WO2018235896A1 - Composition d'isocyanate bloqué, composition de revêtement monocomposant, et film de revêtement - Google Patents

Composition d'isocyanate bloqué, composition de revêtement monocomposant, et film de revêtement Download PDF

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Publication number
WO2018235896A1
WO2018235896A1 PCT/JP2018/023604 JP2018023604W WO2018235896A1 WO 2018235896 A1 WO2018235896 A1 WO 2018235896A1 JP 2018023604 W JP2018023604 W JP 2018023604W WO 2018235896 A1 WO2018235896 A1 WO 2018235896A1
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group
compound
blocked isocyanate
composition
acid
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PCT/JP2018/023604
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English (en)
Japanese (ja)
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祐一 三輪
崇史 福地
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旭化成株式会社
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Priority to JP2019525680A priority Critical patent/JP6751209B2/ja
Priority to CN201880041012.5A priority patent/CN110785450B/zh
Publication of WO2018235896A1 publication Critical patent/WO2018235896A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to a blocked isocyanate composition, a one-pack coating composition and a coating film.
  • urethane coatings formed from polyurethane coatings have very good flexibility, chemical resistance and stain resistance.
  • a coating film using a non-yellowing type polyisocyanate composition obtained from an aliphatic diisocyanate represented by hexamethylene diisocyanate (hereinafter sometimes referred to as "HDI") as a curing agent is more weather resistant. Even better, its demand is increasing.
  • Patent Documents 1 and 2 disclose low viscosity triisocyanate compounds, and the use of these triisocyanate compounds in a coating composition can reduce the amount of organic solvent used.
  • the polyisocyanate composition forms a cross-linked coating at normal temperature with a polyol.
  • Polyisocyanate compositions are widely used for baking paints as heat curing type curing agents together with melamine type curing agents.
  • formalin is generated when a melamine-based curing agent is used. Therefore, a polyisocyanate (blocked polyisocyanate) composition blocked by a blocking agent that dissociates the isocyanate group in the polyisocyanate composition by heating is attracting attention from the viewpoint of global environment, safety, hygiene, and the like.
  • a block polyisocyanate composition capable of forming a crosslinked coating film at a relatively low temperature a block polyisocyanate (pyrazole block polyisocyanate) composition using a pyrazole compound as a blocking agent (see, for example, Patent Document 6) Is disclosed. Further, for example, Patent Literatures 7 and 8 disclose triisocyanate blocked by using a pyrazole compound as a blocking agent (hereinafter sometimes referred to as "blocked triisocyanate").
  • Patent Document 9 has a block polyisocyanate composition containing one or more selected from the group consisting of aliphatic isocyanate and alicyclic isocyanate blocked by using a pyrazole compound and an oxime compound as a blocking agent. Objects are disclosed.
  • Japanese Patent Application Laid-Open No. 05-222007 Patent 3055197 gazette Japanese Patent Publication No. 63-015264 Japanese Patent Application Laid-Open No. 53-135931 Japanese Patent Application Laid-Open No. 60-044561 European Patent Application Publication No. 159117 Patent No. 4671668 Unexamined-Japanese-Patent No. 2005-154778 JP 2011-236388 A
  • the present invention has been made in view of the above circumstances, and provides a blocked isocyanate composition having a low viscosity, and low crystallinity, low temperature curability, and storage stability of a paint.
  • the present invention also provides a one-component coating composition and a coating film using the above-mentioned blocked isocyanate composition.
  • a blocked isocyanate composition comprising a blocked isocyanate compound obtained from a triisocyanate compound represented by the following general formula (I) and at least two blocking agents.
  • a plurality of Y 1 s each independently represent a single bond or a divalent C 1 -C 20 divalent group which may contain at least one selected from the group consisting of an ester structure and an ether structure It is a hydrocarbon group.
  • the plurality of Y 1 may be identical to or different from each other.
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • a blocked isocyanate composition which has a low viscosity and is low in crystallinity, low temperature curability, and storage stability of a paint. Moreover, a one-component coating composition and a coating film can be provided by using the blocked isocyanate composition.
  • polyisocyanate means a polymer in which a plurality of monomers having one or more isocyanate groups (—NCO) are bonded.
  • polyol means a compound having two or more hydroxy groups (-OH).
  • (meth) acrylic includes methacryl and acrylic.
  • (meth) acrylate is intended to encompass methacrylate and acrylate.
  • the blocked isocyanate composition according to one embodiment of the present invention comprises at least two types of blocks, a triisocyanate compound represented by the following general formula (I) (hereinafter sometimes referred to as "triisocyanate compound (I)”) And a blocked isocyanate compound obtained from the agent.
  • a triisocyanate compound represented by the following general formula (I) hereinafter sometimes referred to as "triisocyanate compound (I)
  • a blocked isocyanate compound obtained from the agent a blocked isocyanate compound obtained from the agent.
