KR20170106824A - Dual cross-linkable low temperature cure blocked isocyanates and composition comprising the same - Google Patents
Dual cross-linkable low temperature cure blocked isocyanates and composition comprising the same Download PDFInfo
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- KR20170106824A KR20170106824A KR1020160030458A KR20160030458A KR20170106824A KR 20170106824 A KR20170106824 A KR 20170106824A KR 1020160030458 A KR1020160030458 A KR 1020160030458A KR 20160030458 A KR20160030458 A KR 20160030458A KR 20170106824 A KR20170106824 A KR 20170106824A
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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
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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
- C08G18/80—Masked polyisocyanates
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- 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
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Abstract
The present invention relates to a novel block isocyanate of a bifunctional reaction type structure having different dissociation temperatures, and more particularly to an isocyanate group of a polyisocyanate compound which is an aliphatic, aromatic, alicyclic or aromatic aliphatic diisocyanate as a radical initiator Crosslinkable block isocyanate prepared by block polymerization and a monomer or oligomer having both block isocyanate and an ethylenic or acrylic unsaturated double bond and hydroxyl group at the same time. The block isocyanate according to the present invention can be rapidly worked by forming a curing reaction at the surface and interface first by dissociating the blocking group capable of dissociation at a low temperature. Thereafter, cross-linking inside the block isocyanate is prebonded And therefore, it is very useful in coatings, paints, and adhesive technologies that require surface hardening at the process level.
Description
The present invention is directed to a novel block isocyanate of a dual cure reaction type structure having dissociation temperatures different from each other.
More specifically, a double-cured product prepared by blocking an isocyanate group of a polyisocyanate compound which is an aliphatic, aromatic, alicyclic or aromatic aliphatic diisocyanate with a radical initiator capable of generating a radical by heat or ultraviolet light Crosslinkable block isocyanate, and a low-temperature crosslinkable composition comprising such a block or isocyanate and a monomer or oligomer having both an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time.
Blocked isocyanate is blocked by an isocyanate group to prevent the reaction between an isocyanate group (-NCO) and a hydroxyl group (-OH) or an amine group (-NH 2 ) to produce a one-part coating composition . Blocked isocyanates can be used in organic solvents and waterborne systems, and cross-linking reactions of isocyanate groups and hydroxyl groups are widely used in industry as paints, adhesives, coatings, and the like.
In recent years, automobile steel materials have been replaced by plastic materials, which are lightweight materials, in order to address climate change and environmental problems such as carbon dioxide reduction and fuel efficiency improvement. The mass production of automobiles using such lightweight plastic materials calls for a revolutionary change in the chemical structures of coatings, coatings and adhesives used as commercial products in existing production lines and the reaction processes that can control them. Especially, the conventional high temperature curing process is a low temperature curing process due to the problems of denaturation of plastic materials and various color matching. In addition, automotive coating systems based on conventional high-temperature curing type crosslinking methods are required to avoid the emission of a large amount of volatile organic compounds (VOCs) and harmful substances and to control the emission of carbon dioxide due to enormous energy consumption, which is the main cause of warming In advanced overseas countries, it is necessary to have a source technology for automotive coating system based on environment friendly low temperature curing technology to cope with new climate change as a main technology to replace this.
Blocking groups used in conventional block isocyanates have been used mainly for oxime, caprolactams, and pyrazole. Japanese Patent Publication JP 4879557B discloses a method for producing a block isocyanate compound using a pyrazole compound, and Korean Patent Publication No. KR2007-0064857A discloses an adhesive composition for a tire cord containing a blocked isocyanate compound And U.S. Patent No. US1988-290157A discloses a powder coating composition using a block diisocyanate using acetone oxime.
However, existing blocking groups have high dissociation temperature and require excessive high temperature energy. When the blocking group is deblocked, it becomes volatile organic compounds (VOC) instead of participating in the reaction, . Therefore, there is a need for a new block isocyanate system capable of curing reaction at low temperatures and simultaneously reducing VOC, a toxic chemical.
The present invention has been developed in order to solve the above problems, and it is an object of the present invention to provide a novel block isocyanate capable of curing reaction at a low temperature and simultaneously reducing VOC which is a harmful chemical substance.
In the present invention, the isocyanate group of an aliphatic, aromatic, alicyclic or aromatic aliphatic diisocyanate compound is blocked with a radical initiator capable of generating radicals by heat or ultraviolet light, Crosslinkable block isocyanate capable of crosslinking at low temperature.
In the present invention, a composition capable of crosslinking at a low temperature is used as 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, or a monomer having an unsaturated double bond and a hydroxyl group simultaneously To provide a low temperature crosslinkable composition comprising an oligomer.
The present invention provides a low temperature crosslinkable block isocyanate capable of being cured by a urea bond formation reaction between a compound represented by the following formula (A) and a polyisocyanate compound.
≪ Formula (A)
Wherein R 1 , R 2 , R 3 and R 4 are independently alkyl or together with the carbon to which they are attached form a cyclic ring or cycloalkyl of C3-C12.
In the present invention, the compound of formula (A) may preferably be represented by the following formula (1) or (2).
≪ Formula 1 >
(2)
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound may contain two or more isocyanate groups in the molecular structure as an aliphatic, aromatic, alicyclic, or aromatic, aliphatic compound. More preferably 2 to 6 isocyanate groups.
