WO2017094883A1 - Composition de polyisocyanate et composition de revêtement l'utilisant - Google Patents

Composition de polyisocyanate et composition de revêtement l'utilisant Download PDF

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Publication number
WO2017094883A1
WO2017094883A1 PCT/JP2016/085899 JP2016085899W WO2017094883A1 WO 2017094883 A1 WO2017094883 A1 WO 2017094883A1 JP 2016085899 W JP2016085899 W JP 2016085899W WO 2017094883 A1 WO2017094883 A1 WO 2017094883A1
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Prior art keywords
polyisocyanate
polyisocyanate composition
group
composition
flip
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PCT/JP2016/085899
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English (en)
Japanese (ja)
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長岡毅
喜多求
岸本龍介
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東ソー株式会社
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Priority claimed from JP2016135701A external-priority patent/JP2018002972A/ja
Priority claimed from JP2016208838A external-priority patent/JP6840991B2/ja
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Publication of WO2017094883A1 publication Critical patent/WO2017094883A1/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
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • 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 polyisocyanate composition useful as a curing agent for obtaining a polyurethane resin and a coating composition using this as a curing agent.
  • non-yellowing polyisocyanates derived from aliphatic isocyanates such as 1,6-hexamethylene diisocyanate have excellent weather resistance.
  • the polyisocyanate type containing an isocyanurate bond has high chemical and thermal stability, and is particularly excellent in weather resistance, heat resistance and durability, and is therefore widely used according to its application.
  • the coating composition using this polyisocyanate has a high-grade appearance, it is often used for automobiles, information terminal equipment, home appliances, architecture, and the like.
  • the clear top is required to have a high-grade appearance and excellent durability, and in particular, it needs strength at high temperatures assuming high temperatures in summer.
  • a polyisocyanate composition obtained by nurating a diisocyanate such as HDI described in Patent Document 1 or a diisocyanate such as HDI described in Patent Document 2 A polyisocyanate composition having a higher number of functional groups has been used by isocyanuration using a monohydric alcohol as a raw material.
  • this isocyanate composition has good strength at high temperatures, but flip-flop properties when forming an aqueous base layer and a multilayer coating film are considered insufficient at the present time when high designability is required. Yes.
  • Patent Document 3 describes that a part of the polyisocyanate in the clear top paint mainly composed of a hydroxyl group-containing resin and a polyisocyanate compound is transferred to the lower layer to improve interlayer adhesion.
  • the polyisocyanate described in Patent Document 1 has a biuret structure, it has a problem of low strength and low weather resistance.
  • Patent Document 4 describes that by using an uretdione dimer of HDI as a clear-top curing agent, the base layer can be sufficiently cross-linked and good coating properties can be obtained.
  • the isocyanate has a uretdione structure, there is a problem that strength is low and weather resistance is low.
  • isocyanate compositions obtained by reacting diisocyanates such as HDI described in Patent Documents 5 and 6 with alcohols having a cyclic structure to form allophanates have been proposed.
  • the performance of the coating film obtained using this isocyanate composition is high strength and high hardness, but the flip-flop property when a multilayer coating film is formed is insufficient.
  • the present invention has been made in view of the background art described above.
  • the first problem of the present invention is that it has excellent mechanical properties at high temperatures when used as a curing agent for clear top, and has a flip-flop property when an aqueous base layer and a multilayer coating film are formed.
  • An object is to provide an isocyanate composition and a coating composition using the same as a curing agent.
  • the second problem of the present invention is that when used as a curing agent for clear top, it has excellent permeability from the clear top layer to the base layer for improving interlayer adhesion, excellent weather resistance, and mechanical properties at high temperatures.
  • An object of the present invention is to provide a polyisocyanate composition having high flip-flop properties when a metallic base layer and a multilayer coating film are formed, a coating composition using this as a curing agent, and a coating film using the same.
  • the present inventors have found that the first problem can be solved by a polyisocyanate composition (a) obtained by reacting a specific diol with an aliphatic polyisocyanate.
  • a polyisocyanate composition (a) capable of solving one problem and a polyisocyanate composition (b) having an allophanate group which is a reaction product of a specific monool and an aliphatic polyisocyanate;
  • the second problem can be solved by including a polyisocyanate composition (c) having an isocyanurate group, and has led to the present invention.
  • the present invention includes the following embodiments.
  • a polyisocyanate composition comprising a reaction product with a diol, wherein the reaction product contains an allophanate group.
  • a polyisocyanate composition comprising polyisocyanate compositions (a), (b), and (c),
  • the polyisocyanate composition (a) is the polyisocyanate composition according to any one of the above [1] to [4], Reaction product of polyisocyanate composition (b) of at least one isocyanate compound selected from the group consisting of aliphatic polyisocyanates and isocyanate group-terminated prepolymers of aliphatic polyisocyanates with monoalcohols having 1 to 3 carbon atoms
  • the polyisocyanate composition (c) is a polyisocyanate group that is a cyclopolymerized product of at least one isocyanate compound selected from the group consisting of aliphatic polyisocyanates and isocyanate group-terminated prepolymers of aliphatic polyisocyanates.
  • Isocyanate composition A polyisocyanate composition characterized by the above.
  • the molar ratio of the total allophanate groups and isocyanurate groups contained in the polyisocyanate compositions (a) to (c) is 85/15 to 35/65, Polyisocyanate composition.
  • the calculated value of the flip-flop value according to the following formula 1 is higher than the calculated value of the flip-flop value of the coating film using only the hexamethylene diisocyanate polyisocyanurate as the polyisocyanate composition, The coating film using the polyisocyanate composition in any one of said [1] thru
  • Flip-flop value 2.69 ⁇ (L * 15 ° ⁇ L * 110 °) 1.11 / (L * 45 °) 0.86 (Formula 1) (L * 15 °, L * 45 °, and L * 110 ° in Equation 1 above represent L * measurement values at angles of 15 °, 45 °, and 110 ° by a multi-angle colorimeter, respectively).
  • Flip-flop value 2.69 ⁇ (L * 15 ° ⁇ L * 110 °) 1.11 / (L * 45 °) 0.86 (Formula 1) (L * 15 °, L * 45 °, and L * 110 ° in Equation 1 above represent L * measurement values at angles of 15 °, 45 °, and 110 ° by a multi-angle colorimeter, respectively).
  • a two-component coating composition containing the polyisocyanate composition according to any one of [1] to [8] above and a polyol.
