WO2017160016A1 - Dual-curable low-temperature crosslinked blocked isocyanate and composition comprising same - Google Patents

Abstract

The present invention pertains to a novel blocked isocyanate having a dual curing reaction type structure having different dissociation temperatures, and more specifically pertains to a dual-curable low-temperature crosslinked blocked isocyanate formed by using a radical initiator to block an isocyanate group of a polyisocyanate compound that is an aliphatic, aromatic, alicyclic or araliphatic diisocyante, and to a low-temperature crosslinked composition which comprises the blocked isocyanate and an oligomer or a monomer having simultaneously a hydroxyl group and an ethylene or acrylic unsaturated double bond.

Description

Low temperature crosslinkable block isocyanate capable of dual curing and composition comprising the same

The present invention relates to a novel block isocyanate having a double cure reactive structure with different dissociation temperatures.

More specifically, 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 isocyanates and hydroxyl groups of these block isocyanates and ethylene- or acryl-based A low temperature crosslinkable composition comprising a monomer or oligomer.

This application claims priority based on Korean Patent Application No. 10-2016-0030458 filed on March 14, 2016, and all the contents disclosed in the specification and drawings of the application are incorporated in this application.

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.

Recently, automotive steel materials are being replaced with plastic materials, which are lightweight materials, to cope with climate change and environmental problems such as carbon dioxide reduction and fuel economy improvement. Mass production of automobiles using these lightweight plastic materials requires a radical transformation of chemical structures such as paints, coatings and adhesives used as commercial products in existing production lines and reaction processes to control them. In particular, the existing high temperature hardening process is a low temperature hardening process due to the problems of plastic material degeneration or various color matching. In addition, the automotive coating system based on the existing high-temperature curing crosslinking method must release a large amount of VOC (Volatile Organic Compounds) and harmful substances, and at the same time avoid the regulation of carbon dioxide emission due to the enormous energy consumption which is the main cause of warming. Overseas developed countries will need the original technology for automotive coating system based on the new environment-friendly low temperature curing technology to cope with climate change.

Meanwhile, 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. However, 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.

In order to improve storage stability of the isocyanate, the blocking group used for the conventional block isocyanate has been used mainly for oxime, caprolactams, pyrazole, and the like. 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.

However, 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. There is a disadvantage that causes a problem. Therefore, 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.

In the present invention, 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 as heat or ultraviolet light as possible.

In the present invention, 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.

In the present invention, in order to solve the above problems, 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.

<Formula A>

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.

In the present invention, the compound of Formula A may preferably be the following Formula 1 or Formula 2.

<Formula 1>

<Formula 2>

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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.

In addition, the present invention provides a low-temperature crosslinkable block isocyanate capable of double curing having a chemical structure of formula (B).

<Formula B>

In 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.

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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). That is, in Formula B, 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.

In this case, 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.

In addition, 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.

In addition, 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.

In addition, in the present invention, 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.

As described above, the new block isocyanate of the double-curing reactive structure having different dissociation temperatures according to the present invention 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.

In addition, 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.

4 is a result of measuring the curing behavior and storage modulus according to the temperature and time of the pre-mixture using the rheology analysis system according to an embodiment of the present invention.

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.

6 is a result of measuring the curing behavior and storage modulus according to the temperature and time of the pre-mixture using the rheology analysis system according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The term polyisocyanate, as used throughout this specification, 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. Further, urethane groups, urea groups, biuret groups (-NH-CO-NR-CO-NH-) and allopa formed by the reaction of isocyanates with polyhydric alcohols and polyamines It includes an etherate group (-OCONRCONH-) or an uretdine-2,4-dione group (-N (CO) ₂ N-) in a molecular structure and contains 2 to 6 isocyanate groups. 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 | disassemble during reaction and dissociate into three molecules containing two isocyanate groups, and finally form six isocyanate groups.

“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. Means a compound having at least one free radical polymerizable unsaturated group such as a krill group, preferably isocyanate functionalized unsaturated acrylic ester, unsaturated urethane acrylate, or molecular chain having two isocyanate groups at the end of the molecular chain 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.