  • a plurality of Y 1 s each independently represent a single bond or a divalent C 1 -C 20 divalent group which may contain at least one selected from the group consisting of an ester structure and an ether structure It is a hydrocarbon group.
  • the plurality of Y 1 may be identical to or different from each other.
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • the blocked isocyanate composition of the present embodiment has a low viscosity by containing the blocked isocyanate compound obtained from the triisocyanate compound (I) and at least two kinds of blocking agents, and has low crystallinity and low temperature curing. And excellent in the storage stability of the paint.
  • the blocked isocyanate compound contained in the blocked isocyanate composition of the present embodiment is obtained from the above triisocyanate compound (I) and at least two kinds of blocking agents.
  • Y 1 a plurality of Y 1 s each independently represent a single bond, or a divalent group having 1 to 20 carbon atoms which may contain at least one selected from the group consisting of an ester structure and an ether structure Is a hydrocarbon group of A plurality of Y 1 s may be identical to or different from each other.
  • the divalent hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic group or an aromatic group.
  • the aliphatic group may be linear, branched or cyclic.
  • an alkanediyl group (alkylene group), an alkylidene group etc. are mentioned, for example.
  • a cycloalkylene group etc. are mentioned, for example.
  • aromatic group arylene groups, such as a phenylene group, are mentioned, for example.
  • an alkylene group having 1 to 6 carbon atoms is preferable.
  • examples of the divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from the group consisting of the ester structure and the ether structure in Y 1 include, for example, a group represented by the following general formula (II) Groups are mentioned. * 1 - (CH 2) n1 -X- (CH 2) n2 - * 2 (II)
  • n1 and n2 are each independently an integer of 0 to 20 satisfying 1 ⁇ n1 + n2 ⁇ 20. That is, both n1 and n2 can not be 0, and it is preferable that n2 connected to NCO be 1 or more.
  • n1 and n2 are each independently more preferably an integer of 0 to 4, and still more preferably an integer of 0 to 2.
  • X is an ester group or an ether group.
  • X is preferably an ester group because the reaction rate is increased.
  • the blocked isocyanate composition of the present embodiment can be made to have a lower viscosity
  • the blocked isocyanate composition of the embodiment can be used as a curing agent for a paint composition to make the resulting coating film more weather resistant.
  • the heat resistance of the blocked isocyanate composition of the present embodiment can be further improved, and the isocyanate when used as a curing agent for the coating composition The reactivity of the group can be further enhanced.
  • the hydrolysis resistance of the blocked isocyanate composition can be further improved.
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • the hydrocarbon group in R 1 is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. Among them, a hydrogen atom is preferable as R 1 .
  • a triisocyanate compound (I) for example, 4-isocyanatomethyl-1,8-octamethylene diisocyanate (hereinafter referred to as "NTI", molecular weight 251) disclosed in JP-B-63-15264 (patent document 3), JP-A-57-198760 1, 3, 6-hexamethylene triisocyanate (hereinafter referred to as "HTI", molecular weight 209) disclosed in Japanese Patent Application Publication No.
  • a triisocyanate compound (I) Is preferably NTI, GTI or LTI, more preferably NTI or LTI, still more preferably LTI.
  • a triisocyanate compound (I) for example, JP-B 4-1033 (reference 2)
  • the LTI molecular weight 267) disclosed in JP-A-53-135931 (Reference 3).
  • a triisocyanate compound (I) for example, JP-B-63-15264 (Patent The NTI (molecular weight 251) disclosed in the literature 3), the HTI (molecular weight 209) disclosed in JP-A-57-198760 (reference 1), and the like can be mentioned.
  • the triisocyanate compound can be obtained, for example, by isocyanation of an amine such as an amino acid derivative, an ether amine and an alkyltriamine.
  • amino acid derivatives examples include 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like. Since these amino acid derivatives are diamine monocarboxylic acid or monoamine dicarboxylic acid, the carboxyl group can be esterified with an alkanolamine such as ethanolamine to give a triamine having an ester group. The triamine having an ester group obtained can be made into a triisocyanate compound containing an ester structure by phosgenation of an amine or the like.
  • ether amine As said ether amine, the brand name "D403" of Mitsui Chemicals Fine Inc. which is polyoxyalkylene triamine etc. are mentioned, for example. These ether amines are triamines and can be converted to triisocyanate compounds containing an ether structure by phosgenation of amines or the like.
  • alkyltriamine examples include triisocyanatononane (4-aminomethyl-1,8-octanediamine) and the like. These alkyltriamines are triamines and can be converted to triisocyanate compounds containing only hydrocarbons by phosgenation of amines or the like.
  • the lower limit value of the molecular weight of the triisocyanate compound is preferably 139 or more, more preferably 150 or more, still more preferably 180 or more, and particularly preferably 200 or more.