  • a two-component paint composition characterized by comprising:
  • the calculated value of the flip-flop value according to the following formula 1 is higher than the calculated value of the flip-flop value of the coating film using only the hexamethylene diisocyanate polyisocyanurate as the polyisocyanate composition, A coating film using the two-component coating composition according to [11] or [12].
  • Flip-flop value 2.69 ⁇ (L * 15 ° ⁇ L * 110 °) 1.11 / (L * 45 °) 0.86 (Formula 1) (L * 15 °, L * 45 °, and L * 110 ° in Equation 1 above represent L * measurement values at angles of 15 °, 45 °, and 110 ° by a multi-angle colorimeter, respectively).
  • the two-component coating composition described in [11] or [12] is cured in an environment of temperature ⁇ 5 ° C. to 120 ° C. and humidity 10 to 95% RH in 0.5 to 168 hours.
  • the manufacturing method of the coating film characterized by the above-mentioned.
  • Embodiment 1 means for solving the first problem is referred to as Embodiment 1
  • Embodiment 2 means for solving the second problem is referred to as Embodiment 2.
  • the polyisocyanate composition of the present invention has excellent mechanical properties at high temperatures when used as a clear-top curing agent, and a flip-flop when an aqueous base layer and a multilayer coating film are formed. It is possible to obtain a polyisocyanate composition having high properties and a two-component coating composition using this as a curing agent.
  • a polyisocyanate composition capable of obtaining the first effect, a polyisocyanate composition having an allophanate group which is a reaction product of a specific monool and an aliphatic polyisocyanate, With a polyisocyanate composition containing a polyisocyanate composition having a nurate group, when used as a curing agent for clear top, it has excellent permeability from the clear top layer to the base layer, weather resistance, and excellent mechanical properties at high temperatures In addition, a polyisocyanate composition having high flip-flop properties when a base layer and a multilayer coating film are formed, a coating composition using this as a curing agent, and a coating film using the same can be obtained.
  • the polyisocyanate composition that solves the first problem of the present invention has at least one isocyanate compound selected from the group consisting of aliphatic polyisocyanates and isocyanate group-terminated prepolymers of aliphatic polyisocyanates, and side chains.
  • a polyisocyanate composition comprising a reaction product with an acyclic aliphatic diol having 2 to 3 carbon atoms between hydroxyl groups, and the reaction product contains an allophanate group (hereinafter referred to as “polyisocyanate composition”).
  • the aliphatic polyisocyanate monomer (hereinafter also simply referred to as aliphatic polyisocyanate) that can be used in the polyisocyanate composition (a) is a polyisocyanate compound that does not contain a benzene ring in its structure.
  • examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. be able to.
  • hexamethylene diisocyanate is preferable from the viewpoint of weather resistance and industrial availability.
  • the aliphatic polyisocyanate may be used alone or in combination, and an alicyclic diisocyanate represented by isophorone diisocyanate or norbornene diisocyanate may be used in combination.
  • the acyclic aliphatic diol having a side chain that can be used in the polyisocyanate composition (a) and having 2 to 3 carbon atoms between hydroxyl groups has a minimum carbon number of 2 to 3 connecting two hydroxyl groups
  • the carbon chain has at least one side chain and is represented by the following chemical formulas 1 and 2.
  • the side chain here is preferably an alkyl group having 1 or more carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 or more carbon atoms, provided that at least one of R 1 to R 4 is an alkyl group).
  • R 1 to R 6 each independently represents a hydrogen atom or an alkyl group having 1 or more carbon atoms, provided that at least one of R 1 to R 6 is an alkyl group).
  • the acyclic aliphatic diol having a side chain and having 2 to 3 carbon atoms between hydroxyl groups in the present invention does not contain a ring structure in the molecule, and specifically includes, for example, 1,2-propane.
  • Examples include diol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol and the like that do not contain a ring structure in the molecule.
  • the above diols may be used alone or in combination.
  • 1,2-propanediol and 2,3-butanediol having a low molecular weight are preferable for increasing the isocyanate content, but 2,2-dimethyl-1 is preferred from the viewpoint of industrial availability.
  • 3-propanediol and 2-butyl-2-ethyl-1,3-propanediol are more preferred.
  • the isocyanate content is low, and the amount of urethane bonds in the urethane coating film using polyisocyanate using this as a curing agent is low. Decreases and mechanical properties deteriorate.
  • the isocyanurate group in the present invention is a cycloisocyanate of diisocyanate monomers, and this is a polyisocyanate having an isocyanurate group which is trimerized, pentamerized or multimerized.
  • R 1 represents a molecule excluding the NCO group of the diisocyanate monomer, and n is an integer of 1 or more).
  • the allophanate group which is an essential component of the polyisocyanate composition (a), is further divided into urethane groups after the hydroxyl group of the diol and the isocyanate group of the aliphatic polyisocyanate react to form a urethane bond. This is obtained by the reaction of an isocyanate group of
  • R 1 represents a molecule excluding the NCO group of the diisocyanate monomer
  • R 2 represents a molecule excluding the hydroxyl group of the diol
  • the molar ratio of allophanate groups and isocyanurate groups contained in the polyisocyanate composition (a) is such that allophanate groups / isocyanurate groups are in the range of 90/10 to 100/0.
  • the flip-flop property of the coating film may be lowered.
  • an aliphatic polyisocyanate and a diol are charged in an amount in which an isocyanate group is excessive with respect to a hydroxyl group, and urethanization and allophanate reaction are carried out at 50 to 150 ° C. in the presence or absence of an organic solvent. It is preferable that the isocyanate group-terminated prepolymer I be produced.
  • the presence or absence of completion is judged by the isocyanate group content and refractive index increase value by neutralization titration method.
  • the reaction it is preferable to stop the reaction by adding a reaction terminator to the isocyanate group-terminated prepolymer I.
  • reaction is allowed to proceed under nitrogen gas or a dry air stream.
  • the third step it is preferable to remove the isocyanate group-terminated prepolymer I by thin film distillation or solvent extraction until the content of free aliphatic polyisocyanate is less than 1% by mass.
  • the “amount of excess isocyanate group” in the first step means that the isocyanate group of the aliphatic polyisocyanate and the hydroxyl group of the acyclic aliphatic diol having 2 to 3 carbon atoms between the hydroxyl groups when the raw materials are charged.
  • the amount is less than the lower limit, the amount of a polyisocyanate composition having a molecular weight higher than that of the target product is increased, which may increase the viscosity.
  • it exceeds the upper limit the increase in viscosity and the product yield due to the decrease in the allophanate body of the polyisocyanate composition may decrease, leading to a decrease in productivity.