On the other hand, derived from the term used throughout is 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.

In addition, in the present invention, 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. Although a thermal initiator is more preferable, you may mix and use a thermal initiator and a photoinitiator as a radical initiator as needed.

Meanwhile, the term TRI, which is used throughout this specification, stands for thermal radical initiator.

In the present invention, in order to solve the above problems, 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.

<Formula A>

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.

In the present invention, the compound of Formula A may preferably be the following Formula 1 or Formula 2.

<Formula 1>

<Formula 2>

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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.

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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. Can.

In the low temperature crosslinkable block isocyanate according to the present invention, 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) fumarate, bis (2 -Isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, 1,3,6-hekisamecirene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyl Octane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl octane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene Glycoldipropyl ether-ω, ω'-diisocyanate, lysine diisocyanato methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanato ethyl-2,6-diisocyanato hexanoate , 2-isocyanato propyl-2,6-diisocyanato hexanoate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanato propyl) benzene, α, α, α ', α'-tetramethyl xylylene diisocyanate, bis (isocyanato butyl) benzene, b (Isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, 2,6-di (isocyanatomethyl) furan, 1,3, -bis (6- Number of one or more aliphatic isocyanates selected from the group consisting of isocyanato hexyl) -uretidine-2,4-dione, 1,3,5-tris (6-isocyanato hexyl) isocyanurate have. More preferably, it is hexamethylene diisocyanate (HDI).

In the low-temperature crosslinkable block isocyanate according to the present invention, 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'-meth Aromatic sulfide-based isocyanates such as oxy benzene thioethylene glycol-3,3'-diisocyanate, Phenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3 '-Dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxy diphenyl disulfide-4,4'-di It may be at least one aliphatic disulfide-based isocyanate selected from the group consisting of isocyanate, at least one aliphatic disulfide-based isocyanate selected from the group consisting of 4,4'-dimethoxy diphenyl disulfide-3,3'- diisocyanate.

In addition, in the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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. Representative examples of such 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. More preferably 1,3,5-tris (6-isocyanato hexyl) isocyanurate of formula (D) or 1,3, -bis (6-isocyanato hexyl)-of formula (G) Retidine-2,4-dione.

<Formula C>

<Formula D>

<Formula 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'-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'-dimethoxybiphenyl-4-4'-diisocyanate, isopropylenephenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diiso Lofilphenylene diisocyanate, trimethyrbenzene triisocyanate, benzene triisocyanate, triphenylmethane triisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyl diphenylmethane-4, It may be one or more aromatic isocyanates selected from the group consisting of 6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ', 4', 6'-penta isocyanate.

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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'-methoxy benzene ethylene disulfone-3,3'-diisocyanate, 4,4'-dichlorophenylsulphone-3,3'-diisocyanate It may be at least one aromatic sulfone-based isocyanate selected from the group consisting of.

In the low temperature crosslinkable block isocyanate according to the present invention, 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, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2 , 2,1] -heptane, 2-isocyanatomethyl-2- (3-isosia Natopropyl) -5-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 [2,2,1] -heptane , 2-isocyanatomethyl-3- (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) At least one alicyclic isocyanate selected from the group consisting of -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, norbornane bis (isocyanatomethyl). More preferably, it is isophorone diisocyanate (IPDI) or 4,4'- dicyclohexyl methane 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), 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, 1,3-bis (isocyanatomethyl) -4,5- Dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,5-dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetramethylbenzene, 1,3- Bis (isocyanatomethyl) -5-tert-butyl benzene, 1,3-bis (isocy Natomethyl) -4-chloro benzene, 1,3-bis (isocyanatomethyl) -4,5-dichlorobenzene, 1,3-bis (isocyanatomethyl) -2,4,5,6-tetrachloro Benzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachloro benzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrabromo benzene , 1,4-bis (2-isocyanatoethyl) benzene, 1,4-bis (isocyanatomethyl) naphthalene may be at least one aromatic aliphatic isocyanate selected from the group consisting of.