  • the upper limit value of the molecular weight of the triisocyanate compound is preferably 1000 or less, more preferably 800 or less, still more preferably 600 or less, and particularly preferably 400 or less. That is, the molecular weight of the triisocyanate compound is preferably 139 or more and 1000 or less, more preferably 150 or more and 800 or less, still more preferably 180 or more and 600 or less, and particularly preferably 200 or more and 400 or less. preferable.
  • crystallinity can be further suppressed
  • the molecular weight is at the upper limit or less, viscosity reduction can be further achieved.
  • the blocked isocyanate compound contained in the blocked isocyanate composition of the present embodiment is a compound in which the isocyanate group of the triisocyanate compound is protected by two or more block agents.
  • the blocking agent include (1) pyrazole compounds, (2) amine compounds, (3) active methylene compounds, (4) oxime compounds, (5) alcohol compounds, (6) alkylphenol compounds, (7) Phenolic compounds, (8) mercaptan compounds, (9) acid amide compounds, (10) acid imide compounds, (11) imidazole compounds, (12) urea compounds, (13) imine compounds , (14) bisulfite, (15) triazole compounds and the like. More specific examples of the blocking agent include those shown below.
  • Pyrazole compounds pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole and the like.
  • Amine compounds diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine, tert-butylbenzylamine and the like.
  • Active methylene compounds dimethyl malonate, diethyl malonate, diisopropyl malonate, di-tert-butyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like.
  • Oxime-type compounds formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime and the like.
  • Alcohol compounds Alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxethanol and 2-butoxyethanol .
  • Alkylphenol-based compounds mono- and dialkylphenols having an alkyl group having 4 or more carbon atoms as a substituent.
  • alkylphenol compound examples include n-propylphenol, iso-propylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol and n-nonylphenol Etc .; di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-t-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol Dialkylphenols such as di-n-nonylphenol. (7) Phenolic compounds: phenol, cresol, ethylphenol, styrenated phenol, hydroxybenzoic acid ester and the like.
  • Acid amide compounds Acetoanilide, acetic acid amide, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and the like.
  • Acid imide compounds Succinimide, maleic imide and the like.
  • Imidazole compounds imidazole, 2-methylimidazole and the like.
  • Urea compounds urea, thiourea, ethylene urea and the like.
  • Imine compounds ethyleneimine, polyethyleneimine and the like.
  • Bisulfite sodium bisulfite and the like.
  • Triazole compounds 3,5-dimethyl-1,2,4-triazole and the like.
  • the at least two blocking agents preferably include a pyrazole compound, and more preferably include at least one member selected from the group consisting of an amine compound, an active methylene compound and an oxime compound, together with the pyrazole compound. . From the viewpoint of low temperature curability, the at least two blocking agents more preferably contain an amine compound or an active methylene compound together with the pyrazole compound.
  • the effects eg, low viscosity, low crystallinity, low temperature curability, etc.
  • 3,5- Dimethylpyrazole is preferred.
  • the amine compound is preferably diisopropylamine or tert-butylbenzylamine.
  • the active methylene compound diethyl malonate or ethyl acetoacetate is preferred.
  • methyl ethyl ketoxime is preferable.
  • the blocking reaction of the triisocyanate compound with the blocking agent can be carried out with or without the presence of a solvent to obtain a blocked isocyanate compound.
  • a solvent inert When using a solvent, it is necessary to use a solvent inert to the isocyanate group.
  • the solvent include ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate and butyl acetate.
  • an organic metal salt such as tin, zinc or lead, a tertiary amine compound, or an alcoholate of an alkali metal such as sodium may be used as a catalyst.
  • the blocking reaction can generally be carried out at -20 ° C or more and 150 ° C or less, preferably 30 ° C or more and 100 ° C or less.
  • the temperature of the block reaction is equal to or higher than the above lower limit value, the reaction rate can be further increased, and by being equal to or lower than the above upper limit value, side reactions can be further suppressed.
  • the proportion of isocyanate groups blocked by the pyrazole compound among the isocyanate groups blocked by the blocking agent is 80 mol% or less from the viewpoint of low crystallinity of the blocked isocyanate composition Is preferably, and more preferably 70 mol% or less.
  • 20 mol% or more is preferable, and 30 mol% or more is more preferable.
  • the blocked isocyanate composition of the polyisocyanate has a structure represented by the following general formula (III), an isocyanurate structure, a burette structure, a uretdione structure, an iminooxadiazine dione structure, a urethane structure and an allophanate It includes a blocked isocyanate compound obtained from a polyisocyanate compound containing at least one member selected from the group consisting of structures, and a blocking agent.
  • Y 1 and R 1 are as described in the general formula (I).
  • the blocked isocyanate composition of the polyisocyanate of the present embodiment is further excellent in low temperature curability.
  • the hydrophilic block isocyanate composition according to one embodiment of the present invention is obtained from the block isocyanate compound in the above-mentioned block isocyanate composition and a compound containing an active hydrogen group and a hydrophilic group (hydrophilic group-containing compound) It contains a hydrophilic block isocyanate compound. Since the hydrophilic block isocyanate composition of the present embodiment is excellent in water dispersibility, it can be easily dispersed in a hydrophilic solvent.