  • the allophanatization reaction in the first step may be performed simultaneously with the urethanization reaction or after the urethanization.
  • the reaction may be performed in the presence of an allophanatization catalyst.
  • allophanatization is performed after urethanization, the urethanization reaction was performed for a predetermined time in the absence of the allophanatization catalyst. Thereafter, an allophanatization catalyst may be added to carry out the allophanatization reaction.
  • the reaction temperature of the urethanization reaction of the present invention is preferably 20 to 70 ° C., more preferably 30 to 60 ° C.
  • a known urethanization catalyst can be used. Specifically, organic metal compounds such as dibutyltin diacetate, dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof are selected and used. These catalysts can be used alone or in combination of two or more.
  • the reaction time of the urethanization reaction varies depending on the presence or absence of the catalyst, the type, and the temperature, but is generally within 10 hours, preferably 1 to 5 hours is sufficient.
  • the allophanatization catalyst generally used is mentioned as an allophanatization catalyst in a 1st process.
  • the allophanatization catalyst can be appropriately selected from known catalysts, and for example, carboxylic acid metal salts can be used.
  • carboxylic acid metal salts include monocarboxylic acids such as saturated aliphatic carboxylic acids, saturated monocyclic carboxylic acids, saturated bicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, araliphatic carboxylic acids, and aromatic carboxylic acids.
  • saturated aliphatic carboxylic acid examples include acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid and the like.
  • saturated monocyclic carboxylic acid examples include cyclohexane carboxylic acid and cyclopentane carboxylic acid.
  • saturated polycyclic carboxylic acid examples include bicyclo [4.4.0] decane-2-carboxylic acid.
  • unsaturated aliphatic carboxylic acids examples include oleic acid, linoleic acid, linolenic acid, soybean oil fatty acid, tall oil fatty acid, and the like.
  • Examples of the araliphatic carboxylic acid include diphenylacetic acid.
  • aromatic carboxylic acids examples include benzoic acid and toluic acid.
  • Polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, kurtaconic acid, azelaic acid, sebacic acid 1,4-cyclohexyldicarboxylic acid, ⁇ -hydromuconic acid, ⁇ -hydromuconic acid, ⁇ -butyl- ⁇ -ethylglutaric acid, ⁇ , ⁇ -diethylsuccinic acid, maleic acid, fumaric acid, trimellitic acid, pyro And merit acid.
  • examples of the metal constituting the metal salt of carboxylic acid include alkali metals, alkaline earth metals, typical metals other than those described above, and transition metals.
  • alkali metal examples include lithium, sodium, and potassium.
  • alkaline earth metals examples include magnesium, calcium, and barium.
  • transition metals include manganese, iron, cobalt, nickel, copper, zinc, and zirconium.
  • carboxylic acid metal salts can be used alone or in combination of two or more.
  • the amount of the allophanatization catalyst used is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.1% by mass, based on the total mass of the polyisocyanate and the diol.
  • organic solvent various organic solvents that do not affect the reaction can be used.
  • organic solvents that do not affect the reaction.
  • aliphatic hydrocarbons aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, glycol ether esters , Ethers, halogenated hydrocarbons, polar aprotic solvents and the like.
  • aliphatic hydrocarbons examples include n-hexane and octane.
  • Examples of the alicyclic hydrocarbons include cyclohexane and methylcyclohexane.
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • esters examples include methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate.
  • glycol ether esters examples include ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, and the like.
  • ethers examples include diethyl ether, tetrahydrofuran, dioxane and the like.
  • halogenated hydrocarbons include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane, and the like.
  • polar aprotic solvent examples include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphonilamide and the like.
  • solvents can be used alone or in combination of two or more.
  • reaction terminator such as phosphoric acid or phosphoric acid ester
  • allophanate-modified polyisocyanate can be obtained by removing unreacted components by a known method such as thin film distillation.
  • allophanated polyisocyanate can be further isocyanurated to adjust the allophanate group / isocyanurate group molar ratio.
  • Examples of the isocyanuration reaction include a method in which polyisocyanate is modified (trimerized) in the presence of an isocyanuration catalyst.
  • a modification method for example, methods described in Japanese Patent Nos. 3371480 and 2002-241458 can be used.
  • isocyanurate-forming catalyst for example, metal salts of aliphatic carboxylic acids, phenolates, amine compounds, and the like can be used.
  • Examples of the metal salt of the aliphatic carboxylic acid include sodium salts, potassium salts, tin salts, and the like of carboxylic acids such as acetic acid, propionic acid, undecyl acid, capric acid, octylic acid, and myristic acid.
  • carboxylic acids such as acetic acid, propionic acid, undecyl acid, capric acid, octylic acid, and myristic acid.
  • 2-hydroxypropyltrimethylammonium octylate (DABCO TMR, manufactured by Sankyo Air Products), potassium octylate (DABCO K-15, manufactured by Sankyo Air Products), and the like.
  • phenolate examples include potassium phenolate.
  • amine compounds examples include 2,4,6-tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, and 2,6-di-t-butyl-4-dimethylaminotrimethylsilanephenol. , Triethylamine, N, N ′, N ′′ -tris (dimethylaminopropyl) hexahydro-S-triazine, diazabicycloundecene and the like.
  • a metal salt of an aliphatic carboxylic acid is preferable, and zirconyl octylate is more preferable because the reaction is easily controlled.
  • the polyisocyanate composition (a) can be produced by a technique in which allophanatization and isocyanurate formation are performed simultaneously, or a technique in which allophanatization and isocyanurate conversion are performed stepwise.
  • the polyisocyanate composition (a) can be used by mixing two or more different molar ratios of allophanate groups and isocyanurate groups. At this time, as long as the mixture satisfies the molar ratio between the allophanate group and the isocyanurate group, a polyisocyanate that does not satisfy the molar ratio between the allophanate group and the isocyanurate group can be used.
  • the reaction terminator in the second step has a function of deactivating the activity of the catalyst.
  • the organic acid has an inorganic acid such as phosphoric acid or hydrochloric acid, a sulfonic acid group, a sulfamic acid group, or the like.
  • known compounds such as esters and acyl halides are used.
  • These reaction terminators can be used alone or in combination of two or more.
  • the addition time is preferably a rapid addition after completion of the reaction.
  • the addition amount of the reaction terminator varies depending on the kind of the reaction terminator and the catalyst used, but is preferably 0.5 to 10 equivalents, particularly preferably 0.8 to 5.0 equivalents of the catalyst.
  • the storage stability of the obtained polyisocyanate composition tends to be lowered, and when it is too much, the polyisocyanate composition may be colored.