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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. Means a compound having at least one isocyanate-reactive group and at least one 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 free radically polymerizable unsaturated groups, such as a vinyl group, an acryl group, and a methacryl group, in the side chain of a molecular chain. 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.

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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).

<Formula H>

However, in Formula C, 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.

<Formula B>

In Formula B, 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.

In the low-temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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 diisocy Anate, 2,6-diisocyanatemethylcaproate, bis (2-isocyanateethyl) fumarate, bis (2-isocyanateethyl) carbonate, 2-isocyanateethyl-2,6-diisocyanatehexanoate, 1 , 3,6-hequisamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyl octane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl Octane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycoldipropyl ether-ω, ω'-diisocyanate, lysine diisocyanato methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanato ethyl-2,6-diisocyanato hexanoate, 2-isocyanato propyl-2,6-diisocyanato hexanoate, xylylene diisocyanate , Bis (isocyanatoethyl) benzene, bis (isocyanatope) Phil) Benzene, α, α, α ', α'-tetramethyl xylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether , Bis (isocyanatoethyl) phthalate, 2,6-di (isocyanatomethyl) furan, 1,3, -bis (6-isocyanato hexyl) -uretidine-2,4-dione, 1 , 3,5-tris (6-isocyanatohexyl) isocyanurate may be derived from one or more selected from the group consisting of. More preferably, it may be derived from hexamethylene diisocyanate (HDI).

In addition, in the low-temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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 -Diisocyanato dibenzyl thioether, bis (4-isocyana) Tomethyl benzene) sulfide, aromatic sulfide-based isocyanates such as 4,4'-methoxy benzene thioethylene glycol-3,3'-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyl Diphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-6,6'-diisocyanate, 4, 4'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxy diphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxy diphenyl disulfide-3,3 ' -At least one aliphatic disulfide-based isocyanate selected from the group consisting of diisocyanates.

In addition, in the low-temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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. Representative examples of such 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. More preferably 1,3,5-tris (6-isocyanato hexyl) isocyanurate of formula (D) or 1,3, -bis (6-isocyanato hexyl)-of formula (G) Retidine-2,4-dione.

<Formula C>

<Formula D>

<Formula E>

<Formula F>

<Formula G>

In the low-temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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, triazine diisocyanate, bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4-4'-diisocyanate Isopropylenephenyl Diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethyrylene triisocyanate, benzene triisocyanate, triphenylmethane triisocyanate, naphthalene triisocyanate, diphenylmethane- 2,4,4'-triisocyanate, 3-methyl diphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ', 4', 6'-penta isocyanate It may be derived from one or more selected from the group consisting of.

In the low-temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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'-di-tert-butyl diphenyl sulfone-3,3'-diisocyanate, 4,4'-methoxy benzene ethylene disulfone- At least one selected from the group consisting of 3,3'-diisocyanate, 4,4'-dichlorophenylsulfon-3,3'-diisocyanate Hyangjok settings can be pongye isocyanate.

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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), 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) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-r Cyclo [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 [2,2,1] -heptane, 2-isocyanatomethyl-3- (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- (2-isocyanatoethyl)- Diisocyanate consisting of bicyclo [2,2,1] -heptane, norbornane bis (isocyanatomethyl) and 1,3-bis (6-isocyanate hexyl) -1,3-diazetidine-2, 4- It is derived from at least one member selected from the group consisting of ions, 1,3,5-tris (3-isocyanatopropyl) -1,3,5-triazin-2,4,6-trione Can be. More preferably isophorone diisocyanate (IPDI), or 4,4'-dicyclohexylmethane diisocyanate (HMDI), 1,3, -bis (6-isocyanato hexyl) -uretidine-2, 4-dione, 1,3,5-tris (6-isocyanato hexyl) isocyanurate may be derived.