  • ⁇ Hydrophilic block isocyanate compound> By reacting the isocyanate group of the blocked isocyanate compound in the above-described blocked isocyanate composition with the hydrophilic group-containing compound, a hydrophilic blocked isocyanate compound to which a hydrophilic group is added can be obtained.
  • a hydrophilic group containing compound which can be reacted with an isocyanate group For example, the compound containing hydrophilic groups, such as nonionicity, cationic property, anionic property, is mentioned.
  • Nonionic hydrophilic group Although it does not specifically limit as a compound containing a nonionic hydrophilic group, for example, the compound etc. which added ethylene oxide to the hydroxyl group of alcohol, such as methanol, ethanol, butanol, ethylene glycol, diethylene glycol, etc. are mentioned. These compounds have active hydrogen which reacts with isocyanate groups. Among them, since the water dispersibility of the hydrophilic polyisocyanate composition can be improved with a small amount used, a monoalcohol having ethylene oxide is preferable as the compound containing a nonionic hydrophilic group.
  • a content number of ethylene oxide in the compound containing a nonionic hydrophilic group 4 or more and 30 or less are preferable, and 4 or more and 20 or less are more preferable.
  • the number of ethylene oxide contained is equal to or more than the above lower limit value, it tends to be easy to secure water-ization.
  • the precipitate of the hydrophilic block isocyanate composition tends to be less likely to be generated during low temperature storage.
  • a cationic hydrophilic group When a cationic hydrophilic group is introduced into the above-mentioned blocked isocyanate compound to obtain a hydrophilic blocked isocyanate compound, for example, a compound having both a cationic hydrophilic group and a functional group having hydrogen which reacts with an isocyanate group is used.
  • a method to be used a method of adding a functional group such as a glycidyl group to an isocyanate group in advance, and then allowing this functional group to react with a specific compound such as sulfide or phosphine may be mentioned.
  • the compound having both the cationic hydrophilic group and a functional group having hydrogen which reacts with an isocyanate group is not particularly limited, and examples thereof include dimethylethanolamine, diethylethanolamine, diethanolamine, methyldiethanolamine, N, N-dimethyl Aminohexanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N- (dimethylaminopropyl) aminoethanol, etc. It can be mentioned.
  • hydrophilic block isocyanate compound When the hydrophilic block isocyanate compound has a tertiary amino group as a cationic hydrophilic group, it can be quaternized with dimethyl sulfate, diethyl sulfate or the like.
  • a cationic hydrophilic group which a hydrophilic block isocyanate compound has a tertiary amino group is preferable.
  • a compound such as an anionic compound used for neutralization described later tends to be volatilized by heating, and as a result, the water resistance tends to be further improved.
  • introduction of the cationic hydrophilic group to the above-mentioned blocked isocyanate compound can be performed in the presence of a solvent.
  • the solvent preferably does not contain a functional group capable of reacting with an isocyanate group.
  • the solvent is not particularly limited, and examples thereof include ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether and the like.
  • the hydrophilic blocked isocyanate compound has a cationic hydrophilic group
  • the cationic hydrophilic group is preferably neutralized with a compound having an anionic group.
  • anion group For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a halogen group, a sulfuric acid group etc. are mentioned.
  • the compound having one carboxyl group as an anion group is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid and lactic acid.
  • a compound which has a sulfonic acid group as an anion group although it does not specifically limit, an ethane sulfonic acid etc. are mentioned, for example.
  • a compound which has a phosphoric acid group as an anion group although it does not specifically limit, For example, phosphoric acid, an acidic phosphoric acid ester, etc. are mentioned.
  • the compound having a halogen group as an anion group is not particularly limited, and examples thereof include hydrochloric acid and the like.
  • a compound which has a sulfate group as an anion group For example, a sulfuric acid etc. are mentioned. Among them, as a compound having an anion group, a compound having one carboxyl group is preferable, and acetic acid, propionic acid or butyric acid is more preferable.
  • the anionic hydrophilic group is not particularly limited, and examples thereof include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a halogen group and a sulfuric acid group.
  • the hydrophilic blocked isocyanate compound having an anionic hydrophilic group is, for example, reacting the active hydrogen of a compound having an anionic group and the active hydrogen of the compound having an anionic hydrophilic group with the isocyanate group of the above-described blocked isocyanate compound. Can be obtained by
  • the compound having active hydrogen and a carboxylic acid group is not particularly limited, and examples thereof include monohydroxy such as 1-hydroxyacetic acid, 3-hydroxypropanoic acid, 12-hydroxy-9-octadecanoic acid, hydroxypivalic acid, and lactic acid.
  • Carboxylic acids include polyhydroxycarboxylic acids such as dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, and dimethylolpropionic acid. Among them, as a compound having active hydrogen and a carboxylic acid group, hydroxypivalic acid or dimethylol propionic acid is preferable.
