WO2016125769A1 - ポリイソシアネート組成物及びその製造方法、コーティング組成物、水系コーティング組成物、並びにコーティング基材 - Google Patents
ポリイソシアネート組成物及びその製造方法、コーティング組成物、水系コーティング組成物、並びにコーティング基材 Download PDFInfo
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- polyisocyanate
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
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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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
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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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
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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
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- 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
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- 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
- C09D175/08—Polyurethanes from polyethers
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
Definitions
- the present invention relates to a polyisocyanate composition and a method for producing the same, a coating composition, an aqueous coating composition, and a coating substrate.
- the two-component urethane coating composition used as a solvent-based paint is desired to be water-based.
- polyisocyanate used as a curing agent is difficult to disperse in water and easily reacts with water, and carbon dioxide is generated by the reaction. For this reason, development of polyisocyanates having emulsifying properties and suppressing the reaction between isocyanate groups and water even in a water-dispersed state is underway.
- Patent Document 1 discloses a polyisocyanate mixture dispersible in water, which contains a polyisocyanate compound and a polyether containing an ethylene oxide unit. Further, in Patent Document 2, water obtained by reacting a prepolymer obtained from an aliphatic or alicyclic diisocyanate with a nonionic hydrophilic component consisting of 3.0 to 4.9 ethylene oxide repeating units on the average is added to water. An easily dispersible polyisocyanate composition is disclosed.
- Patent Document 3 a polyanion obtained by a reaction between a nonionic hydrophilic component having at least one hydroxyl group and comprising 3 to 50 ethylene oxide repeating units and a long-chain polyol component having a number average molecular weight of 1,000 to 15,000. Isocyanate compositions are disclosed.
- Water-based two-component urethane coating composition is applied to furniture and building materials, woodwork for homes, sports floors, wooden floors for housing and school facilities.
- the two-component urethane coating composition is often prepared on-site, and therefore a strong stirrer cannot often be used. If the stirring is insufficient, the polyisocyanate used as the curing agent is not dispersed in the main agent, the appearance of the coated film is impaired, and the physical properties of the film are adversely affected. Therefore, there is a need for an aqueous two-component urethane coating composition that disperses in the main agent even with a low stirring force and exhibits a good coating film appearance.
- an object of the present invention is to provide a polyisocyanate composition that exhibits a good appearance of a coating film when stirred with a low stirring force and a good water resistance of the coating film.
- the inventors include a specific modified polyisocyanate obtained by a reaction between a polyisocyanate and a polyalkylene glycol alkyl ether having a specific structure, and a polyisocyanate composition having a specific range of isocyanate average functional group number, The inventors have found that the appearance of a good coating film when stirred with a low stirring force and the good water resistance of the coating film are found, and the present invention has been completed.
- a polyisocyanate composition comprising a modified polyisocyanate obtained by a reaction between a polyisocyanate and a polyalkylene glycol alkyl ether represented by the following general formula (1),
- the average isocyanate functional group number is 1.8 or more and 4.0 or less
- the portion derived from the polyalkylene glycol alkyl ether in the modified polyisocyanate with respect to the total amount of the polyisocyanate composition includes 10% by mass or more and 18% by mass or less
- a polyisocyanate composition in which a dispersion ratio of a molecular weight distribution of a portion derived from the polyalkylene glycol alkyl ether is 1.05 or more and 2.00 or less.
- R 1 is an alkylene group having 1 to 4 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms.
- the average number of n is 5.0 or more and 20 or less.
- R 1 is an ethylene group
- the average number of n is 5.0 to 15, the polyisocyanate composition according to [1] or [2].
- polyisocyanate composition according to any one of [1] to [3], wherein the polyalkylene glycol alkyl ether comprises two or more polyalkylene glycol alkyl ethers having different average numbers of n in the formula (1). .
- an average isocyanate functional group number is 1.8 or more and 4.0 or less, and a portion derived from the polyalkylene glycol alkyl ether in the modified polyisocyanate with respect to the total amount of the polyisocyanate composition
- the polyisocyanate containing 10% by mass to 18% by mass and having a molecular weight distribution dispersion ratio of 1.05 to 2.00 in the modified polyisocyanate derived from the polyalkylene glycol alkyl ether
- the manufacturing method of a polyisocyanate composition which is the process of making it react so that a composition may be obtained.
- R 1 is an alkylene group having 1 to 4 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms.
- the average number of n is 5.0 or more and 20 or less.
- R 1 is an ethylene group
- the average number of n is 5.0 to 15, a manufacturing method of the polyisocyanate composition described in [6] or [7].