In the low-temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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-ethylbenzene, 1,3-bis (isosia Natomethyl) -5-methylbenzene, 1,3-bis (isocyanatomethyl) -4,5-dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,5-dimethylbenzene, 1,4 -Bis (iso Anatomethyl) -2,3,5,6-tetramethylbenzene, 1,3-bis (isocyanatomethyl) -5-tert-butyl benzene, 1,3-bis (isocyanatomethyl) -4- Chloro benzene, 1,3-bis (isocyanatomethyl) -4,5-dichlorobenzene, 1,3-bis (isocyanatomethyl) -2,4,5,6-tetrachloro benzene, 1,4- Bis (isocyanatomethyl) -2,3,5,6-tetrachloro benzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrabromo benzene, 1,4-bis It may be derived from one or more selected from the group consisting of (2-isocyanatoethyl) benzene, 1,4-bis (isocyanatomethyl) naphthalene.

In the low temperature crosslinkable block isocyanate capable of double curing according to the present invention, 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. Preferably isocyanate functionalized unsaturated acrylic ester, unsaturated urethane acrylate, or two radical isocyanate groups at the end of the molecular chain, and free radical polymerizable unsaturated groups such as vinyl group, acrylic group, methacryl group, etc. 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.

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

<Formula 10>

<Formula 11>

<Formula 12>

<Formula 13>

<Formula 14>

<Formula 15>

<Formula 16>

<Formula 17>

However, in Formula 17, n is an integer of 1 to 5.

In addition, 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.

On the other hand, 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.

In addition, the monomer or oligomer having an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time according to an embodiment of the present invention can be used as the main resin (main resin) and may have a chemical structure of the formula (18).

<Formula 18>

In addition, 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. Preferably, the reactive diluent according to one embodiment of the present invention may be 1,6-hexanediol diacrylate.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. In particular, the technical spirit of the present invention and its core configuration and operation are not limited by this. In addition, the content of the present invention may be implemented in various other forms of equipment, not limited to the embodiments and embodiments 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, may be prepared according to Scheme 1 below.

<Formula 1>

<Scheme 1>

First, 30.0 g (265 mmol) of cyclohexanone oxime was stirred in 300 ml of tetrahydrofuran under argon atmosphere, followed by adding 1.06 g (26.5 mmol) of sodium hydroxide and 45.6 g (221 mmol) of dicyclohexylmethanediimine. Stir at room temperature for hours. After the completion of the reaction, dichloromethane was added, followed by stirring for 30 minutes, followed by filtration under reduced pressure. Concentrated under reduced pressure to remove the solvent, dissolved in hexane and acetonitrile was added and stirred for 1 hour. Thereafter, only the hexane layer was obtained, and the residue was concentrated under reduced pressure to remove 50.47 g (158 mmol) of the compound of <Formula 1>.

Preparation Example 2 Preparation of Compound of Formula 2

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.

<Formula 2>

<Scheme 2>

30.0 g (303 mmol) of cyclopentanone oxime was stirred in 300 ml of tetrahydrofuran in an argon atmosphere, followed by adding 1.21 g (30.3 mmol) of sodium hydroxide and 52.0 g (252 mmol) of dicyclohexylmethanediimine for 24 hours. Stir at room temperature. After the completion of the reaction, dichloromethane was added, followed by stirring for 30 minutes, followed by filtration under reduced pressure. Concentrated under reduced pressure to remove the solvent, dissolved in hexane and acetonitrile was added and stirred for 1 hour. Then, only the hexane layer was obtained, and the residue was concentrated under reduced pressure to obtain 44.8 g (147 mmol) of the compound of <Formula 2>.

Preparation Example 3 Preparation of Compound of Formula 3

Compound of Formula 3 according to an embodiment of the present invention may be prepared according to the following Scheme 3.

<Formula 3>

<Scheme 3>

16.8 g (52.6 mmol) of the compound of Formula 1 are stirred in 50 ml of dichloromethane in an argon atmosphere. Then 3 g (11.4 mmol) of 4,4′-dicyclohexylmethane diisocyanate (HMDI) were added and stirred at 35 ° C. for 60 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent, dissolved in a small amount of dichloromethane, and reprecipitated using diethyl ether / hexane to obtain 4.3 g (4.77 mmol) of the compound of <Formula 3>.

Preparation Example 4 Preparation of Compound of Formula 4

Compound of Formula 4 according to an embodiment of the present invention may be prepared according to the following Scheme 4.