Also, the present invention provides a low temperature crosslinkable block isocyanate capable of being cured with a chemical structure represented by the following formula (B).
≪ Formula B >
In formula (B), R 1 , R 2 , R 3 , R 4 is independently alkyl or forms a cyclic ring with the carbon to which they are attached or is cycloalkyl of C3-C12, n is an integer of 2 or greater, X is a C2-C30 aliphatic, aromatic, cycloaliphatic, or aromatic Aliphatic.
In the low-temperature crosslinkable block isocyanate according to the present invention, the compound of the formula (B) is a urea bond between a C2-C30 aliphatic, aromatic, alicyclic or aromatic aliphatic polyisocyanate and a compound of the formula (A) Forming reaction. That is, in the above formula (B), X may be derived from a C2-C30 aliphatic, aromatic, alicyclic or aromatic aliphatic polyisocyanate.
In the present invention, the low-temperature crosslinkable composition capable of being cured by double-curing comprises the double-curable low-temperature crosslinkable block isocyanate according to the present invention; And a monomer or oligomer having both an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time.
In the present invention, the low-temperature crosslinkable composition comprises the double-curable low-temperature crosslinkable block isocyanate according to the present invention; And monomers or oligomers containing only either an unsaturated double bond or a hydroxyl group.
As described above, the new block isocyanate having a double-cure reaction structure having different dissociation temperatures according to the present invention dissociates the blocking group capable of dissociation at a low temperature and forms a hardening reaction at the surface and interface first, And since the internal cross-linking proceeds with the progress of the deblocked pre-isocyanate as the temperature rises, it is very advantageous in application to coatings, paints, and bonding technologies that require rapid surface hardening in the automobile mass production process .
In addition, a novel block isocyanate having a double-cure reaction structure having a dissociation temperature different from each other is prepared by mixing a monomer or an oligomer having both an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time to form a crosslinking reaction with both unsaturated double bonds and hydroxyl groups Double curing is possible. Also, it can be cured by mixing with a monomer or an oligomer containing only either an unsaturated double bond or a hydroxyl group, so that it can be applied to various coatings, paints, and bonding techniques.
1 shows FT-IR spectrum of a block isocyanate through reaction of a radical initiator with a diisocyanate compound according to an embodiment of the present invention.
FIG. 2 is a schematic view showing a preparation example of a pre-mixture of a low-temperature crosslinking composition according to an embodiment of the present invention and a rheology analysis system for analyzing the curing behavior using the same.
FIG. 3 is a graph showing the results of measurement of curing behavior and storage elastic modulus of a pre-mixture using a rheology analysis system according to an embodiment of the present invention with respect to temperature and time.
Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
As used throughout this specification, the term " polyisocyanate " refers to an isocyanate having two or more isocyanate groups in its molecular structure. More specifically an aliphatic, aromatic, alicyclic, or aromatic aliphatic compound containing 2 to 6 isocyanate groups in the molecular structure. Further, a urea group, a urea group, a biuret group (-NH-CO-NR-CO-NH-) formed by the reaction of an isocyanate with a polyhydric alcohol and a polyhydric amine, A group having 2 to 6 isocyanate groups in the molecular structure and having an allophanate group (-OCONRCONH-) or a uretdine-2,4-dione group (-N (CO) 2 N-) It means. It is also meant to include a dimer of an aliphatic diisocyanate, a symmetrical or asymmetric trimer, or a compound containing an oligomer in the molecular structure containing 2 to 6 isocyanate groups. In particular, in the case of a timer, it may be decomposed in the reaction to dissociate into three molecules containing two isocyanate groups to finally form six isocyanate groups.
The term " derived " as used throughout the term refers to the molecular structure of the corresponding polyisocyanate except the urea group, which is a linking chemical bond, in blocking the isocyanate group by reaction of the isocyanate group of the polyisocyanate and the radical initiator .
The term " radical initiator " in the present invention includes both a thermal initiator that generates radicals by heat and a photo initiator that generates radicals by light such as ultraviolet light. In the present invention, The radical initiator is more preferably a thermal initiator, but may also be used as a radical initiator by mixing a thermal initiator and a photoinitiator as necessary.
The term " TRI " used throughout this specification is an abbreviation for a thermal radical initiator and means a thermal radical initiator.
The present invention provides a low temperature crosslinkable block isocyanate capable of being cured by a urea bond formation reaction between a compound represented by the following formula (A) and a polyisocyanate compound.
≪ Formula (A)
Wherein R 1 , R 2 , R 3 R 4 are independently alkyl or together with the carbon to which they are attached form a cyclic ring or cycloalkyl of C3-C12.
In the present invention, the compound of formula (A) may preferably be represented by the following formula (1) or (2).
≪ Formula 1 >
(2)
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound may contain two or more isocyanate groups in the molecular structure as an aliphatic, aromatic, alicyclic, or aromatic, aliphatic compound. More preferably 2 to 6 isocyanate groups.
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound is at least one selected from the group consisting of ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, Diisocyanate, dodecamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene- Isocyanate, isocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate , Bis (2-isocyanatoethyl) fumarate, bis (2 -Isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyl Diisocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene Glycol dipropyl ether-omega, omega-diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatoethyl-2,6-diisocyanatohexanoate (Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene,?,?,? ', And the like are used as the isocyanate- tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (Isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, 2,6-di (isocyanatomethyl) Isocyanatohexyl) -uretidine-2,4-dione, 1,3,5-tris (6-isocyanatohexyl) isocyanurate, have. More preferred is hexamethylene diisocyanate (HDI).
