -C 12 cycloalkyl or aromatic.
  • the compound of Formula A may preferably be the following Formula 1 or Formula 2.
  • the polyisocyanate compound may contain two or more isocyanate groups in the molecular structure as aliphatic, aromatic, alicyclic, or aromatic, aliphatic compounds. More preferably, it may contain 2-6 isocyanate groups.
  • the polyisocyanate compound is an aliphatic, aromatic, alicyclic, or aromatic aliphatic compound containing two or more isocyanate groups in a molecular structure
  • the isocyanate At least one compound selected from the group of isocyanate blocking compounds comprising an isocyanate group of a compound containing a group including caprolactam, methylethylketome, dimethylpyrazole, or diethylmaloate Or a diisomer, trimer, or oligomer of a blocked isocyanate, or a compound containing two or more isocyanate groups in its molecular structure.
  • isocyanate blocking compounds comprising an isocyanate group of a compound containing a group including caprolactam, methylethylketome, dimethylpyrazole, or diethylmaloate Or a diisomer, trimer, or oligomer of a blocked isocyanate, or a compound containing two or more isocyanate groups in its
  • the polyisocyanate compound is ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonnamethylene Diisocyanate, dodecamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-di Isocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate , Bis (2-isocyanateethyl) fuma
  • the polyisocyanate compound is thiodiethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithio dimethyl diisocyanate, dithi At least one sulfur-containing aliphatic isocyanate or diphenyl sulfide-2,4'-diisocyanate selected from the group consisting of diethyl diisocyanate, dithio propyl diisocyanate, dicyclohexyl sulfide-4,4'- diisocyanate Phenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanato dibenzyl thioether, bis (4-isocyanatomethyl benzene) sulfide, 4, 4'-me
  • the polyisocyanate compound is a dimer, trimer, or oligomer of aliphatic isocyanate or aliphatic isocyanate and alcohol, It may be a compound containing two or more isocyanate groups in the molecule after reaction with an organic acid or organic amine.
  • polyisocyanates include the following Formula C, a trimer isocyanate containing a biuret group derived from hexamethylene diisocyanate (HDI), a molecular structure, an asymmetric timer Formula (E) containing an iminooxadiazinedione group, Formula (F) containing an allophanate group in a molecular structure, dimer, uretidine-2,4-dione (uretidine-2) It may be an isocyanate of the formula (G) containing a, 4-dione) group in the molecular structure.
  • Formula C a trimer isocyanate containing a biuret group derived from hexamethylene diisocyanate (HDI), a molecular structure, an asymmetric timer Formula (E) containing an iminooxadiazinedione group, Formula (F) containing an allophanate group in a molecular structure, dimer, uretidine-2,4-dione (
  • the polyisocyanate compound is 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI) , 2,6-tolylene diisocyanate, 4,4'-diphenylene methane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, ethyl phenylene diisocyanate, 4,4'- diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, naphthalene diisocyanate, methyl naphthalene diisocyanate, triazine diisocyanate, bis (Isocyanatophenyl) ethylene, 3,3'-dimethoxybiphen
  • the polyisocyanate compound is diphenyl sulfone-4,4'-diisocyanate, diphenyl sulfone-3,3'-diisocyanate, benzidinesulfone 4, 4'-diisocyanate, diphenylmethane sulfone-4,4'-diisocyanate, 4-methyl diphenylmethane sulfone-2,4'-diisocyanate, 4,4'-dimethoxy diphenyl sulfone-3,3 ' -Diisocyanate, 3,3'-dimethoxy-4,4'- diisocyanate dibenzyl sulfone, 4,4'-dimethyldiphenylsulfone-3,3'- diisocyanate, 4,4'-di-tert- With butyl diphenyl sulfone-3,3'-diisocyanate, 4,4'-di-tert- With butyl diphen
  • the polyisocyanate compound is isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), cyclohexylene diisocyanate, Methylcyclohexylene diisocyanate, bis (2-isocyanateethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, 2 , 2-dimethyl dicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanato propyl ) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane
  • IPDI isophorone diisocyanate
  • the polyisocyanate compound is 1,3-bis (isocyanatomethyl) benzene (m-xylene diisocyanate, m-XDI), 1,4-bis (Isocyanatomethyl) benzene (p-xylene diisocyanate, p-XDI), 1,3-bis (2-isocyanato propan-2-yl) benzene (m-tetramethyl xylene diisocyanate, m-TMXDI) , 1,4-bis (2-isocyanato propan-2-yl) benzene (p-tetramethyl xylene diisocyanate, p-TMXDI), 1,3-bis (isocyanatomethyl) -4-methylbenzene, 1,3-bis (isocyanatomethyl) -4-ethylbenzene, 1,3-bis (isocyanatomethyl) -5-methylbenzene
  • the compound having at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group is an aliphatic, aromatic, cycloaliphatic, or aromatic aliphatic compound of C2-C40.
  • free radical polymerizable unsaturated group such as vinyl group, acrylic group, methacryl group in the molecular structure, preferably isocyanate functionalized unsaturated acrylic ester, unsaturated urethane acrylate, or It is a monomer or oligomer which has two isocyanate groups in the sock end of a molecular chain, and has one or more
  • it is a urethane acrylate or urethane methacrylate oligomer which has an isocyanate group in a sock end, and has an acryl group or a methacrylate group in the side chain of a molecular chain.
  • the compound having at least one isocyanate-reactive group and at least one free radical polymerizable unsaturated group may have a chemical structure of the formula (H).
  • n is an integer of 1 to 5.
  • the present invention provides a low-temperature crosslinkable block isocyanate capable of double curing having a chemical structure of the formula (B) to solve the above problems.