<Formula 4>

<Scheme 4>

11.9 g (38.8 mmol) of the compound are stirred in 50 ml of dichloromethane in an argon atmosphere. Then 3 g (11.4 mmol) of 4,4′-dicyclohexylmethane diisocyanate (HMDI) were added and stirred at 35 ° C. for 60 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent, dissolved in a small amount of dichloromethane, and then reprecipitated using diethyl ether / hexane to obtain 3.4 g (3.89 mmol) of the compound of <Formula 4>.

Preparation Example 5 Preparation of Compound of Formula 5

Compound of Formula 5 according to an embodiment of the present invention may be prepared according to the following Scheme 5.

<Formula 5>

Scheme 5

13.8 g (43.2 mmol) of the compound of Formula 1 are stirred in 50 ml of dichloromethane in an argon atmosphere. Then 3 g (13.5 mmol) of isophorone diisocyanate were added and stirred at 35 ° C. for 60 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent, dissolved in a small amount of dichloromethane, and then reprecipitated using diethyl ether / hexane to obtain 2.91 g (3.38 mmol) of the compound of <Formula 5>.

Preparation Example 6 Preparation of Compound of Formula 6

Compound of Formula 6 according to an embodiment of the present invention 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.

<Formula 6>

Preparation Example 7 Preparation of Compound of Formula 7

Compound of formula 7 according to an embodiment of the present invention may be prepared according to the following Scheme 6.

<Formula 7>

<Scheme 6>

5.97 g (18.7 mmol) of the compound of Formula 1 are stirred in 30 ml of dichloromethane in an argon atmosphere. Thereafter, 3 g (8.92 mmol) of 1,3, -bis (6-isocyanato hexyl) -uretidine-2,4-dione, which is <Formula G>, was added thereto, and the mixture was stirred at room temperature for 6 hours. Concentration under reduced pressure after the completion of the reaction to remove the solvent to obtain 7.92 g (8.12 mmol) of the compound of the formula (7).

Preparation Example 8 Preparation of Compound of Formula 8

Compound of Formula 8 according to an embodiment of the present invention 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.

<Formula 8>

Preparation Example 9 Preparation of Compound of Formula 9

Compound of formula 9 according to an embodiment of the present invention can be prepared according to the following Scheme 7.

<Formula 9>

Scheme 7

7.99 g (25.0 mmol) of the compound of Formula 1 are stirred in 50 ml of dichloromethane in an argon atmosphere. Then 3 g (7.93 mmol) of 1,3,5-tris (6-isocyanatohexyl) isocyanurate (trimer of hexamethylene diisocyanate: HDI trimer) of formula (D) were added and the reaction As the NCO peak disappears as shown in FIG. 1, the mixture was stirred for 6 hours at room temperature after confirming with an IR spectrum. Concentration under reduced pressure after the completion of the reaction 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

Compound of Formula 10 according to an embodiment of the present invention 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.

<Formula 10>

Preparation Example 11 Preparation of Compound of Formula 11

Compound of formula 11 according to an embodiment of the present invention 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.

<Formula 11>

Scheme 8

Preparation Example 12 Preparation of Compound of Formula 12

Compound of formula 12 according to an embodiment of the present invention by the reaction of the compound of formula (2) and 1,2,4-tris (6-isocyanato hexyl) iminooxadiazinedione of formula (E) It was prepared, and the preparation method was prepared in the same manner as in Preparation Example 9.

<Formula 12>

Preparation Examples 13 to 16: Preparation of Compounds of Formulas 13 to 16

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.

<Formula 13>

<Formula 14>

<Formula 15>

<Formula 16>

Preparation Example 17 Preparation of Compound of Formula 17

Compound of formula 17 according to an embodiment of the present invention may be prepared according to the following Scheme 9.

<Formula 17>

However, in Formula 17, n is an integer of 1 to 5.