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound may be selected from the group consisting of thiodiethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, ditodimethyl diisocyanate, Diisocyanate, dicyclopropyldisocyanate, dicyclohexylsulfide-4,4'-diisocyanate, at least one sulfide aliphatic isocyanate or diphenyl sulfide-2,4'-diisocyanate, di 4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzyl thioether, bis (4-isocyanatomethylbenzene) sulfide, 4,4'- Aromatic sulfide isocyanates such as ethoxy benzene thioethylene glycol-3,3'-diisocyanate, Phenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyl diphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyl diphenyl disulfide-5,5'-diisocyanate, '-Dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-dimethyl diphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxy diphenyl disulfide-4,4'-di At least one aliphatic disulfide isocyanate selected from the group consisting of isocyanate, isocyanate, and 4,4'-dimethoxy diphenyl disulfide-3,3'-diisocyanate.
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound may be a dimer, a trimer, or an oligomer of an aliphatic isocyanate or an aliphatic isocyanate and an alcohol, An organic acid, an organic amine or the like, and contains two or more isocyanate groups in the molecule after the reaction. Representative examples of such polyisocyanates include, but are not limited to, the following structural formula C, which contains a biuret group derived from hexamethylene diisocyanate (HDI) in the molecular structure, a trimer isocyanate represented by the following formula D, asymmetric trimers (E), which contains an allophanate group, which contains an iminooxadiaquinodimer, in the molecular structure, and a dimer of uretidine-2, 4-dione , 4-dione) group in the molecular structure. More preferably 1,3,5-tris (6-isocyanatohexyl) isocyanurate of the following formula D or 1,3, -bis (6-isocyanatohexyl) 4-dione. ≪ / RTI >
≪ EMI ID =
<Formula D>
(E)
<Formula F>
<Formula G>
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound is 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI) , 2,6-tolylene diisocyanate, 4,4'-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, ethylphenylene diisocyanate, 4,4'-diisocyanate biphenyl, Dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, naphthalene diisocyanate, methylnaphthalene diisocyanate, trinidine diisocyanate, bis (Isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, isopropylenephenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisocyanate Benzene triisocyanate, triphenylmethane triisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4, diphenylmethane diisocyanate, triphenylmethane diisocyanate, At least one aromatic isocyanate selected from the group consisting of 6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ', 4', 6'-pentaisocyanate.
In the low-temperature crosslinkable block isocyanate capable of being cured in accordance with the present invention, the polyisocyanate compound is selected from the group consisting of diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidine- Diisocyanate, diphenylmethane sulfone-4,4'-diisocyanate, 4-methyldiphenylmethane sulfone-2,4'-diisocyanate, 4,4'-dimethoxy diphenyl sulfone-3,3 ' Diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'- Butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-methoxybenzene ethylenedisulfone-3,3'-diisocyanate, 4,4'-dichlorophenylsulfone-3,3'-diisocyanate And at least one aromatic sulfonic acid isocyanate selected from the group consisting of
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound is at least one selected from the group consisting of isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), cyclohexylene diisocyanate, Bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, 2 , 2-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, dimeric acid diisocyanate, 2-isocyanatomethyl-3- ) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2- isocyanatomethyl-3- (3- isocyanatopropyl) -6- isocyanatomethyl-bicyclo [ , 2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanate Isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [ , 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2-isocyanatomethyl- - (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2- isocyanatomethyl-2- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane. The alicyclic isocyanate may be at least one selected from the group consisting of: More preferred is isophorone diisocyanate (IPDI) or 4,4'-dicyclohexylmethane diisocyanate (HMDI).
In the low temperature crosslinkable block isocyanate according to the present invention, the polyisocyanate compound is 1,3-bis (isocyanatomethyl) benzene (m-xylene diisocyanate, m-XDI) (Isocyanatomethyl) benzene (p-xylene diisocyanate, p-XDI), 1,3-bis (2-isocyanatopropan-2-yl) benzene (m-tetramethylxylene diisocyanate, m- Benzene (p-tetramethylxylene diisocyanate, p-TMXDI), 1,3-bis (isocyanatomethyl) -4-methylbenzene, (Isocyanatomethyl) -4-ethylbenzene, 1,3-bis (isocyanatomethyl) -5-methylbenzene, 1,3-bis (isocyanatomethyl) Dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,5-dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetramethylbenzene, 1,3- Bis (isocyanatomethyl) -5-tert-butylbenzene, 1,3-bis (isoshi Bis (isocyanatomethyl) -4,4-dichlorobenzene, 1,3-bis (isocyanatomethyl) -2,4,5,6-tetrachloro Benzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrabromobenzene , 1,4-bis (2-isocyanatoethyl) benzene, and 1,4-bis (isocyanatomethyl) naphthalene.
The present invention provides a low temperature crosslinkable block isocyanate capable of being cured with a chemical structure represented by the following chemical formula (B).
≪ Formula B >
In formula (B), R 1 , R 2 , R 3 , R 4 is independently alkyl or forms a cyclic ring with the carbon to which they are attached or is cycloalkyl of C3-C12, n is an integer of 2 or greater, X is a C2-C30 aliphatic, aromatic, cycloaliphatic, or aromatic Aliphatic.