  • a free unreacted aliphatic polyisocyanate present in the reaction mixture is removed by, for example, thin film distillation at 120 to 150 ° C. under a high vacuum of 10 to 100 Pa or an organic solvent.
  • the residual content is adjusted to 1.0% by mass or less by the extraction method according to 1.
  • the residual content rate of aliphatic polyisocyanate exceeds an upper limit, there exists a possibility of causing the generation
  • the viscosity of the polyisocyanate composition (a) is not particularly limited, but is preferably 8,000 mPa ⁇ s or less at 25 ° C., more preferably 7,000 mPa ⁇ s or less, More preferably, it is 000 mPa ⁇ s or less.
  • the viscosity of the polyisocyanate exceeds 8,000 mPa ⁇ s, the viscosity of the coating composition increases, and it may be difficult to handle.
  • the lower limit of the viscosity is not particularly limited, but is preferably 50 mPa ⁇ s or more from the viewpoint of handling.
  • the polyisocyanate composition (a) obtained by refining can be made into a blocked isocyanate using a known blocking agent for the purpose of extending the pot life or making the coating composition one component.
  • a known blocking agent for the purpose of extending the pot life or making the coating composition one component.
  • the blocked polyisocyanate is inactive at room temperature, but when heated, the blocking agent dissociates, and the isocyanate group is activated again, thereby causing a potential function to react with the active hydrogen group. Can be added.
  • the blocking agent that can be used in the present invention is a compound having one active hydrogen group in the molecule, and examples thereof include alcohols, alkylphenols, phenols, active methylenes, mercaptans, acid amides, and acid imides. , Imidazole, urea, oxime, amine, imide, and pyrazole compounds.
  • the polyisocyanate composition (a) thus obtained has an average functional group number determined from the number average molecular weight obtained from GPC analysis in the range of 3.0 to 7.0. If it is less than the lower limit, the crosslinking density may decrease, and the solvent resistance and physical properties of the coating film may decrease. Moreover, when exceeding an upper limit, there exists a possibility of causing the raise of the viscosity of a polyisocyanate composition.
  • polyisocyanate composition that solves the second problem is a polyisocyanate composition (a) containing the above-described polyisocyanate composition (a) and polyisocyanate compositions (b) and (c) described later ( Hereinafter, it is referred to as “polyisocyanate composition (d)”.
  • the polyisocyanate composition (a) is a polyisocyanate composition that solves the first problem, and is at least one isocyanate selected from the group consisting of aliphatic polyisocyanates and isocyanate group-terminated prepolymers of aliphatic polyisocyanates.
  • a polyisocyanate composition having an allophanate group which is a reaction product of a compound and a diol having no side chain structure hereinafter also referred to as acyclic) and having a side chain and having 2 to 3 carbon atoms between hydroxyl groups.
  • the polyisocyanate composition (b) is a reaction product of at least one isocyanate compound selected from the group consisting of aliphatic polyisocyanates and isocyanate group-terminated prepolymers of aliphatic polyisocyanates with monoalcohols having 1 to 3 carbon atoms. It is a polyisocyanate composition having an allophanate group.
  • the polyisocyanate composition (c) is a polyisocyanate having an isocyanurate group obtained by cyclopolymerizing at least one isocyanate compound selected from the group consisting of an aliphatic polyisocyanate and an isocyanate group-terminated prepolymer of the aliphatic polyisocyanate. It is a composition.
  • the aliphatic polyisocyanate that can be used in the polyisocyanate compositions (a) to (c) of the present invention is a polyisocyanate compound that does not contain a benzene ring in its structure, and includes the above-described aliphatic polyisocyanates. it can. Of these, hexamethylene diisocyanate is preferable from the viewpoint of weather resistance and industrial availability. Aliphatic polyisocyanates may be used alone or in combination of two or more, and alicyclic diisocyanates represented by isophorone diisocyanate and norbornene diisocyanate may be used in combination.
  • Examples of the monoalcohol that can be used in the polyisocyanate composition (b) of the present invention include methanol, ethanol, 1-propanol, and 2-propanol, which are monoalcohols having 1 to 3 carbon atoms.
  • the above monoalcohols may be used alone or in combination of two or more. Among these, methanol and ethanol are more preferable for increasing the isocyanate content.
  • Examples of the monoalcohol having 4 or more carbon atoms include 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, 1-tridecanol, 2-tridecanol, 2-octyldodecanol, pentadecanol, palmityl alcohol, stearyl alcohol, cyclopentanol, cyclo Examples include hexanol, methylcyclohexanol, trimethylcyclohexanol, etc., but when these are used as modifiers, the isocyanate content is reduced, and the urethane bond in the urethane coating film using polyisocyanate as a curing agent is used. There was a decrease
  • the allophanate group which is the main constituent of the polyisocyanate composition (a) of the present invention is further separated into urethane groups after the hydroxyl group of the diol and the isocyanate group of the aliphatic diisocyanate react to form a urethane bond.
  • the above-mentioned isocyanate group is reacted, and is shown in the above Chemical Formula 4.
  • the allophanate group which is the main constituent of the polyisocyanate composition (b) of the present invention is a urethane group after the hydroxyl group of the monoalcohol reacts with the isocyanate group of the aliphatic diisocyanate to form a urethane bond. Further reacted with another isocyanate group is shown in the following chemical formula 5.
  • R 1 represents a molecule excluding the NCO group of the diisocyanate monomer
  • R 3 represents a molecule excluding the hydroxyl group of the monool
  • the isocyanurate group which is one of the constituent components of the polyisocyanate composition (c) of the present invention, is obtained by cyclopolymerizing diisocyanate monomers, and is represented by the above chemical formula 3.
  • This is a polyisocyanate having an isocyanurate group that is trimerized, trimerized, or polymerized.
  • the molar ratio of allophanate groups and isocyanurate groups (allophanate groups / isocyanurate groups) contained in the polyisocyanate compositions (a) to (c) of the present invention is 85/15 to 35/65 (molar ratio). It is preferable that it is the range of these.
  • the molar ratio of isocyanurate groups exceeds the upper limit, the flip-flop property of the coating film may be lowered, and when it is lower than the lower limit, the weather resistance and the coating film strength may be deteriorated.
  • the monoallophanate body contained in the polyisocyanate composition (b) contained in the polyisocyanate composition of the present invention preferably has a peak area area ratio in the range of 4 to 12% as measured by GPC.
  • the peak area ratio of the monoallophanate body exceeds the upper limit value, the weather resistance, the coating film strength, and the flip-flop property may be lowered.