  • R 1 , R 2 , R 3 , R 4 independently with the carbon to which they are attached, forms a normal alkyl, a cyclic ring, or a cycloalkyl or aromatic of C 3 -C 12, n is an integer of 1 or more, and X is an aliphatic, aromatic, alicyclic of C 2 -C 30 Or C2-C30 aliphatic, aromatic, cycloaliphatic, or aliphatic aliphatic or which contains one or more free radically polymerizable unsaturated groups.
  • Formula B is prepared through a urea bond formation reaction of a compound of Formula A and a polyisocyanate, wherein X in Formula B is ethylene diisocyanate, Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diis
  • the formula B is prepared through the urea bond formation reaction of the compound of formula A and the polyisocyanate compound, the polyisocyanate compound is thiodi Ethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, dithio dimethyl diisocyanate, dithio diethyl diisocyanate, dithio propyl diisocyanate, dicyclohexyl sulfide-4,4'-di At least one sulfur-containing aliphatic isocyanate or diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4 'selected from the group consisting of isocyanates
  • the formula B is prepared through a urea bond formation reaction of the compound of formula A and the polyisocyanate compound, the polyisocyanate compound is an aliphatic isocyanate. It may be a dimer, trimer, or oligomer, or a compound containing two or more isocyanate groups in a molecule after reaction with an aliphatic isocyanate with an alcohol, an organic acid or an organic amine.
  • polyisocyanates include the following Formula C, a trimer isocyanate containing a biuret group derived from hexamethylene diisocyanate (HDI), a molecular structure, an asymmetric timer Formula (E) containing an iminooxadiazinedione group, Formula (F) containing an allophanate group in a molecular structure, dimer, uretidine-2,4-dione (uretidine-2) It may be an isocyanate of the formula (G) containing a, 4-dione) group in the molecular structure.
  • Formula C a trimer isocyanate containing a biuret group derived from hexamethylene diisocyanate (HDI), a molecular structure, an asymmetric timer Formula (E) containing an iminooxadiazinedione group, Formula (F) containing an allophanate group in a molecular structure, dimer, uretidine-2,4-dione (
  • the formula B is prepared through a urea bond formation reaction of a compound of formula A and a polyisocyanate, wherein X in Formula B is 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-diphenylene methane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, ethyl phenylene diisocyanate, 4,4'- diisocyanate biphenyl, 3,3'-dimethyl-4,4'- diisocyanate biphenyl, 3,3'-dimethyl-4 , 4'- diisocyanate diphenylmethane, naphthalene diisocyanate, methyl naphthalene diisocyanate, tri
  • the formula B is prepared through a urea bond formation reaction of a compound of formula A and a polyisocyanate, wherein X in formula B is diphenyl sulfone- 4,4'-diisocyanate, diphenyl sulfone-3,3'-diisocyanate, benzidine thruhorn 4,4'-diisocyanate, diphenylmethane sulfone-4,4'- diisocyanate, 4-methyl diphenylmethane Sulfone-2,4'-diisocyanate, 4,4'-dimethoxy diphenyl sulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzyl sulfone, 4, 4'-dimethyldiphenylsulfone-3,3'-diisocyanate, 4, 4'-dimethyldiphenylsulfone-3,3'-diisocyan
  • Chemical Formula B is prepared through a urea bond formation reaction of a compound of Chemical Formula A and a polyisocyanate, wherein X in Chemical Formula B is isophorone diisocyanate.
  • IPDI 4,4'-dicyclohexylmethane diisocyanate
  • HMDI 4,4'-dicyclohexylmethane diisocyanate
  • cyclohexylene diisocyanate methylcyclohexylene diisocyanate, bis (2-isocyanate ethyl) -4-cyclohexene-1,2-dica Reboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, 2,2-dimethyl dicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) Pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanato propyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isosia Natomethyl-3- (3-iso Anatopropyl
  • IPDI isophorone diisocyanate
  • HMDI 4,4'-dicyclohexylmethane diisocyanate
  • 1,3, -bis (6-isocyanato hexyl) -uretidine-2, 4-dione, 1,3,5-tris (6-isocyanato hexyl) isocyanurate may be derived.
  • the formula B is prepared through a urea bond formation reaction of a compound of formula A and a polyisocyanate, wherein X in Formula B is 1,3- Bis (isocyanatomethyl) benzene (m-xylene diisocyanate, m-XDI), 1,4-bis (isocyanatomethyl) benzene (p-xylene diisocyanate, p-XDI), 1,3-bis ( 2-isocyanato propan-2-yl) benzene (m-tetramethyl xylene diisocyanate, m-TMXDI), 1,4-bis (2-isocyanato propan-2-yl) benzene (p-tetramethyl xylene Diisocyanate, p-TMXDI), 1,3-bis (isocyanatomethyl) -4-methylbenzene, 1,3-bis (isocyanatomethyl) -4-methylbenzene, 1,3-bis (isocyanatomethyl)
  • the formula (B) is a urea bond formation reaction of a compound having a compound of Formula (A) with at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group.
  • X is represented by the formula B is one or more isocyanate-reactive groups in the molecular structure of the aliphatic, aromatic, cycloaliphatic, or aliphatic compound of C2-C40 free radical polymerizable unsaturated, such as vinyl, acrylic, methacryl group It may be derived from a compound having at least one group.
  • the at least two may be derived from monomers or oligomers. More preferably, it may be derived from a urethane acrylate or urethane methacrylate monomer or oligomer having an isocyanate group in the sock end and an acrylic group or methacrylate group in the side chain of the molecular chain.
  • the low temperature crosslinkable block isocyanate according to the present invention may have a chemical structure of any one of the following Chemical Formulas 3 to 17.
  • n is an integer of 1 to 5.
  • the present invention is a low-temperature cross-linked block isocyanate capable of double curing; And it provides a low-temperature cross-linkable composition comprising a monomer or oligomer having an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time.