In the low temperature crosslinkable block isocyanate according to the present invention, the formula (B) is prepared through a urea bond formation reaction between a compound of the formula (A) and a polyisocyanate, wherein X in the formula (B) is ethylene diisocyanate, But are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4- Hexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (2-isocyanatoethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, 1 (isocyanatomethyl ethyl) fumarate, , 3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl (Isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-omega, omega-diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate, Diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, xylylene diisocyanate , Bis (isocyanatoethyl) benzene, bis (isocyanato) (Isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether (isocyanatomethyl) benzene, bis (isocyanatomethyl) , Bis (isocyanatoethyl) phthalate, 2,6-di (isocyanatomethyl) furan, 1,3, -bis (6-isocyanatohexyl) -uretidine- , 3,5-tris (6-isocyanatohexyl) isocyanurate, and the like. More preferably, it may be derived from hexamethylene diisocyanate (HDI).
In the low temperature crosslinkable block isocyanate according to the present invention, the formula (B) is prepared through a urea bond formation reaction between a compound of the formula (A) and a polyisocyanate compound, wherein the polyisocyanate compound is an aliphatic isocyanate Dimer, trimer, or oligomer of the aliphatic isocyanate, or a compound containing two or more isocyanate groups in the molecule after reaction with an aliphatic isocyanate and an alcohol, an organic acid, or an organic amine. Representative examples of such polyisocyanates include, but are not limited to, the following structural formula C, which contains a biuret group derived from hexamethylene diisocyanate (HDI) in the molecular structure, a trimer isocyanate represented by the following formula D, asymmetric trimers (E), which contains an allophanate group, which contains an iminooxadiaquinodimer, in the molecular structure, and a dimer of uretidine-2, 4-dione , 4-dione) group in the molecular structure. More preferably 1,3,5-tris (6-isocyanatohexyl) isocyanurate of the following formula D or 1,3, -bis (6-isocyanatohexyl) 4-dione. ≪ / RTI >
≪ EMI ID =
<Formula D>
(E)
<Formula F>
<Formula G>
In the low-temperature crosslinkable block isocyanate according to the present invention, the formula (B) is prepared through a urea bond formation reaction between a compound of the formula (A) and a polyisocyanate, wherein X in the formula (B) 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, ethylphenylene diisocyanate, 4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'- , 4'-diisocyanatodiphenylmethane, naphthalene diisocyanate, methylnaphthalene diisocyanate, trinidine diisocyanate, bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4-4'-diisocyanate , Isopropylene phenyl There may be mentioned, for example, aromatic diisocyanates such as diisocyanate, diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, triphenylmethane triisocyanate, naphthalene triisocyanate, 2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ', 4', 6'-pentaisocyanate ≪ RTI ID = 0.0 > and / or < / RTI >
In the low temperature crosslinkable block isocyanate according to the present invention, the formula (B) is prepared through a urea bond forming reaction between a compound of the formula (A) and a polyisocyanate, wherein X in the formula (B) is isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene- Norbornane diisocyanate, 2,6-norbornane diisocyanate, 2,2-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) Pentaerythritol, dimeric acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] Natomethyl-3- (3-iso 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] heptane, Bicyclo [2,2,1] -heptane, 2- isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [ (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- - isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2- isocyanatomethyl-2- (3- isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2- isocyanatomethyl-2- (3- isocyanatopropyl) -6- Diisocyanate comprising bicyclo [2,2,1] -heptane and norbornane bis (isocyanatomethyl) and 1,3-bis (6-isocyanatohexyl) -1,3- 4- Ions, 1,3,5-tris (3-isocyanatopropyl) -1,3,5-triazine, and 2,4,6-trione. . More preferred is isophorone diisocyanate (IPDI) or 4,4'-dicyclohexylmethane diisocyanate (HMDI), 1,3, -bis (6-isocyanatohexyl) 4-dione, 1,3,5-tris (6-isocyanatohexyl) isocyanurate.
In the low-temperature crosslinkable block isocyanate according to the present invention, the formula (B) is prepared through a urea bond formation reaction between a compound of the formula (A) and a polyisocyanate, wherein X in the formula (B) (Isocyanatomethyl) benzene (m-xylene diisocyanate, m-XDI), 1,4-bis (isocyanatomethyl) benzene (p-xylene diisocyanate, p- 2-isocyanatopropane-2-yl) benzene (m-tetramethylxylene diisocyanate, m-TMXDI), 1,4-bis Diisocyanate, p-TMXDI), 1,3-bis (isocyanatomethyl) -4-methylbenzene, 1,3-bis (isocyanatomethyl) (Isocyanatomethyl) -2,5-dimethylbenzene, 1,4-bis (isocyanatomethyl) -4,5-dimethylbenzene, 1,4-bis - Bis (Isocyanatomethyl) -5-tert-butylbenzene, 1,3-bis (isocyanatomethyl) -4- (Isocyanatomethyl) -4,5-dichlorobenzene, 1,3-bis (isocyanatomethyl) -2,4,5,6-tetrachlorobenzene, 1,4- Bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrabromobenzene, 1,4-bis (2-isocyanatoethyl) benzene, and 1,4-bis (isocyanatomethyl) naphthalene.