  • the compound having active hydrogen and a sulfonic acid group is not particularly limited, and examples thereof include isethionic acid.
  • the anionic hydrophilic group is preferably neutralized with a compound having a cationic group.
  • the compound having a cationic group is not particularly limited, and examples thereof include amine compounds which are basic substances.
  • amine compound For example, ammonia, a water-soluble amino compound, etc. are mentioned.
  • water-soluble amino compounds include, but are not limited to, monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, and the like.
  • Primary or secondary amines such as ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine and morpholine; and tertiary amines such as triethylamine and dimethylethanolamine.
  • the one-pack type paint composition which concerns on one Embodiment of this invention contains the above-mentioned blocked isocyanate composition and a polyol.
  • the above-described blocked isocyanate composition can be suitably used as a curing agent or the like of the one-component coating composition of the present embodiment. Therefore, the one-component coating composition of the present embodiment can improve the weather resistance of the resulting coating film by including the above-described blocked isocyanate composition.
  • the one-component coating composition of the present embodiment contains the above-described blocked isocyanate composition and a polyol as a resin component.
  • resin components other than polyols include polyamines and polythiols.
  • polyol examples include polyester polyol, polyether polyol, acrylic polyol, polyolefin polyol, fluorine polyol and the like.
  • acrylic polyol is preferable as the polyol from the viewpoint of weather resistance, chemical resistance and hardness.
  • polyester polyols are preferable from the viewpoint of mechanical strength and oil resistance.
  • polyester polyol The polyester polyol can be obtained, for example, by condensation reaction of a dibasic acid alone or a mixture of two or more with a polyhydric alcohol alone or a mixture of two or more.
  • dibasic acid examples include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid and the like.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin and pentaerythritol. And 2-methylolpropanediol, ethoxylated trimethylolpropane and the like.
  • the condensation reaction can be carried out by mixing the above-mentioned components and heating at about 160 to 220 ° C.
  • polycaprolactones obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone using polyhydric alcohol can also be used as the polyester polyol.
  • These polyester polyols can be modified with aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, polyisocyanates obtained therefrom, and the like. Among them, from the viewpoint of weatherability, yellowing resistance and the like, it is preferable to modify the polyester polyol using aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained therefrom.
  • the one-component coating composition of the present embodiment is used as a water-based base coating
  • some carboxylic acid derived from a dibasic acid or the like in the polyester polyol is left, and a base such as amine or ammonia is used.
  • the polyester polyol can be made water soluble or water dispersible resin.
  • polyether polyol The polyether polyol can be obtained, for example, using any of the following methods (1) to (3).
  • a method of obtaining polyether polyols by random or block addition of an alkylene oxide alone or a mixture with a polyhydroxy compound alone or a mixture using a catalyst examples include hydroxides (lithium, sodium, potassium, etc.), strongly basic catalysts (alcoholate, alkylamines, etc.), complex metal cyanide complexes (metal porphyrin, zinc hexacyanocobaltate complex, etc.), etc.
  • the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide and the like.
  • polyvalent hydroxy compound examples include the following.
  • diglycerin ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.
  • Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, rhamnitol and the like.
  • Tetrasaccharides such as stachyose.
  • Acrylic polyols for example, polymerize a polymerizable monomer having one or more active hydrogens in one molecule, or, if necessary, a polymerizable monomer having one or more active hydrogens in one molecule. It can be obtained by copolymerizing the polymerizable monomer and the other copolymerizable monomer.
  • Examples of the polymerizable monomer having one or more active hydrogens in one molecule include the following. These may be used alone or in combination of two or more.
  • Examples of the other monomer copolymerizable with the polymerizable monomer include the following. These may be used alone or in combination of two or more.
  • Unsaturated amides such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like (unsaturated carboxylic acids such as acrylamide, N-methylol acrylamide, diacetone acrylamide and the like).
  • Vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ - (meth) acrylopropyltrimethoxysilane and the like.
  • Other polymerizable monomers such as styrene, vinyl toluene, vinyl acetate, acrylonitrile and dibutyl fumarate.
  • the above-mentioned monomer (monomer) component is solution-polymerized in the presence of a known radical polymerization initiator such as peroxide or azo compound, and, if necessary, Examples thereof include a method of obtaining an acrylic polyol by dilution with an organic solvent or the like.
  • the one-component coating composition of the present embodiment is used as a water-based base coating
  • a known method such as solution polymerization of the above-mentioned monomer component and conversion to an aqueous layer or emulsion polymerization is used.
  • a water-based acrylic polyol can be produced.
  • polyolefin polyol examples include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, polyisoprene having two or more hydroxyl groups, hydrogenated polyisoprene having two or more hydroxyl groups, and the like. Further, in the polyolefin polyol, the number of hydroxyl groups is preferably 3 because higher coating strength can be obtained.