  • the monomers or oligomers that can be used in the low-temperature crosslinking composition according to the present invention may be any monomer or oligomer having an ethylenic or acrylic unsaturated double bond or a hydroxyl group in the divalent structure, but ethylene-based for effective low-temperature crosslinking. Or it is more preferable to have an acryl-type unsaturated double bond and a hydroxyl group simultaneously.
  • Such monomers or oligomers can be used as the main resin of the low-temperature crosslinkable composition, wherein the block isocyanates according to the invention can act simultaneously as initiators for generating radicals and as crosslinkers for effective crosslinking.
  • the monomer or oligomer having an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time can be used as the main resin (main resin) and may have a chemical structure of the formula (18).
  • the low-temperature crosslinkable composition according to the present invention may include various additives according to specific uses, such as reactive diluents such as diacrylate and inorganic fillers, if necessary.
  • the reactive diluent according to one embodiment of the present invention may be 1,6-hexanediol diacrylate.
  • the compound of Formula 1 which is a thermal radical initiator (TRI) according to one embodiment of the present invention, may be prepared according to Scheme 1 below.
  • the compound of formula 2 which is a thermal radical initiator (TRI) according to one embodiment of the present invention, may be prepared according to Scheme 2 below.
  • Compound of Formula 6 can be prepared through the reaction of the compound of ⁇ Formula 2> and isophorone diisocyanate, except that using the compound of ⁇ Formula 2> is prepared Same as Example 5.
  • Compound of Formula 8 is a compound of Formula 2 and 1,3, -bis (6-isocyanato hexyl) -uretidine-2,4-dione of ⁇ Formula G> It was prepared in the same manner as in Preparation Example 7 through the reaction with.
  • Compound of Formula 10 is prepared through the compound of ⁇ Formula 2> and ⁇ 1,3,5-tris (6-isocyanato hexyl) isocyanurate of the formula (D) It prepared in the same manner as 9.
  • Compound of formula 11 is a compound of formula (1) and 1,2,4-tris (6-isocyanato hexyl) iminooxadiazinedione of the formula (E) and the following scheme It was prepared according to 8, the preparation method was prepared in the same manner as in Preparation Example 9.
  • Compounds of Formula 13 to Formula 16 according to an embodiment of the present invention is a biuret, an allophanate compound of the compounds of ⁇ Formula 1>, ⁇ Formula 2> and the corresponding hexamethylene diisocyanate It was prepared through the reaction with C>, ⁇ Formula F>, the preparation method was carried out under the same conditions as in Preparation Examples 3 to 12.
  • n is an integer of 1 to 5.
  • the compound of Chemical Formula 9 prepared according to Preparation Example 9 was used as the low temperature crosslinkable block isocyanate capable of double curing.
  • a pre-mixture was prepared using 1,6-hexanediol diacrylate as a reactive diluent and a monomer having an acrylic unsaturated double bond and a hydroxyl group (DCR-4274: Chemical Formula 18) and a rotational rheometer (MCR). -301, Anton Paar, Austria) was used to measure the storage modulus with curing temperature and time.
  • the embodiment according to the present invention can significantly accelerate the curing time when compared to the comparative example, and thus can provide surface dryness and curing quickly, thereby minimizing contact with various dusts and deterioration of physical properties in process conditions.
  • a higher degree of polymer crosslinking as a double curing to give a high modulus there is an advantage that can provide a relatively excellent properties to the mechanical / chemical properties applied from the outside.
  • the low temperature crosslinkable block isocyanate As the low temperature crosslinkable block isocyanate, a compound of Formula 17 prepared according to Preparation Example 17 is used, and an acrylic unsaturated double A pre-mixture was prepared using 1,6-hexanediol diacrylate as a reactive diluent and a monomer having a bond and a hydroxyl group at the same time (DCR-4274: Formula 18), and a rotation rheometer (MCR-301, Anton Paar, Austria) was used to measure the storage modulus with curing temperature and time.
  • DCR-4274 1,6-hexanediol diacrylate
  • the embodiment according to the present invention can significantly accelerate the curing time compared to the comparative example and thereby can provide a surface hardness and curing quickly to minimize contact with various dusts and property degradation under process conditions, double By providing a higher degree of polymer crosslinking as a hardening to give a high modulus there is an advantage that can provide relatively excellent properties to the mechanical / chemical properties applied from the outside.
  • the conventional Laromer 9000 is applied to a two-component system compared to the present invention can maintain the storage stability can be used as a one-component and easy to use it can be applied to various fields.
  • the block isocyanate and the composition including the same according to the present invention exhibits a new block isocyanate having a double curing reaction structure having different dissociation temperatures, and undergoes a curing reaction at the surface and the interface while the blocking group capable of dissociating at low temperature is dissociated. It can be formed first and can be used for rapid coating process. After that, the crosslinking in the inside will proceed with diblocked pre-isocyanate as the temperature rises. This is very big.