The low temperature crosslinkable block isocyanate capable of being cured according to the present invention may have a chemical structure of any one of the following Chemical Formulas (3) to (16).
(3)
≪
≪
(6)
≪ Formula 7 >
(8)
≪ Formula 9 >
≪
≪ Formula 11 >
≪ Formula 12 >
≪ Formula 13 >
≪ Formula 14 >
≪
≪ Formula 16 >
In the present invention, low temperature crosslinkable block isocyanate capable of being cured at a low temperature; And a low-temperature crosslinkable composition comprising a monomer or an oligomer having both an ethylenic or acrylic unsaturated double bond and a hydroxyl group simultaneously.
Meanwhile, monomers or oligomers which can be used in the low-temperature crosslinkable composition according to the present invention have ethylenic or acrylic unsaturated double bonds in their branching structure or monomers or oligomers having hydroxyl groups can be used. However, for effective low- Or an acrylic unsaturated double bond and a hydroxyl group at the same time. Such monomers or oligomers can be used as the main resin of the low-temperature crosslinkable composition, and the block isocyanate according to the present invention can simultaneously serve as a radical generating initiator and as a crosslinking agent for effective crosslinking.
Also, the monomer or oligomer having both an ethylenic or acrylic unsaturated double bond and a hydroxyl group according to an embodiment of the present invention may be used as a main resin and may have a chemical structure represented by the following chemical formula (17).
≪ Formula 17 >
In addition, the low-temperature crosslinkable composition according to the present invention may contain various additives depending on the specific use, such as a reactive diluent such as diacrylate and an inorganic filler, if necessary. Preferably, the reactive diluent according to one embodiment of the present invention may be 1,6-hexanediol diacrylate.
BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. In particular, the technical idea of the present invention and its core structure and action are not limited by this. In addition, the content of the present invention can be implemented by various other types of equipment, and is not limited to the embodiments and examples described herein.
Preparation Example 1: Preparation of compound of formula (1)
The compound of formula (1), which is a thermal radical initiator (TRI) according to one embodiment of the present invention, can be prepared according to the following reaction formula (1).
≪
<
First, 30.0 g (265 mmol) of cyclohexanone oxime was stirred in 300 ml of tetrahydrofuran in an argon atmosphere, and then 1.06 g (26.5 mmol) of sodium hydroxide and 45.6 g (221 mmol) of dicyclohexylmethaneindiimine were added thereto. Lt; / RTI > at room temperature. After completion of the reaction, dichloromethane was added, followed by stirring for 30 minutes, followed by vacuum filtration. The solvent was removed by concentration under reduced pressure, and the residue was dissolved in hexane, followed by addition of acetonitrile, followed by stirring for 1 hour. Thereafter, only a hexane layer was obtained and concentrated under reduced pressure to remove the solvent to obtain 50.47 g (158 mmol) of the compound of the formula (1).
Preparation Example 2: Preparation of the compound of formula (2)
The compound of
(2)
<
After 30.0 g (303 mmol) of cyclopentanone oxime was stirred in 300 ml of tetrahydrofuran in an argon atmosphere, 1.21 g (30.3 mmol) of sodium hydroxide and 52.0 g (252 mmol) of dicyclohexylmethaneindiimine were added and the mixture was stirred for 24 hours The mixture was stirred at room temperature. After completion of the reaction, dichloromethane was added, followed by stirring for 30 minutes, followed by vacuum filtration. The solvent was removed by concentration under reduced pressure, and the residue was dissolved in hexane, followed by addition of acetonitrile, followed by stirring for 1 hour. Thereafter, only a hexane layer was obtained, and the solvent was removed by concentration under reduced pressure to obtain 44.8 g (147 mmol) of the compound of the formula (2).
Preparation Example 3: Preparation of compound of formula (3)
The compound of
(3)
<
16.8 g (52.6 mmol) of the compound of the formula (1) are stirred in 50 ml of dichloromethane in an argon atmosphere. 3 g (11.4 mmol) of 4,4'-dicyclohexylmethane diisocyanate (HMDI) was then added and stirred at 35 DEG C for 60 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent. The residue was dissolved in a small amount of dichloromethane and then redeposited with diethyl ether / hexane to obtain 4.3 g (4.77 mmol) of the compound of the formula (3).
Production Example 4: Preparation of a compound represented by the formula (4)
The compound of
≪
<
Compound (11.9 g, 38.8 mmol) was stirred in 50 ml of dichloromethane in an argon atmosphere. 3 g (11.4 mmol) of 4,4'-dicyclohexylmethane diisocyanate (HMDI) was then added and stirred at 35 DEG C for 60 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent. The residue was dissolved in a small amount of dichloromethane and then redissolved in diethyl ether / hexane to obtain 3.4 g (3.89 mmol) of the compound of the formula (4).
Preparation Example 5: Preparation of compound of formula (5)
The compound of
≪
<
13.8 g (43.2 mmol) of the compound of the formula (1) are stirred in 50 ml of dichloromethane in an argon atmosphere. 3 g (13.5 mmol) of isophorone diisocyanate was then added and the mixture was stirred at 35 DEG C for 60 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent. The residue was dissolved in a small amount of dichloromethane and then redeposited using diethyl ether / hexane to obtain 2.91 g (3.38 mmol) of the compound of the formula (5).