- polyisocyanate composition according to any one of [6] to [8], wherein the polyalkylene glycol alkyl ether comprises two or more polyalkylene glycol alkyl ethers having different average numbers of n in the formula (2).
- Manufacturing method [10] [1] A coating composition comprising the polyisocyanate composition according to any one of [5]. [11] [10] A water-based coating composition comprising the coating composition according to [10] and water. [12] A coated substrate comprising: a substrate; and a coating film coated with the coating composition according to [10] or the aqueous coating composition according to [11].
- the polyisocyanate composition according to the present invention it is possible to obtain a good appearance of the coating film and a good water resistance of the coating film when stirred with a low stirring force.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the following embodiment is an exemplification for explaining the present invention, and the present invention is not limited to the following embodiment.
- the present invention can be appropriately modified within the scope of the gist.
- the polyisocyanate composition of this embodiment contains the modified polyisocyanate obtained by reaction of polyisocyanate and the polyalkylene glycol alkyl ether represented by the following general formula (1).
- the polyisocyanate composition has an average isocyanate functional group number of 1.8 or more and 4.0 or less, and the polyalkylene in the modified polyisocyanate with respect to the total amount (100% by mass) of the polyisocyanate composition.
- a portion derived from glycol alkyl ether is contained in an amount of 10% by mass to 18% by mass.
- the dispersion ratio of the molecular weight distribution of the portion derived from the polyalkylene glycol alkyl ether is 1.05 or more and 2.00 or less.
- R 1 is an alkylene group having 1 to 4 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms.
- the average number of n is 5.0 or more and 20 or less.
- the polyisocyanate composition of the present embodiment includes the polyisocyanate not reacted with the polyalkylene glycol alkyl ether (hereinafter also referred to as “unreacted polyisocyanate”), and the polyalkylene glycol not reacted with the polyisocyanate.
- An alkyl ether hereinafter also referred to as “unreacted polyalkylene glycol alkyl ether”
- various physical properties or characteristics of the polyisocyanate composition of the present embodiment to be described later are modified polyisocyanate obtained by reaction with the polyalkylene glycol alkyl ether (hereinafter, simply referred to as “modified polyisocyanate”) unless otherwise specified. And a state containing unreacted polyisocyanate.
- the ratio of unreacted polyisocyanate and modified polyisocyanate can be determined by measurement by liquid chromatography.
- the polyisocyanate of the present embodiment is not limited to the following, but for example, at least one diisocyanate compound selected from aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, and a polyisocyanate derived from these diisocyanate compounds.
- An isocyanate compound is mentioned.
- the polyisocyanate used in the present embodiment is at least one diisocyanate compound selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates from the viewpoint of industrial availability. preferable.
- aliphatic diisocyanate examples include, but are not limited to, for example, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, ethyl (2,6-diisocyanato) hexanoate, 1,6-diisocyanate.
- Natohexane hereinafter also referred to as “HDI”), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, and 2,2,4- or 2,4,4-trimethyl-1,6 -Diisocyanatohexane.
- the alicyclic diisocyanate is not limited to the following, but for example, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (hereinafter also referred to as “hydrogenated XDI”), 1,3- Or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl 1-isocyanato-3- (isocyanatomethyl) cyclohexane (hereinafter also referred to as “IPDI”), 4-4′-diisocyanato-dicyclohexylmethane ( Hereinafter, also referred to as “hydrogenated MDI”), and 2,5- or 2,6-diisocyanatomethylnorbornane.
- hydroxDI 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane
- IPDI 1,3- Or 1,4-diisocyanatocyclohexane
- IPDI 1,3- Or 1,
- aromatic diisocyanates include, but are not limited to, xylylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.
- HDI high-density polyethylene
- IPDI low-density polyethylene
- hydrogenated XDI high-density polyethylene
- MDI low-density polyethylene
- the polyisocyanate derived from the above-mentioned diisocyanate is not limited to the following, but for example, a polyisocyanate compound having a uretdione structure obtained by cyclizing and dimerizing two isocyanate groups, and cyclizing three isocyanate groups.
- a polyisocyanate compound having an isocyanurate structure obtained by quantification, an iminooxadiazinedione structure, a polyisocyanate compound having a biuret structure obtained by reacting three isocyanate groups and one water molecule, and two isocyanate groups A polyisocyanate compound having an oxadiazine trione structure obtained by reacting with one molecule of carbon dioxide, a polyisocyanate compound having a plurality of urethane groups obtained by reacting one isocyanate group and one hydroxyl group, 2
- a polyisocyanate compound having a urea structure obtained by reacting with one primary or secondary amine A polyisocyanate compound having an isocyanurate structure
- polyisocyanate compound means a compound containing polyisocyanate obtained by reacting with a compound other than diisocyanate (for example, alcohol, water, amine).