  • fluorine polyol means a polyol containing fluorine in the molecule.
  • fluorine polyol include fluoroolefins, cyclovinyl ethers and hydroxy compounds disclosed in, for example, JP-A-57-34107 (Reference 4) and JP-A-61-275311 (Reference 5).
  • Copolymers, such as alkyl vinyl ether and monocarboxylic acid vinyl ester, etc. are mentioned.
  • the lower limit value of the hydroxyl value of the polyol is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, and still more preferably 30 mg KOH / g or more.
  • the upper limit value of the hydroxyl value of the polyol is not particularly limited, and may be, for example, 200 mg KOH / g or less.
  • the hydroxyl value of the polyol is preferably 10 mg KOH / g or more and 200 mg KOH / g or less, more preferably 20 mg KOH / g or more and 200 mg KOH / g or less, and further preferably 30 mg KOH / g or more and 200 mg KOH / g or less preferable.
  • the acid value of a polyol is 0 mgKOH / g or more and 30 mgKOH / g or less.
  • the hydroxyl value and the acid value can be measured in accordance with JIS K1557.
  • [NCO / OH] 0.2 or more and 5.0 or less are preferable, and 0.4 or more and 3.0 or less of the molar equivalent ratio (NCO / OH) of the isocyanate group of the above-mentioned block isocyanate composition to the hydroxyl group of the said polyol are more preferable, 0 More preferably, it is not less than 0.5 and not more than 2.0.
  • the molar equivalent ratio is equal to or more than the above lower limit value, it is possible to obtain a tougher coating. By the said molar equivalent ratio being below the said upper limit, the smoothness of the coating film obtained can be improved further.
  • the one-component coating composition of the present embodiment may contain a melamine-based curing agent such as a complete alkyl type, methylol type alkyl, imino group type alkyl, etc., as necessary.
  • the one-component coating composition of the present embodiment may contain an organic solvent.
  • the said polyol and the above-mentioned blocked isocyanate composition may contain the organic solvent.
  • an organic solvent what is necessary is just to have a functional group which reacts with a hydroxyl group and an isocyanate group.
  • Specific examples of the organic solvent include ester compounds such as butyl acetate, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, polyethylene glycol dicarboxylate compounds, hydrocarbon solvents, aroma And organic solvents generally used as paint solvents such as group solvents.
  • the one-pack type paint composition of the present embodiment is a catalyst for promoting curing, a pigment, a leveling agent, an antioxidant, an ultraviolet absorber, and the like within the range not to impair the effects of the present embodiment depending on the purpose and application. It may contain various additives used in the art such as light stabilizers, plasticizers, surfactants and the like. Moreover, the said polyol and the above-mentioned block isocyanate composition may contain the said various additive.
  • metal salts such as dibutyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt salt, etc .; triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N-dimethyldimethylamine And tertiary amines such as cyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N'-endoethylenepiperazine, N, N'-dimethylpiperazine and the like.
  • the one-component coating composition of the present embodiment can be used, for example, as a coating such as roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating and the like.
  • the one-component coating composition of the present embodiment is useful as, for example, a primer for a material such as metal (steel sheet, surface-treated steel sheet, etc.), plastic, wood, film, inorganic material, and upper middle coat.
  • the one-component coating composition of the present embodiment imparts, for example, a precoat metal including a rust-proof steel plate, a coated part of an automobile, etc. with a cosmetic property, weather resistance, acid resistance, rust resistance, chipping resistance, etc.
  • the one-component coating composition of the present embodiment is also useful as a urethane raw material such as, for example, an adhesive, a pressure-sensitive adhesive, an elastomer, a foam, and a surface treatment agent.
  • the one-component coating composition of the present embodiment may be either solvent-based or water-based.
  • the one-pack coating composition is solvent-based, it can be prepared by the following method. First, if necessary, additives such as other resins, catalysts, pigments, leveling agents, antioxidants, UV absorbers, light stabilizers, plasticizers, surfactants, etc. are added to the polyol or its solvent diluent. . Next, the above-described blocked isocyanate composition is added as a curing agent, and if necessary, a solvent is further added to adjust the viscosity. Then, the solvent-based one-component coating composition can be obtained by stirring with a hand or using a stirring device such as Magellar.
  • the one-pack type paint composition When the one-pack type paint composition is water-based, it can be prepared by the following method. First, according to need, other resins, catalysts, pigments, leveling agents, antioxidants, UV absorbers, light stabilizers, plasticizers, surfactants, as needed, to water dispersions or water soluble substances of polyols containing resins Add additives such as Then, the above-described blocked isocyanate composition is added as a curing agent, and water and a solvent are further added, if necessary, and then forced agitation is performed using a stirring device to obtain an aqueous-based one-component coating composition. Can.
  • the coating film which concerns on one Embodiment of this invention hardens the above-mentioned one-component-type coating composition.