Manufacturing example
6: Preparation of compound of
The compound of formula (6) according to one embodiment of the present invention can be prepared through the reaction of a compound of formula (2) with isophorone diisocyanate, This is the same as Example 5.
(6)
Preparation Example 7: Preparation of Compound (7)
Compounds of formula 7 according to one embodiment of the invention may be prepared according to
≪ Formula 7 >
<
5.97 g (18.7 mmol) of the compound of the formula (1) are stirred in 30 ml of dichloromethane in an argon atmosphere. Then, 3 g (8.92 mmol) of 1,3, -bis (6-isocyanatohexyl) -uretidine-2,4-dione having the formula G was added and stirred at room temperature for 6 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent to obtain 7.92 g (8.12 mmol) of the compound of the formula (7).
Preparation Example 8: Preparation of the compound of formula (8)
The compound of Formula 8 according to one embodiment of the present invention is a compound of
(8)
Preparation 9: Preparation of the compound of formula 9
The compound of formula (9) according to one embodiment of the present invention can be prepared according to the following reaction formula (7).
≪ Formula 9 >
<Reaction Scheme 7>
7.99 g (25.0 mmol) of the compound of the formula (1) is stirred in 50 ml of dichloromethane in an argon atmosphere. Thereafter, 3 g (7.93 mmol) of 1,3,5-tris (6-isocyanatohexyl) isocyanurate (trimer of hexamethylene diisocyanate: HDI trimer) As shown in FIG. 1, the disappearance of the NCO peak was confirmed by the IR spectrum, followed by stirring at room temperature for 6 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent to obtain 9.54 g (7.14 mmol) of the compound of the formula (9).
Preparation Example 10: Preparation of compound of formula (10)
The compound of formula (10) according to one embodiment of the present invention is obtained by reacting a compound of formula (2) with 1,3,5-tris (6-isocyanatohexyl) isocyanurate of formula 9, < / RTI >
≪
Preparation Example 11: Preparation of compound of formula (11)
The compound of formula (11) according to one embodiment of the present invention is obtained by reacting a compound of formula (1) with 1,2,4-tris (6-isocyanatohexyl) iminooxy- 8, and the preparation method was the same as that of Production Example 9.
≪ Formula 11 >
<Reaction Scheme 8>
Preparation Example 12: Preparation of the compound of the formula (12)
The compound of formula (12) according to one embodiment of the present invention is obtained by reacting a compound of formula (2) with 1,2,4-tris (6-isocyanatohexyl) iminooxyadiazin dione of formula And the production method was the same as that of Production Example 9. [
≪ Formula 12 >
Production Example 13 to Production Example 16: Preparation of the compounds of the formulas (13) to (16)
The compounds of formulas (13) to (16) according to one embodiment of the present invention can be prepared by reacting a compound of the formula (1), a biuret of the corresponding hexamethylene diisocyanate, an allophanate compound C >, < Formula F >, and the preparation method was carried out under the same conditions as those of Production Examples 3 to 12 above.
≪ Formula 13 >
≪ Formula 14 >
≪
≪ Formula 16 >
Test Example 1: Preparation and curing of pre-mixture
In order to test the low temperature crosslinking of the low temperature crosslinking block isocyanate according to one embodiment of the present invention, as shown in FIG. 2, the compound of the formula (9) prepared according to Production Example 9 was used as the low temperature crosslinking block isocyanate capable of double curing (DCR-4274: Formula 17) having acryl unsaturated double bonds and hydroxyl groups at the same time and 1,6-hexanediol diacrylate as a reactive diluent were used to prepare a pre-mixture, and this was subjected to a rotation rheometer (MCR -301, Anton Paar, Austria) was used to measure the storage modulus with respect to curing temperature and time.
The preparation method and measurement conditions of the specific pre-mixture are as follows. First, 2 g of HFUMO (DCR-4274, Formula 17), which is a main resin containing a 60% double bond (-C═C-) and 80 mg of KOH / g hydroxy (-OH) group, 1 g of hexanediol diacrylate, 1 g of commercialized block isocyanate (PL350, Bayer Material Science, Desmodur ( R) PL 350 MPA / SN, Blocked Aliphatic Polyisocyanate based on HDI along with Dimethyl Pyrazole (Comparative Example 1) 0.42 g of isocyanate (Example 1) or 0.42 g of block isocyanate (Example 2) were mixed and mixed to prepare a pre-mixture. In order to measure the curing behavior and modulus of the mixed composition with temperature, (MCR-301, Anton) under a temperature raising rate condition (UV light: 6.0 mW / cm 2 , Temperature: 25 ° C, Strain: 2%, Frequency: 5 Hz) from 20 ° C. to 170 ° C. for 25 minutes, Paar, Austria) and the results are summarized in FIG. 3 and Table 1 below.
(° C)
(Pa)
As shown in Table 1, the crosslinking composition prepared using the block isocyanate compound of Comparative Example 1, commercialized block isocyanate (PL350, Formula 17), Example 1 (Formula 3) and Example 2 (Formula 9) As a result of the measurement of the behavior, it was found that the curing temperatures of Formulas (3) and (9) were cured at a much lower temperature than 165 ° C of PL 350 (Comparative Example 1) commercialized at 98 and 82 ° C, respectively. Example 1 (Formula 3) shows a modulus value equal to or higher than 1.3 x 10 < 7 > Pa of PL350 (Comparative Example 1) that was used at 1.4 x 10 6 and 1.3 x 10 7 Pa, respectively, .