  • the peak ratio is below the lower limit value, the permeability may be insufficient. .
  • the specific method for producing the polyisocyanate composition (a) is as described above.
  • an aliphatic polyisocyanate and a monool are charged in an amount in which an isocyanate group is excessive with respect to a hydroxyl group, and in the presence or absence of an organic solvent, 50 to It is preferable to produce the isocyanate group-terminated prepolymer I by urethanization and allophanatization reaction at 150 ° C.
  • the presence or absence of completion is judged by the isocyanate group content and refractive index increase value by neutralization titration method.
  • the reaction it is preferable to stop the reaction by adding a reaction terminator to the isocyanate group-terminated prepolymer I.
  • reaction is allowed to proceed under nitrogen gas or a dry air stream.
  • the third step it is preferable to remove the isocyanate group-terminated prepolymer I by thin film distillation or solvent extraction until the content of free aliphatic polyisocyanate is less than 1% by mass.
  • R isocyanate group
  • the amount is less than the lower limit, the amount of a polyisocyanate composition having a molecular weight higher than that of the target product is increased, which may increase the viscosity.
  • the upper limit is exceeded, the product yield decreases, which may lead to a decrease in productivity.
  • the allophanatization reaction in the first step of the polyisocyanate composition (b) may be performed simultaneously with the urethanization reaction or after the urethanization.
  • the reaction may be performed in the presence of an allophanatization catalyst.
  • allophanatization is performed after urethanization, the urethanization reaction was performed for a predetermined time in the absence of the allophanatization catalyst. Thereafter, an allophanatization catalyst may be added to carry out the allophanatization reaction.
  • the reaction temperature of the urethanization reaction of the present invention is preferably 20 to 70 ° C., more preferably 30 to 60 ° C.
  • a known urethanization catalyst can be used. Specifically, organic metal compounds such as dibutyltin diacetate, dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof are selected and used. These catalysts can be used alone or in combination of two or more.
  • the reaction time of the urethanization reaction varies depending on the presence or absence of the catalyst, the type, and the temperature, but is generally within 10 hours, preferably 1 to 5 hours is sufficient.
  • Examples of the allophanatization catalyst in the first step of the polyisocyanate composition (b) include commonly used allophanate catalysts.
  • the allophanatization catalyst examples include the allophanatization catalyst described above. Among these, a metal salt of an aliphatic carboxylic acid is preferable, and zirconyl octylate is more preferable from the viewpoint of easy control of the reaction.
  • carboxylic acid metal salts can be used alone or in combination of two or more.
  • the amount of the allophanatization catalyst used is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.1% by mass, based on the total mass of the polyisocyanate and the diol.
  • solvents can be used alone or in combination of two or more.
  • reaction terminator such as phosphoric acid or phosphoric acid ester is added to the reaction system, and the reaction is stopped at 30 to 100 ° C. for 1 to 2 hours to stop the allophanate reaction.
  • allophanate-modified polyisocyanate can be obtained by removing unreacted components by a known method such as thin film distillation.
  • Examples of the method for producing the polyisocyanate composition (c) include a method of modifying (trimerizing) the aliphatic polyisocyanate in the presence of an isocyanurate-forming catalyst.
  • a modification method for example, methods described in Japanese Patent Nos. 3371480 and 2002-241458 can be used.
  • isocyanuration catalyst for example, metal salts of aliphatic carboxylic acids, phenolates, amine compounds, and the like can be used, and specific examples include the aforementioned isocyanuration catalysts.
  • the reaction terminator has an action of deactivating the activity of the catalyst.
  • inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having a sulfonic acid group, a sulfamic acid group, and the like and esters thereof And known compounds such as acyl halides are used.
  • These reaction terminators can be used alone or in combination of two or more.
  • the addition time is preferably a rapid addition after completion of the reaction.
  • the addition amount of the reaction terminator varies depending on the kind of the reaction terminator and the catalyst used, but is preferably 0.5 to 10 equivalents, particularly preferably 0.8 to 5.0 equivalents of the catalyst.
  • the storage stability of the obtained polyisocyanate composition tends to be lowered, and when it is too much, the polyisocyanate composition may be colored.
  • free unreacted aliphatic polyisocyanate present in the reaction mixture is removed by thin film distillation or extraction with an organic solvent at 120 to 150 ° C. under a high vacuum of 10 to 100 Pa, for example.
  • the residual content is set to 1.0% by mass or less.
  • the residual content rate of aliphatic polyisocyanate exceeds an upper limit, there exists a possibility of causing the generation
  • the polyisocyanate compositions (a) to (c) of the present invention are produced by a technique of simultaneously performing allophanation and isocyanuration, or a technique of performing allophanatization and isocyanuration stepwise. be able to.
  • polyisocyanate compositions (a) to (c) of the present invention can be used in a mixture of two or more having different molar ratios of allophanate groups and isocyanurate groups. At this time, as long as the mixture satisfies the molar ratio between the allophanate group and the isocyanurate group, a polyisocyanate that does not satisfy the molar ratio between the allophanate group and the isocyanurate group can be used.
  • the polyisocyanate compositions (a) to (c) thus obtained had a molar ratio of allophanate groups to isocyanurate groups of 85/15 to 35/35 in terms of allophanate groups / isocyanurate groups.
  • the ratio is adjusted so that the monoallophanate derived from (b) is in the range of 4 to 12% in terms of the peak area ratio by GPC measurement in the range of 65 and used as the polyisocyanate composition (d). Is preferred.
  • a monool is added to form a polyisocyanate composition (b), and then an isocyanurate catalyst is added to the polyisocyanate composition (c). ) To form an allophanate group and an isocyanurate group in one shot.
  • a diol is added to form the polyisocyanate composition (a), and then an isocyanurate catalyst is added to the polyisocyanate composition (c). It is also possible to form the allophanate group and the isocyanurate group in one shot by forming.
  • the viscosity of the polyisocyanate composition (d) obtained in the present invention is not particularly limited, but is preferably 8,000 mPa ⁇ s or less at 25 ° C., and preferably 7,000 mPa ⁇ s or less. More preferably, it is 6,000 mPa ⁇ s or less.
  • the viscosity of the polyisocyanate composition exceeds 8,000 mPa ⁇ s, the viscosity of the coating composition increases and it may be difficult to handle.
  • the lower limit of the viscosity is not particularly limited, but is preferably 50 mPa ⁇ s or more from the viewpoint of handling.
  • the polyisocyanate composition (d) obtained by purification can be made into a blocked isocyanate using a known blocking agent for the purpose of extending the pot life or making the coating composition one component.