  • the coating film of this embodiment is obtained by coating and curing the above-described one-component coating composition using a known method such as roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating and the like. Be
  • the coating film of the present embodiment has good weatherability and hardness.
  • NCO content (% by mass) was determined by back titration with 1N hydrochloric acid after neutralizing the isocyanate group in the measurement sample with excess 2N amine.
  • ⁇ Viscosity> The viscosity was measured at 25 ° C. using an E-type viscometer (manufactured by Tokimec). In measurement, a standard rotor (1 ° 34 ′ ⁇ R24) was used. The rotation speed was set as shown below.
  • ⁇ Method for evaluating viscosity reduction degree of blocked isocyanate composition Two hours after the synthesis, the viscosity at 25 ° C. of the blocked isocyanate composition was measured using an E-type viscometer (manufactured by Tokimec) as described above. As the evaluation method, the case where the viscosity is less than 800 mPa ⁇ s is ⁇ , and the case where the viscosity is 800 mPa ⁇ s or more is x.
  • ⁇ Method for evaluating crystallization of blocked isocyanate composition 40 g of the blocked isocyanate composition was charged in a 50 mL sample bottle, stored at 23 ° C., and crystallization was visually observed. As an evaluation method, the case where it does not crystallize in 30 days or more is ⁇ , the case where it crystallizes in 2 days or more and less than 30 days is ⁇ , the case where it crystallizes in 1 day or more and less than 2 days is ⁇ , the crystals in less than 1 day The case of conversion was regarded as x.
  • Each block isocyanate composition after evaluation of crystallinity and acrylic polyol (trade name “SETALUX 1152” manufactured by Nuplex Resin, resin content concentration 61%, hydroxyl value 84.6 mg KOH / g), molar equivalent of isocyanate group / hydroxy group
  • the paint composition was prepared so as to be formulated at a ratio of 1.0 and to have a solid content of 50% by mass with butyl acetate.
  • Each prepared coating composition was coated on a PP plate to a dry film thickness of 40 ⁇ m. Then, the film was heated at 110 ° C. for 30 minutes to be cured to obtain a coating.
  • the gel fraction of the obtained coating film was calculated using the method shown below, and low temperature curability was evaluated. Specifically, the gel fraction (% by mass) was obtained by immersing the obtained coated film in acetone at 23 ° C. for 24 hours, and then the ratio of the mass of the undissolved portion to the coated film mass before immersion was calculated. In addition, as the evaluation method, the case where the gel fraction is 85% by mass or more is ⁇ , the case where 70% by mass or more and less than 85% by mass is ⁇ , the case where 20% by mass or more and less than 70% by mass is ⁇ , less than 20% by mass The combination of was marked x.
  • Synthesis Example 1 Synthesis of NTI 4-Aminomethyl-1,8-octamethylenediamine (hereinafter sometimes referred to as “triamine”) in a four-necked flask equipped with a stirrer, thermometer, and gas inlet tube 1060 g was dissolved in 1500 g of methanol, and to this, 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise while cooling. It was then concentrated under reduced pressure to remove methanol and water, and dried at 60 ° C./5 mmHg for 24 hours to obtain triamine hydrochloride as a white solid.
  • triamine 4-Aminomethyl-1,8-octamethylenediamine
  • the obtained triamine hydrochloride (650 g) was suspended as a fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was raised while stirring. Then, when the reaction solution reached 100 ° C., phosgene was started to be blown at a rate of 200 g / hr and heating was continued further. Then, when the reaction solution reached 180 ° C., the temperature was maintained and phosgene was kept blowing for 12 hours.
  • Synthesis Example 2 Synthesis of LTI 122.2 g of ethanolamine, 100 mL of o-dichlorobenzene, and 420 mL of toluene are placed in a four-necked flask equipped with a stirrer, thermometer, and gas inlet tube, and ice-cold hydrogen chloride gas is added It was introduced and ethanolamine was converted to hydrochloride. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to a temperature of 80 ° C., ethanolamine hydrochloride was dissolved, and hydrogen chloride gas was introduced to form lysine dihydrochloride.
  • Example 1 Production of Blocked Isocyanate Composition 1
  • a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blow-in pipe was made to have a nitrogen atmosphere, and NTI (10.0 g), butyl acetate (9. 9 g). 0 g) was charged and the temperature was adjusted to 70.degree.
  • NTI 10.0 g
  • butyl acetate 9. 9 g
  • 0 g was charged and the temperature was adjusted to 70.degree.
  • 3,5-dimethylpyrazole (5.7 g, 50 mol%) and methyl ethyl ketoxime (5.2 g, 50 mol%) were added dropwise to a four-necked flask and maintained for 2 hours.
  • an NCO content of 0.0% by mass was confirmed, and a blocked isocyanate composition 1 was obtained.
  • the calculated NCO content of the resulting blocked isocyanate composition 1 was 16.8% by mass. Furthermore, the evaluation of degree of viscosity reduction was ⁇ , the evaluation of crystallization was ⁇ , the evaluation of low temperature curability was ⁇ , and the storage stability evaluation of the paint was ⁇ . The results are shown in Table 1.