That is, as shown in FIG. 3, the low-temperature crosslinkable composition comprising the block isocyanate compound according to the present invention exhibits an increase in modulus from 6 minutes in Example 2 (Formula 9) to 7 minutes in Example 2 (Formula 3) , Whereas Comparative Example 1 shows an increase in modulus, that is, curing, at 13 minutes, so that the low temperature crosslinkable block isocyanate capable of being cured according to the present invention exhibits a cured product of Comparative Example 1 It can be seen that the curing starts within a short time as compared with the phosphorus isocyanate.
As a result, according to the present invention, the curing time can be significantly shortened in comparison with the comparative example, and the surface quality and hardening can be rapidly provided, so that the contact with various dusts and the deterioration of physical properties under the process conditions can be minimized, As a dual cure, it provides a higher molecular crosslinking degree and gives a high modulus, which is advantageous in that it can provide relatively excellent properties in mechanical / chemical properties externally applied.
As described above, the block isocyanate according to the present invention and the composition containing the block isocyanate having a dissociation temperature different from each other have a double curing reaction structure, and the blocking group capable of dissociation at a low temperature is dissociated and the curing reaction at the surface and interface It is possible to perform a quick coating process by first forming and then cross-linking in the inside, since the prebonded pre-isocyanate progresses as the temperature rises, so that coatings and paints that require rapid surface hardening at the process level, This provides a very great advantage.
Claims (10)
≪ Formula (A)
Wherein R 1 , R 2 , R 3 and R 4 are independently alkyl or together with the carbon to which they are attached form a cyclic ring or cycloalkyl of C3-C12.
≪ Formula B >
In formula (B), R 1 , R 2 , R 3 , R 4 is independently alkyl or forms a cyclic ring with the carbon to which they are attached or is cycloalkyl of C3-C12, n is an integer of 2 or greater, X is a C2-C30 aliphatic, aromatic, cycloaliphatic, or aromatic Aliphatic.
Wherein the compound of formula (A) is a double-curable low-temperature crosslinking block isocyanate represented by the following formula (1) or (2).
≪ Formula 1 >
(2)
Wherein the polyisocyanate compound is an aliphatic, aromatic, alicyclic, or aromatic aliphatic compound and contains at least two isocyanate groups in the molecular structure.
The polyisocyanate compound may be at least one selected from the group consisting of ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene diisocyanate, 2,2- Isocyanate, isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis (2-isocyanate ethyl) fumarate, bis (2-isocyanate) Ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate 1,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanato-5- (Isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-omega, omega-diisocyanate, lysine diisocyanato methyl ester, Diisocyanatohexanoate, 2-isocyanatoethyl-2,6-diisocyanatoheptanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, (Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene,?,?,? ',?' - tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, Bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (Isocyanatoethyl) phthalate, 2,6-di (isocyanatomethyl) furan, 1,3, -bis (6-isocyanatohexyl) -uretidine-2,4- -Tris (6-isocyanatohexyl) isocyanurate, at least one aliphatic isocyanate selected from the group consisting of thiodiethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, At least one sulfoaliphatic isocyanate selected from the group consisting of dodecyl diisocyanate, dithiodiethyl diisocyanate, ditopropyl diisocyanate, dicyclohexyl sulfide-4,4'-diisocyanate, or diphenyl sulfide-2,4 Diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) Zenz) sulfide, and 4,4'-methoxybenzenethioethylene glycol-3,3'-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl Disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, -Dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxy diphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxy diphenyl disulfide-3,3'-di Isocyanate, isobicyclic isocyanate and isobicyclic isocyanate capable of being cured at a low temperature, characterized in that it is at least one aliphatic disulfide isocyanate selected from the group consisting of isocyanate and isocyanate.
The polyisocyanate compound may be at least one selected from the group consisting of 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, (MDI), 2,4-diphenylmethane diisocyanate, ethylphenylene diisocyanate, 4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate biphenyl , 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, naphthalene diisocyanate, methylnaphthalene diisocyanate, trinidine diisocyanate, bis (isocyanatophenyl) ethylene, Phenyl-4,4'-diisocyanate, isopropylenephenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene tri Isocyanate, triphenylmethane triisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl- Methane-3,5,2 ', 4', 6'-pentaisocyanate or diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'- Diisocyanate, diphenylmethane sulfone-4,4'-diisocyanate, 4-methyldiphenylmethane sulfone-2,4'-diisocyanate, 4,4'-dimethoxy diphenyl sulfone-3,3'-diisocyanate , 3,3'-dimethoxy-4,4'-diisocyanate dibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di- Sulfone-3,3'-diisocyanate, 4,4'-methoxybenzene ethylene disulfone-3,3'-diisocyanate, 4,4'-dichlorophenylsulfone-3,3'-diisocyanate Jin isocyanate low temperature cross-linkable block is a dual curable, characterized in that at least one aromatic sulfone isocyanates selected from the group.