  • a known blocking agent for the purpose of extending the pot life or making the coating composition one component.
  • the blocked polyisocyanate is inactive at room temperature, but when heated, the blocking agent dissociates, and the isocyanate group is activated again, thereby causing a potential function to react with the active hydrogen group. Can be added.
  • blocking agent examples include the blocking agents described above.
  • the polyisocyanate composition (d) thus obtained has an average number of functional groups determined from the number average molecular weight obtained from GPC analysis in the range of 3.0 to 7.0. If it is less than the lower limit, the crosslinking density may decrease, and the solvent resistance and physical properties of the coating film may decrease. Moreover, when exceeding an upper limit, there exists a possibility of causing the raise of the viscosity of a polyisocyanate composition.
  • the two-component coating composition of the present invention includes the above-described polyisocyanate composition (a) and a polyol (hereinafter referred to as “two-component coating composition (x)”), or the above The polyisocyanate composition (d) of the present invention and a polyol (hereinafter referred to as “two-component coating composition (y)”).
  • the polyol used in the two-component coating composition of the present invention is not particularly limited, but is a compound containing an active hydrogen group as a reactive group with an isocyanate group, a polyester polyol, Suitable examples include polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, fluorine-based polyols, transesterification products of two or more polyols, and hydroxyl-terminated prepolymers that have undergone a urethanization reaction with polyisocyanates. These can be used as one kind or a mixture of two or more kinds.
  • polyester polyol examples include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid.
  • Sebacic acid 1,4-cyclohexyl dicarboxylic acid, ⁇ -hydromuconic acid, ⁇ -hydromuconic acid, ⁇ -butyl- ⁇ -ethylglutaric acid, ⁇ , ⁇ -diethylsuccinic acid, maleic acid, fumaric acid, etc.
  • One or more of acids or their anhydrides and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4- Low molecular weight polyols having a molecular weight of 500 or less, such as dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis ( ⁇ -hydroxyethyl)
  • lactone polyester polyols obtained from ring-opening polymerization of cyclic ester (so-called lactone) monomers such as ⁇ -caprolactone, alkyl-substituted ⁇ -caprolactone, ⁇ -valerolactone, and alkyl-substituted ⁇ -valerolactone.
  • lactone cyclic ester
  • a polyester-amide polyol obtained by replacing a part of the low molecular polyol with a low molecular polyamine such as hexamethylene diamine, isophorone diamine or monoethanolamine or a low molecular amino alcohol can also be used.
  • polyether polyol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol , Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis ( ⁇ -hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pent
  • polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., or alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether And polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as tetrahydrofuran.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc.
  • alkyl glycidyl ethers such as methyl glycidyl ether
  • aryl glycidyl ethers such as phenyl glycidyl ether
  • polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as tetrahydrofuran.
  • polycarbonate polyol examples include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A ethylene oxide and propylene oxide adducts, bis ( ⁇ -hydroxyethyl) benzene, xylylene
  • a polyol obtained by a transesterification reaction between a polycarbonate polyol, a polyester polyol, and a low molecular weight polyol can be suitably used.
  • polyolefin polyol examples include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene and the like.
  • acrylic polyol acrylic acid ester and / or methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester), acrylic acid hydroxy compound and / or methacrylic acid having at least one hydroxyl group in the molecule that can be a reaction point.
  • acrylic acid ester and / or methacrylic acid ester acrylic acid hydroxy compound and / or methacrylic acid having at least one hydroxyl group in the molecule that can be a reaction point.
  • acrylic acid ester and / or methacrylic acid ester acrylic acid hydroxy compound and / or methacrylic acid having at least one hydroxyl group in the molecule that can be a reaction point.
  • acrylic acid ester and / or methacrylic acid ester acrylic acid hydroxy compound and / or methacrylic acid having at least one hydroxyl group in the molecule that can be a reaction point.
  • examples thereof include those obtained by copolymerizing an acrylic monomer using a thermal compound, a light energy such as an ultraviolet
  • (meth) acrylic acid esters include alkyl esters having 1 to 20 carbon atoms.
  • Specific examples of such (meth) acrylate esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate.
  • Alkyl esters of acrylic acid esters of (meth) acrylic acid with cycloaliphatic alcohols such as cyclohexyl (meth) acrylate, phenyl (meth) acrylate, aryl (meth) acrylates such as benzyl (meth) acrylate Mention may be made of esters.
  • Such (meth) acrylic acid esters can be used singly or in combination of two or more.
  • (Meth) acrylic acid hydroxy compound have at least one hydroxyl group in the molecule that can be a reaction point with polyisocyanate.
  • 2-hydroxyethyl acrylate 2-hydroxy
  • 2-hydroxy Examples include hydroxy acrylate compounds such as hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and pentaerythritol triacrylate.
  • hydroxy methacrylate compounds such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, and pentaerythritol trimethacrylate are exemplified.
  • acrylic acid hydroxy compounds one or a combination of two or more may be mentioned.
  • silicone polyol examples include a vinyl group-containing silicone compound obtained by polymerizing ⁇ -methacryloxypropyltrimethoxysilane and the like, and ⁇ , ⁇ -dihydroxypolydimethylsiloxane having at least one terminal hydroxyl group in the molecule, ⁇ And polysiloxanes such as ⁇ -dihydroxypolydiphenylsiloxane.
  • castor oil-based polyol examples include linear or branched polyester polyols obtained by a reaction between a castor oil fatty acid and a polyol. Dehydrated castor oil, partially dehydrated castor oil partially dehydrated, hydrogenated castor oil added with hydrogen, and the like can also be used.
  • the fluorine-based polyol include linear or branched polyols obtained by a copolymerization reaction using a fluorine-containing monomer and a monomer having a hydroxy group as essential components.
  • the fluorine-containing monomer is preferably a fluoroolefin, for example, tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyl trifluoroethylene.
  • Examples of the monomer having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and vinyl hydroxyalkyl crotonates.
  • Examples thereof include monomers having a hydroxyl group, such as hydroxyl group-containing vinyl carboxylate or allyl ester.
  • the polyol preferably has an active hydrogen group number (average functional group number) in one molecule of 1.9 to 30.0.
  • the number of active hydrogen groups is less than the lower limit, the physical properties of the coating film may be reduced.
  • an upper limit there exists a possibility that adhesiveness may fall.