Scheme 9

2.59 g (36.9 mmol) of the compound of Formula 1 are stirred in an argon atmosphere in 250 ml of dichloromethane. Thereafter, 2 g of Laromer® LR 9000 of Formula 17, which is a compound having two isocyanate reactive groups and one or more free radical polymerizable unsaturated groups of Scheme 9, was added and stirred at 35 ° C. for 24 hours. As the reaction proceeds, the NCO peak disappears as shown in FIG. 2, and the reaction mixture was concentrated under reduced pressure after completion of the reaction while checking in an IR spectrum to obtain 4.6 g of the compound of <Formula 17>.

Test Example 1 Preparation and Curing of Pre-mixture

In order to test the low temperature crosslinkability of the low temperature crosslinked block isocyanate according to one embodiment of the present invention, as the low temperature crosslinkable block isocyanate capable of double curing, the compound of Chemical Formula 9 prepared according to Preparation Example 9 was used. In addition, 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.

Specific manufacturing method and measurement conditions of pre-mixture are as follows. First, 2 g of HFUMO (DCR-4274, Formula 18), a main resin containing 60% double bond (-C = C-) and 80 mg KOH / g hydroxy (-OH) group, 1,6-reactive diluent 1,6- 1 g of hexanediol diacrylate, commercially available block isocyanates (PL350, Bayer Material Science, Desmodur  PL 350 MPA / SN, Blocked Aliphatic Polyisocyanate based on HDI along with Dimethyl Pyrazole, Comparative Example 1), Block Isocyanate of <Formula 3> (Example 1) or Block Isocyanate of <Formula 9> (Example 2) Pre-mixture was prepared by mixing the mixture, and the temperature increase rate condition (UV light: 6.0 mW / for 25 minutes as shown in Figure 4 to measure the curing behavior and modulus according to the temperature of the mixed composition for 25 minutes) cm ₂ , Temperature: 25 _° C., Strain: 2%, Frequency: 5 Hz) was measured with a rotation rheometer (MCR-301, Anton Paar, Austria) and the results are summarized in FIG. 4 and Table 1 below.

Sample	Curing start temperature (℃)	Storage Modulus (Pa)
Comparative Example 1 (PL350)	165	1.7 × 10 6
Example 1 (Formula 3)	98	1.4 × 10 6
Example 2 (Formula 9)	82	1.3 × 10 7

Hardening of the crosslinked composition prepared using the block isocyanate compounds of the commercialized block isocyanate (PL350, Formula 17), Example 1 (Formula 3) and Example 2 (Formula 9), which are Comparative Example 1, as shown in Table 1 above. As a result of the measurement, the curing temperature of Formula 3 and Formula 9 was cured at a temperature much lower than 165 ℃ of PL350 (Comparative Example 1) commercialized at 98 and 82 ℃, respectively. Example 1 Formula 3 Example 2 shows a modulus value equal to or greater than 1.3 × 10 ⁷ Pa of PL350 (Comparative Example 1) commercialized at 1.4 × 10 ⁶ and 1.3 × 10 ⁷ Pa, respectively. .

That is, in the low-temperature crosslinkable composition comprising the block isocyanate compound according to the present invention, as shown in FIG. It can be seen that the curing starts quickly, while Comparative Example 1 increases the modulus, that is, curing starts at 13 minutes, so that the double-curable low-temperature crosslinked block isocyanate according to the present invention is compared under the same elevated temperature conditions It can be seen that curing starts in a short time compared to phosphorus commercial block isocyanates.

As a result, 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. By providing 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.

Test Example 2: Preparation and Curing of Pre-mixture

In order to test the low temperature crosslinkability of the low temperature crosslinked block isocyanate according to one embodiment of the present invention, 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.

Specific manufacturing method and measurement conditions of pre-mixture are as follows. First, 2 g of HFUMO (DCR-4274, Formula 18), a main resin containing 60% double bond (-C = C-) and 80 mg KOH / g hydroxy (-OH) group, (1,6) -Hexanediol diacrylate) 1 g, 0.42 g of the block isocyanate of <Formula 17> were added and mixed to prepare a pre-mixture, shown in Figure 6 to measure the curing behavior and modulus according to the temperature of the mixed composition As measured by a rotation rheometer (MCR-301, Anton Paar, Austria) under a temperature increase rate condition from 20 ° C to 170 ° C for 25 minutes, the results are summarized in FIG. 6.