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Abstract

La présente invention concerne un nouvel isocyanate bloqué présentant une structure de type à double réaction de durcissement présentant des températures de dissociation différentes, et plus particulièrement un isocyanate bloqué réticulé à basse température et à durcissement double formé à l'aide d'un initiateur radicalaire pour bloquer un groupe isocyanate d'un composé polyisocyanate qui est un diisocyanate aliphatique, aromatique, alicyclique ou araliphatique, et une composition réticulée à basse température qui comprend l'isocyanate bloqué et un oligomère ou un monomère présentant simultanément un groupe hydroxyle et une double liaison insaturée éthylénique ou acrylique.
PCT/KR2017/002465 2016-03-14 2017-03-07 Isocyanate bloqué réticulé à basse température et à double durcissement et composition le comprenant WO2017160016A1 (fr)

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KR10-2016-0030458 2016-03-14

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CN110204678A (zh) * 2019-05-21 2019-09-06 中国船舶重工集团公司第七二五研究所 一种基于二硫键交换反应的聚二甲基硅氧烷自修复材料及其制备方法
WO2023190410A1 (fr) * 2022-03-28 2023-10-05 三菱ケミカル株式会社 Composé, composition polymérisable, produit durci, filtre coloré, paroi de séparation et dispositif d'affichage d'image

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KR102147655B1 (ko) * 2019-10-14 2020-08-25 한국화학연구원 저온경화용 조성물, 이를 이용한 가교결합된 수지 및 이를 포함하는 제품
KR102480995B1 (ko) * 2021-05-12 2022-12-22 한국화학연구원 저온경화반응 제어형 자동차용 일액형 클리어코트 조성물
KR102643078B1 (ko) 2021-10-14 2024-02-29 한국화학연구원 라디칼 반응이 가능한 저온가교형 피라졸계 블록이소시아네이트 및 이를 포함하는 조성물

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JP2004523636A (ja) * 2001-03-29 2004-08-05 ビーエーエスエフ　コーティングス　アクチェンゲゼルシャフト ポリウレタンで変性されたコポリマー、その製造方法およびその使用
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WO2023190410A1 (fr) * 2022-03-28 2023-10-05 三菱ケミカル株式会社 Composé, composition polymérisable, produit durci, filtre coloré, paroi de séparation et dispositif d'affichage d'image

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