  • the number average molecular weight of the polyol is preferably in the range of 750 to 50,000. If it is less than the lower limit, if it is less than the lower limit, the adhesion may be lowered, and if it exceeds the upper limit, the solubility in a low-polar organic solvent may be lowered or the adhesion may be lowered.
  • the blending ratio of the polyisocyanate composition (d) and the polyol in the two-component coating composition is not particularly limited, but the isocyanate group in the polyisocyanate composition (d) and the hydroxyl group in the polyol are not limited. These are preferably blended so that the molar ratio (isocyanate group / hydroxyl group) is 0.5 to 2.5 (molar ratio). If it is less than the lower limit, the hydroxyl group becomes excessive, which may cause a decrease in adhesion. Moreover, there exists a possibility that a crosslinking density may fall and durability and the mechanical strength of a coating film may fall. When the upper limit is exceeded, the isocyanate group becomes excessive and reacts with moisture in the air, which may cause swelling of the coating film and a decrease in adhesion.
  • organic solvent used as a diluting solvent ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate and cellosolve, alcohols such as butanol and isopropyl alcohol, toluene, xylene, From the group consisting of hydrocarbons such as cyclohexane, mineral spirits, naphtha and the like, it can be appropriately selected and used according to the purpose and application. These solvents may be used alone or in combination of two or more.
  • a known urethanization catalyst can be appropriately used in consideration of pot life, curing conditions, working conditions, and the like.
  • organic metal compounds such as dibutyltin diacetate, dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof are selected and used. These catalysts can be used alone or in combination of two or more.
  • the curing conditions of the two-component coating composition are not particularly limited because it varies depending on the catalyst and the like, but the curing temperature is -5 to 120 ° C., the humidity is 10 to 95% RH, and the curing time is. It is preferably 0.5 to 168 hours.
  • an antioxidant such as 2,6-di-tert-butyl-4-methylphenol
  • an ultraviolet absorber such as 2,6-di-tert-butyl-4-methylphenol
  • Additives such as a flame retardant, a hydrolysis inhibitor, a lubricant, a plasticizer, a filler, an antistatic agent, a dispersant, a catalyst, a storage stabilizer, a surfactant, and a leveling agent can be appropriately blended.
  • the two-component coating composition obtained by the present invention is applied onto the surface of an adherend by a known method such as spraying, brushing, dipping, or coater to form a coating film.
  • the adherend is not particularly limited, and is stainless steel, phosphated steel, zinc steel, iron, copper, aluminum, brass, glass, slate, acrylic resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin. , Polybutylene phthalate resin, polystyrene resin, AS resin, ABS resin, polycarbonate-ABS resin, 6-nylon resin, 6,6-nylon resin, MXD6 nylon resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyurethane resin, phenol resin , Melamine resin, polyacetal resin, chlorinated polyolefin resin, polyolefin resin, polyamide resin, polyether ether ketone resin, polyphenylene sulfide resin, NBR resin, chloroprene resin, SBR resin, SE An adherend formed of a material such as S resin, an olefin resin such as polyethylene or polypropylene subjected to corona discharge treatment or other surface treatment, or a coating layer that can
  • the polyisocyanate compositions (a) and (d) and the two-component paint compositions (x) and (y) of the present invention can be suitably used for automotive paint applications.
  • the coating film using the polyisocyanate composition (a), (d) of the present invention and the coating film using the two-component coating composition (x), (y) are flip-flop values determined by the following formula 1. However, since it is higher than the flip-flop value of the coating film using only polyisocyanurate as the polyisocyanate composition, and further, the flip-flop value is 8.00 or more, the design is more excellent.
  • the permeability value to the base coat is higher than when a general isocyanurate composition is used for a clear top coat. Excellent interlayer adhesion and coating strength when a multilayer coating is formed.
  • polyisocyanate composition (d) of the present invention exhibits coating strength and weather resistance equal to or higher than those of a general isocyanurate composition.
  • the polyisocyanate composition and the two-component coating composition of the present invention can be suitably used for various coating applications, mainly for automotive coating applications.
  • ⁇ NMR measurement of allophanate group / nurate group / urethane group content>
  • Measuring device ECX400M (manufactured by JEOL Ltd., 1H-NMR) (2) Measurement temperature: 23 ° C (3) Sample concentration: 0.1 g / 1 ml (4) Integration count: 16 (5) Relaxation time: 5 seconds (6)
  • Solvent Deuterium dimethyl sulfoxide (7)
  • Chemical shift criteria Hydrogen atom signal of methyl group in deuterium dimethyl sulfoxide (2.5 ppm)
  • Evaluation method Bonded from the area ratio of the signal of the hydrogen atom bonded to the nitrogen atom of the allophanate group near 8.5 ppm and the signal of the hydrogen atom signal of the methylene group adjacent to the nitrogen atom of the nurate group near 3.7 ppm. Measure group content.
  • HDI isocyanurate-based polyisocyanate a general polyisocyanate for paints (product name: Coronate HXR, NCO content 21.8% by mass, viscosity (25 ° C.) 2600 mPa ⁇ s, free HDI content 0.2% by mass, Tosoh was used as a reference for performance comparison.
  • acrylic polyol trade name: ACRYDIC A-829, hydroxyl value: 43 mgKOH / g, solid content: 30%, manufactured by DIC
  • organic solvent (F) is used as organic solvent (F).
  • Butyl acetate was used.
  • aqueous metallic base coat composition for flip-flop evaluation As shown in Table 3, the blending amounts are as follows: polyol (D), aluminum flake (trade name: STAPA IL Hydrolan 2154, manufactured by BYK), anti-settling agent (trade name: BYK-425, manufactured by BYK), antifoaming An agent (trade name: BYK-012, manufactured by BYK), a wetting and dispersing agent (trade name: DISPERBYK-192, manufactured by BYK), and an organic solvent (G) were blended to prepare a one-pack coating composition.
  • polyol (D) aluminum flake
  • anti-settling agent trade name: BYK-425, manufactured by BYK
  • antifoaming An agent (trade name: BYK-012, manufactured by BYK), a wetting and dispersing agent (trade name: DISPERBYK-192, manufactured by BYK)
  • G organic solvent
  • an aqueous acrylic polyol (trade name: Vernock WE-303, hydroxyl value: 84 mgKOH / g, solid content: 45%, manufactured by DIC Corporation) is used, and the organic solvent (G) is used as the organic solvent (G). , Methanol was used.
  • acrylic polyol trade name: ACRYDIC A-801, hydroxyl value: 50 mg KOH / g, solid content: 50%, manufactured by DIC
  • organic solvent (F) is used for organic solvent (F).
  • Butyl acetate was used.