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. In addition, 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.

As described above, 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.

Claims (12)

1. A double curable low temperature crosslinkable block isocyanate, which is prepared through a urea bond formation reaction of a compound having a compound of Formula A with a polyisocyanate or at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group .

   <Formula A>

   

   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.
2. A low temperature crosslinkable block isocyanate having a chemical structure of formula (B) is possible.

   <Formula B>

   

   In Formula B, 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-C40 aliphatic, aromatic, cycloaliphatic, or aliphatic aliphatic or which contains one or more free radically polymerizable unsaturated groups.
3. The method according to claim 1,

   The compound of formula A is a low temperature crosslinkable block isocyanate capable of double curing, characterized in that the formula (1) or (2).

   <Formula 1>

   

   <Formula 2>

   
4. The method according to claim 1,

   The polyisocyanate compound is an aliphatic, aromatic, alicyclic or aromatic aliphatic compound containing two or more isocyanate groups in the molecular structure, and the isocyanate group of the compound containing the 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 A low crosslinkable block isocyanate capable of double curing, characterized in that at least one selected from the group consisting of dimers, trimers, or oligomers of the compound containing a group.
5. The method according to claim 1,

   The polyisocyanate compound is ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene diisocyanate, 2,2-dimethylpentane diisocyanate Isocyanate, 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 diisocyanate, 2,6-diisocyanate methylcaproate, bis (2-isocyanate ethyl) fumarate, bis (2-isocyanate Ethyl) carbonate, 2-isocyanateethyl-2,6-diisocyanate Sanoate, 1,3,6-hekisamermetrenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyl octane, 2,5,7-trimethyl-1,8-diisocyanato-5- Isocyanatomethyl octane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysine diisocyanato methyl ester, Lysinetriisocyanate, 2-isocyanatoethyl-2,6-diisocyanato ethyl-2,6-diisocyanato hexanoate, 2-isocyanato propyl-2,6-diisocyanato hexanoate, Silylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanato propyl) benzene, α, α, α ', α'-tetramethyl xylylene diisocyanate, bis (isocyanato butyl) benzene, Bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (iso Socyanatoethyl) phthalate, 2,6-di (isocyanatomethyl) furan, 1,3, -bis (6-isocyanatohexyl) -uretidine-2,4-dione, 1,3,5 One or more aliphatic isocyanates or thiodiethyl diisocyanates, thiopropyl diisocyanates, thiodihexyl diisocyanates, dimethylsulfone diisocyanates, ditis selected from the group consisting of tris (6-isocyanato hexyl) isocyanurate At least one sulfur-containing aliphatic isocyanate or diphenyl sulfide-2,4 selected from the group consisting of dimethyl diisocyanate, dithio diethyl diisocyanate, dithio propyl diisocyanate, dicyclohexyl sulfide-4,4'- diisocyanate '-Diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanato dibenzyl thioether, bis (4-isocyanatomethyl Xen) sulfide, at least one aromatic sulfide-based isocyanate selected from the group consisting of 4, 4'-methoxy benzene thioethylene glycol-3,3'- diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2 , 2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-6,6'- Diisocyanate, 4,4'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxy diphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxy diphenyl disulfide A low crosslinkable block isocyanate capable of double curing, characterized in that at least one aliphatic disulfide-based isocyanate selected from the group consisting of -3,3'- diisocyanate.
6. The method according to claim 1,

   The polyisocyanate compound is thiodiethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithio dimethyl diisocyanate, dithio diethyl diisocyanate, dithio propyl diisocyanate, dicyclohexyl sulfide At least one sulfur-containing aliphatic isocyanate or diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'- selected from the group consisting of -4,4'- diisocyanate Dimethoxy-4,4'-diisocyanato dibenzyl thioether, bis (4-isocyanatomethyl benzene) sulfide, group consisting of 4,4'-methoxy benzene thioethylene glycol-3,3'-diisocyanate At least one aromatic sulfide based isocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'- Methyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-6,6'-diisocyanate, 4 , 4'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxy diphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxy diphenyl disulfide-3,3 A low-curing block type isocyanate capable of double curing, characterized in that at least one aliphatic disulfide-based isocyanate selected from the group consisting of '-diisocyanate.
7. The method according to claim 1,