- polyisocyanates may be modified with a sulfonic acid amine salt having a hydroxyl group, a vinyl polymer having a hydroxyl group and a nonionic hydrophilic group, or the like. These can also be used 1 type or in combination of 2 or more types.
- the polyalkylene glycol alkyl ether used in the present embodiment has a structure represented by the following general formula (1).
- R 1 is an alkylene group having 1 to 4 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms.
- the average number of n is 5.0 or more and 20 or less.
- the polyalkylene glycol alkyl ether is not a single component but an aggregate of substances having different degrees of polymerization (hereinafter, also referred to as “polymerization degree n” or simply “n”). Therefore, the degree of polymerization n is expressed by its average value.
- the polyalkylene glycol alkyl ether is not a single component but has a molecular weight distribution. Therefore, a dispersion ratio is used to represent the molecular weight distribution. In this embodiment, the dispersion ratio of the molecular weight distribution is determined from the mass-to-charge ratio (m / z) in the mass spectrum of polyalkylene glycol alkyl ether obtained by mass spectrometry after being separated by liquid chromatography.
- the calculation is performed as follows.
- a sample for example, polyalkylene glycol alkyl ether in the polyisocyanate composition of the present embodiment
- GPC gel permeation chromatography
- the dispersion ratio of the molecular weight distribution can be obtained.
- the “polyalkylene glycol alkyl ether” referred to here is a polyalkylene glycol alkyl ether used as a raw material of the polyisocyanate composition of the present embodiment, an unreacted polyalkylene glycol alkyl ether in the polyisocyanate composition, or a polyisocyanate.
- the dispersion ratio of the molecular weight distribution is 1.00 or more and less than 1.05.
- the dispersion ratio of the molecular weight distribution of the portion derived from the polyalkylene glycol alkyl ether is 1.05 or more and 2.00 or less, preferably from the viewpoint of water dispersion stability and coating film appearance. Is 1.06 or more and 1.50 or less, more preferably 1.08 or more and 1.45 or less, and further preferably 1.10 or more and 1.40 or less.
- the dispersion ratio of the molecular weight distribution is 1.05 or more and 2.00 or less, a component that maintains a distance between particles and a component that lowers the interaction between water molecules and a component that forms a thick hydrated layer are mixed appropriately.
- the viscosity can be suppressed and the particles can be stably dispersed while improving the appearance of the coating film. Further, when the dispersion ratio of the molecular weight distribution is 1.05 or more and 2.00 or less, it is possible to achieve both suppression of increase in viscosity and water dispersion stability even in a state where the content of polyalkylene glycol alkyl ether is small. .
- a method for controlling the dispersion ratio of the molecular weight distribution of the part derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate to the above range for example, a polyalkylene glycol alkyl having a molecular weight distribution dispersion ratio of 1.05 to 2.00
- a method of adjusting by using ether or combining two or more types having different average numbers of n may be mentioned.
- the dispersion ratio of the molecular weight distribution is measured by the method described in the examples.
- R 1 of the polyalkylene glycol alkyl ether is an alkylene group having 1 to 4 carbon atoms from the viewpoint of imparting hydrophilicity. From the viewpoint of imparting more hydrophilicity, an ethylene group having 2 carbon atoms is preferable. From the viewpoint of imparting hydrophilicity, R 2 is an alkyl group having 1 to 4 carbon atoms. From the viewpoint of imparting more hydrophilicity, a methyl group having 1 carbon atom is preferable.
- n is 5.0 or more, preferably 5.2 or more, and preferably 5.4 or more from the viewpoint of water dispersibility, water dispersion stability, and coating film appearance. More preferably, it is more preferably 6.0 or more.
- the emulsifying power is increased, so that the dispersibility is improved and the dispersion can be easily performed. Therefore, the dispersibility to a main ingredient improves more and the external appearance of a coating film is more excellent.
- n is 20 or less, preferably 15 or less, more preferably 14 or less, and further preferably 11 or less, from the viewpoint of water dispersibility and coating film appearance. More preferably, it is 9.4 or less.
- n When the average number of n is 20 or less, an excessive increase in viscosity such as gelation can be further prevented and the dispersion can be easily performed. Therefore, the dispersibility to a main ingredient improves more and the external appearance of a coating film is more excellent.