  • the two-component coating composition prepared in Table 4 was applied using an applicator, left at room temperature for 10 minutes, and then forced-dried with a dryer at a temperature of 90 ° C. for 30 minutes. And forcibly dried in a dryer at 80 ° C. for 10 hours to obtain a two-layer coating film for flip-flop evaluation.
  • ⁇ Flip-flop evaluation method The flip-flop evaluation of the prepared two-layer coating film was performed by measuring L * at each angle of 15 °, 45 °, and 110 ° using a multi-angle colorimeter BYK-mac (manufactured by BYK). The value calculated in this way was used as the flip-flop value.
  • ⁇ NMR measurement of allophanate group / nurate group content>
  • Measuring device ECX400M (manufactured by JEOL Ltd., 1H-NMR) (2) Measurement temperature: 23 ° C (3) Sample concentration: 0.1 g / 1 ml (4) Integration count: 16 (5) Relaxation time: 5 seconds (6)
  • Solvent Deuterium dimethyl sulfoxide (7)
  • Chemical shift criteria Hydrogen atom signal of methyl group in deuterium dimethyl sulfoxide (2.5 ppm)
  • Evaluation method Bonded from the area ratio of the signal of the hydrogen atom bonded to the nitrogen atom of the allophanate group near 8.5 ppm and the signal of the hydrogen atom signal of the methylene group adjacent to the nitrogen atom of the nurate group near 3.7 ppm. Measure group content.
  • HDI isocyanurate-based polyisocyanate a general polyisocyanate for paints (product name: Coronate HXR, NCO content 21.8% by mass, viscosity (25 ° C.) 2600 mPa ⁇ s, free HDI content 0.2% by mass, Tosoh was used as a reference for performance comparison.
  • aqueous acrylic polyol (trade name: Bernock WE-303, hydroxyl value: 84 mg KOH / g, solid content: 45%, manufactured by DIC Corporation), aluminum flake (trade name: WXM-D5660, Toyo Aluminum Co., Ltd.) Manufactured), anti-settling agent (trade name: BYK-425, manufactured by BYK), antifoaming agent (trade name: BYK-012, manufactured by BYK), wetting and dispersing agent (trade name: DISPERBYK-192, manufactured by BYK) , And methanol were blended to prepare a one-pack coating composition.
  • the one-component coating composition prepared in Table 12 was applied to each steel plate (JIS G3141, trade name: SPCC-SB, PF-1077, manufactured by Partec Co.) degreased with methyl ethyl ketone by spraying. After leaving still for 30 minutes at a humidity of 50%, forced drying was performed in a dryer at a temperature of 60 ° C. for 30 minutes to form a metallic base layer having a dry film thickness of 30 ⁇ m. Subsequently, after standing at 23 ° C.
  • the two-component coating composition prepared in Tables 13 and 14 was applied using an applicator and allowed to stand at room temperature for 10 minutes, and then at a temperature of 90 ° C. Forcibly dried for 30 minutes, and further forcedly dried for 10 hours with a dryer at 80 ° C. to obtain a two-layer coating film for flip-flop evaluation.
  • ⁇ Flip-flop evaluation method The flip-flop evaluation of the prepared two-layer coating film was performed by measuring L * at each angle of 15 °, 45 °, and 110 ° using a multi-angle colorimeter BYK-mac (manufactured by BYK). The value calculated in this way was used as the flip-flop value.
  • Tables 19 to 21 show measurement results that can be said to be sufficient when the flip-flop exceeds the measured value when coronate HXR, which is a general HDI isocyanurate-based polyisocyanate, is used.
  • an aqueous acrylic polyol product name: Vernock WE-303, manufactured by DIC
  • Vernock WE-303 manufactured by DIC
  • the two-component coating composition was applied from above the primer using an applicator, preliminarily dried at room temperature for 15 minutes, and then heat-treated in a dryer at 90 ° C. for 30 minutes. Thereafter, the coating film was peeled off from the PP plate, and the primer side coating surface was measured by IR.
  • ⁇ Weather resistance evaluation method> The coating film prepared from the paint obtained by the formulation shown in Table 17 and Table 18 was subjected to a weather resistance acceleration test under the following conditions.
  • each coating composition UJ and UH indicates the sample name corresponding to each characteristic evaluation item.

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Abstract

La présente invention concerne : une composition de polyisocyanate qui fait preuve d'excellentes propriétés mécaniques aux températures élevées si elle est utilisée comme agent de durcissement pour les matériaux de revêtement ; une composition de polyisocyanate qui fait preuve d'excellentes propriétés mécaniques aux températures élevées, de résistance aux intempéries et de perméabilité à partir d'une couche supérieure claire jusqu'à une couche de base si elle est utilisée comme agent de durcissement pour les revêtements supérieurs clairs ; et une composition pour matériaux de revêtement polyisocyanates, qui présente des propriétés flip flop élevées si chaque composition de polyisocyanate est formée en un film de revêtement multicouche avec une couche de base aqueuse. Les solutions prévues sont : l'utilisation d'une composition de polyisocyanate qui est obtenue par la réaction d'un diol aliphatique acyclique spécifique avec au moins un composé isocyanate sélectionné parmi les polyisocyanates aliphatiques et leurs prépolymères terminés par un groupe isocyanate ; et une composition de polyisocyanate qui contient cette composition de polyisocyanate, une composition de polyisocyanate contenant un groupe allophanate qui est un produit réactionnel d'un monool spécifique et d'un polyisocyanate aliphatique, et une composition de polyisocyanate contenant un groupe isocyanurate.
PCT/JP2016/085899 2015-12-04 2016-12-02 Composition de polyisocyanate et composition de revêtement l'utilisant WO2017094883A1 (fr)

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JP2015-237941 2015-12-04
JP2015237941 2015-12-04
JP2016-135701 2016-07-08
JP2016135701A JP2018002972A (ja) 2016-07-08 2016-07-08 ポリイソシアネート組成物およびそれを用いた塗料組成物
JP2016-208838 2016-10-25
JP2016208838A JP6840991B2 (ja) 2015-12-04 2016-10-25 ポリイソシアネート組成物およびそれを用いた塗料組成物

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* Cited by examiner, † Cited by third party
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JP2006193642A (ja) * 2005-01-14 2006-07-27 Nippon Polyurethane Ind Co Ltd アロファネート変性ポリイソシアネート組成物の製造方法
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CN113056617A (zh) * 2019-03-27 2021-06-29 住友理工株式会社 电子照相设备用显影辊以及电子照相设备用显影辊的制造方法

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