   The polyisocyanate compound is 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-di Phenylenemethane 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'-dimethoxy ratio Phenyl-4-4'-diisocyanate, isopropylenephenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimesterbenzene triisocyanate, benzene tri Soocyanate, triphenylmethane triisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyl diphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenyl At least one aromatic isocyanate or diphenyl sulfone-4,4'-diisocyanate, diphenyl sulfone-3,3'- selected from the group consisting of methane-3,5,2 ', 4', 6'-penta isocyanate 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-butyl diphenyl Consisting of sulfone-3,3'-diisocyanate, 4,4'-methoxy benzene ethylene disulfone-3,3'-diisocyanate, 4,4'-dichlorophenylsulphone-3,3'-diisocyanate Low-temperature crosslinkable block isocyanate, characterized in that at least one aromatic sulfone-based isocyanate selected from the group consisting of.
8. The method according to claim 1,

   The polyisocyanate compound is isophorone diisocyanate (IPDI), 4,4'-dicyclohexyl methane diisocyanate (HMDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanate ethyl) -4 -Cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, 2,2-dimethyl dicyclohexylmethane diisocyanate, bis (4-iso Cyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanato propyl) -5-isocyanatomethyl-bicyclo [2,2, 1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2 -(3-isocyanatopropyl) -5-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 [2,2,1] -heptane, 2-isocyanatomethyl-3- (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- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, norbornane bis (isocyanatomethyl Low-crosslinkable block isocyanate capable of double curing, characterized in that at least one alicyclic isocyanate selected from the group consisting of.
9. The method according to claim 1,

   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 propane-2-yl) benzene (m-tetramethyl xylene diisocyanate, m-TMXDI), 1,4-bis (2-isocyanato propane-2- I) 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, 1,3-bis (isocyanatomethyl) -4,5-dimethylbenzene, 1,4-bis (isocyanatomethyl) -2 , 5-dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetramethylbenzene, 1,3-bis (isocyanatomethyl) -5-tert-butyl benzene, 1 , 3-bis (isocyanatomethyl) -4-chloro benzene, 1,3-bis (isocyanatomethyl) -4,5-dichlorobenzene, 1,3-bis ( Isocyanatomethyl) -2,4,5,6-tetrachloro benzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachloro benzene, 1,4-bis (isosia Natomethyl) -2,3,5,6-tetrabromo benzene, 1,4-bis (2-isocyanatoethyl) benzene, 1,4-bis (isocyanatomethyl) naphthalene A low temperature crosslinkable block isocyanate capable of double curing, which is at least one aromatic aliphatic isocyanate.
10. The method according to claim 1,

    And wherein said compound having at least one isocyanate reactive group and at least one free radical polymerizable unsaturated group is an isocyanate functionalized unsaturated acrylic ester or an isocyanate functionalized unsaturated urethane acrylate.
11. The method according to claim 1,

    The block isocyanate has a chemical structure of any one of the following formulas (3) to (17), wherein the low temperature crosslinkable block isocyanate capable of double curing.

    <Formula 3>

    

    <Formula 4>

    

    <Formula 5>

    <Formula 6>

    

    <Formula 7>

    

    <Formula 8>

    

    <Formula 9>

    

    <Formula 10>

    

    <Formula 11>

    

    <Formula 12>

    

    <Formula 13>

    

    <Formula 14>

    

    <Formula 15>

    

    <Formula 16>

    

    <Formula 17>

    

    However, in Formula 17, n is an integer of 1 to 5.
12. Low temperature crosslinkable block isocyanate capable of double curing according to any one of claims 1 to 11; And

    A low-temperature crosslinkable composition capable of double curing comprising an monomer or oligomer having an ethylenic or acrylic unsaturated double bond and a hydroxyl group at the same time.

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