The polyisocyanate compound is selected from the group consisting of isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2- -Cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, 2,2-dimethyl dicyclohexylmethane diisocyanate, bis Dimethicone diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [ 1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] - (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2- isocyanatomethyl-2- (3- Isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanato Ethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3- isocyanatopropyl) -6- (2- isocyanatoethyl) -bicyclo [ , 1] -heptane, 2- isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,1,1] (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, and norbornane bis (isocyanatomethyl) Wherein at least one alicyclic isocyanate is selected from the group consisting of alicyclic isocyanates and alicyclic isocyanates.
The polyisocyanate compound may be at least one selected from the group consisting of 1,3-bis (isocyanatomethyl) benzene (m-xylene diisocyanate, m-XDI), 1,4-bis (isocyanatomethyl) benzene (p- Bis (2-isocyanatopropan-2-yl) benzene (m-tetramethyl xylene diisocyanate, m-TMXDI), 1,4- Benzene (p-tetramethylxylene diisocyanate, p-TMXDI), 1,3-bis (isocyanatomethyl) -4-methylbenzene, 1,3-bis (isocyanatomethyl) Bis (isocyanatomethyl) -5-methylbenzene, 1,3-bis (isocyanatomethyl) -4,5-dimethylbenzene, 1,4-bis Dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetramethylbenzene, 1,3-bis (isocyanatomethyl) -5-tert- , 3-bis (isocyanatomethyl) -4-chlorobenzene, 1,3-bis (isocyanatomethyl) -4,5-dichlorobenzene, 1,3-bis (Isocyanatomethyl) -2,4,5,6-tetrachlorobenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 1,4-bis Bis (isocyanatoethyl) benzene, 1,4-bis (isocyanatomethyl) naphthalene, 1,4-bis A low temperature cross-linkable block isocyanate capable of being cured by double action, characterized in that it is at least one aromatic aliphatic isocyanate.
Wherein the block isocyanate has a chemical structure of any one of the following Chemical Formulas (3) to (16).
(3)
≪ Formula 4 >
≪ Formula 5 >
(6)
≪ Formula 7 >
(8)
≪ Formula 9 >
≪ Formula 10 >
≪ Formula 11 >
≪ Formula 12 >
≪ Formula 13 >
≪ Formula 14 >
≪ Formula 15 >
≪ Formula 16 >
A low temperature crosslinkable composition capable of being cured by double-curing, which comprises a monomer or an oligomer having both an ethylenic or acrylic unsaturated double bond and a hydroxyl group.
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| PCT/KR2017/002465 WO2017160016A1 (en) | 2016-03-14 | 2017-03-07 | Dual-curable low-temperature crosslinked blocked isocyanate and composition comprising same |
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| KR102147655B1 (en) * | 2019-10-14 | 2020-08-25 | 한국화학연구원 | composition for low temperature curable, crosslinked resin using the same, and products comprising the same |
| KR20220153947A (en) * | 2021-05-12 | 2022-11-21 | 한국화학연구원 | Composition of one component clear coat using low temperature curing for automotive |
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| CN110204678B (en) * | 2019-05-21 | 2021-08-10 | 中国船舶重工集团公司第七二五研究所 | Polydimethylsiloxane self-repairing material based on disulfide bond exchange reaction and preparation method thereof |
| KR102643078B1 (en) | 2021-10-14 | 2024-02-29 | 한국화학연구원 | Pyrazole based block isocyanate capable of radical reaction for low temperature curing and composition comprising the same |
| WO2023190410A1 (en) * | 2022-03-28 | 2023-10-05 | 三菱ケミカル株式会社 | Compound, polymerizable composition, cured product, color filter, partition wall and image display device |
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| JP5274743B2 (en) * | 2000-05-19 | 2013-08-28 | チバ ホールディング インコーポレーテッド | Hydroxylamine esters as polymerization initiators |
| DE10115602A1 (en) * | 2001-03-29 | 2002-10-24 | Basf Coatings Ag | Copolymers modified with polyurethanes, process for their preparation and their use |
| KR101485186B1 (en) * | 2008-09-17 | 2015-01-23 | 코오롱인더스트리 주식회사 | Thermosetting resin composition |
| CN102421749B (en) | 2009-05-07 | 2015-03-11 | 巴斯夫欧洲公司 | O-imino-iso-urea compounds and polymerizable compositions thereof |
| EP2638076B1 (en) | 2010-11-12 | 2018-03-28 | Coloplast A/S | Novel photoinitiators |
| JP6068932B2 (en) | 2012-11-01 | 2017-01-25 | 三井化学株式会社 | Block isocyanate, aqueous dispersion, coating composition, and method for producing blocked isocyanate |
| JP6025507B2 (en) | 2012-11-01 | 2016-11-16 | 三井化学株式会社 | Block isocyanate, coating composition, and method for producing blocked isocyanate |
-
2016
- 2016-03-14 KR KR1020160030458A patent/KR101859813B1/en active IP Right Grant
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2017
- 2017-03-07 WO PCT/KR2017/002465 patent/WO2017160016A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102147655B1 (en) * | 2019-10-14 | 2020-08-25 | 한국화학연구원 | composition for low temperature curable, crosslinked resin using the same, and products comprising the same |
| KR20220153947A (en) * | 2021-05-12 | 2022-11-21 | 한국화학연구원 | Composition of one component clear coat using low temperature curing for automotive |
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| Publication number | Publication date |
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| KR101859813B1 (en) | 2018-05-18 |
| WO2017160016A1 (en) | 2017-09-21 |
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