- polyalkylene glycol alkyl ethers include, but are not limited to, polyethylene glycol (mono) methyl ether, poly (ethylene, propylene) glycol (mono) methyl ether, and polyethylene glycol (mono) ethyl ether. . From the viewpoint of imparting hydrophilicity, polyethylene glycol (mono) methyl ether is preferred.
- the number of hydroxyl groups possessed by the polyalkylene glycol alkyl ether is preferably one from the viewpoint of lowering the viscosity of the polyisocyanate composition.
- the polyalkylene glycol alkyl ether contains an alkylene oxide repeating unit — (R 1 O) n — therein.
- the average number of n in the polyalkylene glycol alkyl ether only needs to be 5.0 or more and 20 or less, and may be the number of different alkylene oxide repeating units within the range.
- the average number of alkylene oxide repeating units (hereinafter also referred to as “average number of alkylene oxide repeating units”), that is, the average number of n is 5 from the viewpoint of water dispersibility, water dispersion stability, and coating film appearance. 0.0 or more, preferably 5.2 or more, more preferably 5.4 or more, and still more preferably 6.0 or more.
- the emulsifying power is increased, so that the dispersibility is improved and the dispersion can be easily performed. Therefore, the dispersibility to a main ingredient improves more and the external appearance of a coating film is more excellent.
- n is 20 or less, preferably 15 or less, more preferably 14 or less, and further preferably 11 or less, from the viewpoint of water dispersibility and coating film appearance. More preferably, it is 9.4 or less.
- n When the average number of n is 20 or less, an excessive increase in viscosity such as gelation can be further prevented and the dispersion can be easily performed. Therefore, the dispersibility to a main ingredient improves more and the external appearance of a coating film is more excellent.
- the average number of polymerization degrees n of the polyalkylene glycol alkyl ethers in the polyisocyanate composition of the present embodiment is the average number of polymerization degrees n of the parts derived from the polyalkylene glycol alkyl ethers of the modified polyisocyanate.
- the average number of polymerization degrees n is measured by the method described in the examples.
- polyalkylene glycol alkyl ether two or more polyalkylene glycol alkyl ethers having different average numbers of n may be combined in order to adjust the dispersion ratio of the molecular weight distribution described above to 1.05 or more and 2.00 or less.
- the first component is a group having an average number of n of 3.0 to 10 and the second component is a group having an average number of n of 6.0 to 22 respectively.
- the method of combining the above is mentioned. However, the combinations are of different average numbers.
- the ratio of the polyalkylene glycol alkyl ether modified is the ratio of the polyalkylene glycol alkyl ether modified with respect to 100 equivalents of the isocyanate group of the starting polyisoisocyanate.
- the modification rate is preferably 1.0% or more and 30% or less, more preferably 3.0% or more and 25% or less, and further preferably 5.0% or more and 20% or less.
- the modification rate is 1.0% or more, the interfacial tension is lowered, so that water dispersibility is exhibited, and when the modification rate is 30% or less, the number of isocyanate groups used for crosslinking increases. It tends to be good in crosslinkability.
- the method for controlling the modification rate within the above range is not limited to the following, but examples include a method of adjusting the blending ratio of the polyalkylene glycol alkyl ether and the polyisocyanate.
- the modification rate is measured by the method described in the examples.
- the part derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate with respect to the total amount (100% by mass) of the polyisocyanate composition is 10% by mass or more from the viewpoint of water dispersibility and water dispersion stability. 11% by mass or more, and more preferably 13% by mass or more. Since the part derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate is 10% by mass or more, the hydration layer is formed, so that dispersibility is improved.
- isocyanate group retention and coating film properties it is 18% by mass or less, preferably 17.5% by mass or less, and more preferably 17% by mass or less. Since the portion derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate is 18% by mass or less, the contact between water and the isocyanate group is reduced, so that the retention rate of the isocyanate group is high, and the physical properties of the coating film (hardness, resistance) Solvent resistance and water resistance) are improved. The retention of isocyanate groups is measured by the method described in the examples.
- the method of reacting the polyisocyanate with the polyalkylene glycol alkyl ether is not limited to the following, but for example, there is a method of reacting the terminal isocyanate group possessed by the polyisocyanate with the hydroxyl group possessed by the polyalkylene glycol alkyl ether. Can be mentioned.