  • Examples 2 to 5 and 7 to 12 and Comparative Examples 1 and 2 Preparation of Blocked Isocyanate Composition 2 to 5 and 7 to 14
  • the used mass of the triisocyanate compound, the blocking agent and the diluent, and the addition ratio of the blocking agent Blocked isocyanate compositions 2 to 5 and 7 to 14 were produced in the same manner as in Example 1 except that the conditions were as shown in Table 1 or Table 2.
  • the calculated NCO content, the degree of viscosity reduction, the crystallization evaluation, and the low-temperature curing results of each of the obtained blocked isocyanate compositions are shown in Table 1 or Table 2.
  • Comparative Example 1 the crystallization was so remarkable that the coating composition could not be prepared, and the low temperature curability and the storage stability of the coating could not be evaluated.
  • Example 6 Production of Blocked Isocyanate Composition 6
  • a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blow-in pipe was made to have a nitrogen atmosphere, and NTI (10.0 g), butyl acetate (3. 6 g), diethyl malonate (9.5 g, 50 mol%) was charged and the temperature was brought to 70.degree.
  • a 30% by mass methanol solution (0.05 g) of sodium methylate was added to a four-necked flask and allowed to react at 70 ° C. for 3 hours.
  • Comparative Example 4 Production of Blocked Isocyanate Composition 16 The same method as Comparative Example 3 except that the use amounts of the HDI-based polyisocyanate, the blocking agent and the diluent, and the addition ratio of the blocking agent are as shown in Table 2. To produce a blocked isocyanate composition 16. The calculated NCO content, the degree of viscosity reduction, the crystallization evaluation, and the low temperature curability results of the obtained blocked isocyanate composition 16 are shown in Table 2.
  • the blocked isocyanate compositions obtained in Examples 1 to 12 had low viscosity, low crystallinity and low temperature curability, and were excellent in the storage stability of the paint.
  • the blocked isocyanate composition obtained in Comparative Example 1 the crystallization was so remarkable that the paint composition could not be prepared, and the evaluation of low temperature curability and storage stability of the paint could not be carried out.
  • the blocked isocyanate composition obtained in Comparative Example 2 was inferior in low temperature curability.
  • the blocked isocyanate composition obtained in Comparative Example 3 had a high viscosity.
  • the blocked isocyanate composition obtained in Comparative Example 4 had a high viscosity and was inferior in the storage stability of the paint. From the above, it was confirmed that the blocked isocyanate composition of the present embodiment has a low viscosity and is excellent in low-temperature curability and low crystallinity.
  • the blocked isocyanate composition of the present embodiment has a low viscosity, and has excellent low crystallinity and low temperature curability.
  • the one-component coating composition using the blocked isocyanate composition as a curing agent can be used as a coating for roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating and the like.
  • the one-component coating composition using the block isocyanate composition as a curing agent is a primer such as a steel plate, a metal such as a surface-treated steel plate, and a primer or a top middle coat on a material such as plastic, wood, film or inorganic material. It can be used as a paint.
  • the one-component coating composition using the blocked isocyanate composition as a curing agent imparts heat resistance, cosmetic properties (surface smoothness, sharpness), etc. to a precoated metal containing a rustproof steel plate, automobile coating, etc. It is also useful as a paint.
  • the one-component coating composition using the blocked isocyanate composition as a curing agent is also useful as a urethane material for adhesives, adhesives, elastomers, foams, surface treatment agents and the like.

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

Abstract

L'invention concerne une composition d'isocyanate bloqué, qui contient un composé isocyanate bloqué obtenu à partir d'un composé triisocyanate représenté par la formule générale (I) et d'au moins deux agents bloquants. (Dans la formule générale (I), chacun de la pluralité des fragments Y1 représente d'une manière indépendante une liaison simple ou un groupe hydrocarboné divalent ayant 1 à 20 atomes de carbone, qui peut contenir au moins une structure choisie dans le groupe consistant en une structure ester et une structure éther ; la pluralité de fragments Y1 peuvent être identiques les uns aux autres ou différents les uns des autres ; et R1 représente un atome d'hydrogène ou un groupe hydrocarboné monovalent ayant 1 à 12 atomes de carbone.)
PCT/JP2018/023604 2017-06-23 2018-06-21 Composition d'isocyanate bloqué, composition de revêtement monocomposant, et film de revêtement WO2018235896A1 (fr)

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WO2022059774A1 (fr) * 2020-09-18 2022-03-24 三井化学株式会社 Isocyanate bloqué dispersible dans l'eau, agent de traitement de fibres, agent hydrofuge, composition de revêtement et adhésif
WO2023162870A1 (fr) * 2022-02-28 2023-08-31 旭化成株式会社 Composition d'isocyanate séquencé, composition de matériau de revêtement et film de revêtement

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