- the isocyanate group content of the polyisocyanate composition of the present embodiment is preferably 10% by mass or more and 24% by mass or less, and 11% by mass or more and 23% by mass in a state where the nonvolatile content is substantially 100% by mass. % Or less, more preferably 12% by mass or more and 21% by mass or less. Since the isocyanate group content is 10% by mass or more and 24% by mass or less, the number of isocyanate groups used for crosslinking increases, and the ease of movement of the molecules during curing of the polyisocyanate molecules is improved. It becomes favorable and the physical properties of the coating film tend to be improved.
- the term “isocyanate group” as used herein refers to a combination of an isocyanate group possessed by unreacted polyisocyanate and an isocyanate group possessed by a modified polyisocyanate.
- the method for controlling the isocyanate group content within the above range is not limited to the following, but examples include a method of adjusting the blending ratio of polyalkylene glycol alkyl ether and polyisocyanate.
- the isocyanate group content is measured by the method described in the examples.
- the number average molecular weight of the polyisocyanate containing the modified polyisocyanate and the unreacted polyisocyanate in the polyisocyanate composition of the present embodiment is 450 or more and 1200 or less from the viewpoint of water dispersion stability and dispersibility in the main agent. It is preferably 500 or more and 1100 or less, more preferably 550 or more and 1000 or less. Since the number average molecular weight of the polyisocyanate is 450 or more and 1200 or less, the number of trimer components used for crosslinking increases, and the ease of movement of the molecules during curing of the polyisocyanate molecules is improved. It becomes favorable and the physical properties of the coating film tend to be improved.
- the method for controlling the number average molecular weight within the above range is not limited to the following, and examples thereof include a method of adjusting the blending ratio of polyalkylene glycol alkyl ether and polyisocyanate.
- the number average molecular weight of the polyisocyanate is measured by the method described in the examples.
- the average number of isocyanate functional groups of the polyisocyanate including the modified polyisocyanate and the unreacted polyisocyanate of the present embodiment (hereinafter also referred to as “average isocyanate functional group number”) is as follows. It is 8 or more, preferably 2.3 or more, and more preferably 2.5 or more.
- the average number of isocyanate functional groups is 1.8 or more, the ease of movement of the molecules during curing of the polyisocyanate molecules is improved, so that the crosslinkability of the coating film is improved.
- isocyanate group retention it is 4.0 or less, preferably 3.6 or less, and more preferably 3.4 or less.
- the method for controlling the average number of isocyanate functional groups within the above range is not limited to the following, and examples include a method of adjusting the blending ratio of polyalkylene glycol alkyl ether and polyisocyanate.
- the average number of isocyanate functional groups is measured by the method described in the examples.
- the non-volatile content of the polyisocyanate composition is the ratio (%) of the mass after heating to the mass before heating, and is preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less. .
- the non-volatile content is 10% or more, the viscosity of the polyisocyanate composition is low, so that it tends to be easy to handle.
- the non-volatile content is 100% or less, the amount of organic solvent used can be reduced. Therefore, environmental problems tend to be improved.
- the method for controlling the non-volatile content within the above range is not limited to the following, but examples include a method of adjusting the blending ratio of the polyisocyanate composition and the solvent.
- the nonvolatile content is measured by the method described in the examples.
- the water-dispersed particle size of the polyisocyanate composition of the present embodiment is preferably 30 nm or more, more preferably 40 nm or more, and more preferably 50 nm or more from the viewpoint of water dispersion stability and the appearance of the coating film. More preferably it is.
- the water-dispersed particle size is 30 nm or more, it is easy to arrange between the particles formed by the resin in the main agent and is easily taken into the particles, so that the crosslinking is performed uniformly and the physical properties of the coating film (appearance, hardness) , Solvent resistance, water resistance) tend to be improved.
- the water dispersion particle diameter is preferably 200 nm or less, more preferably 190 nm or less, and further preferably 180 nm or less.
- the water-dispersed particle size is 200 nm or less, it is easy to arrange between the particles formed by the resin in the main agent and is easily taken into the particles, so that the crosslinking is performed uniformly and the physical properties of the coating film (appearance, hardness) , Solvent resistance, water resistance) tend to be improved.
- the method for controlling the water-dispersed particle size within the above range is not limited to the following, and examples thereof include a method of adjusting the blending ratio of polyalkylene glycol alkyl ether and polyisocyanate.
- the water-dispersed particle size is measured by the method described in the examples.
- the polyisocyanate composition of this embodiment may contain other components in addition to the above-described modified polyisocyanate and unreacted polyisocyanate.
- other components include a solvent, an antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant.
- the antioxidant is preferably a phenolic compound from the viewpoint of improving the appearance of the coating film when it is stirred with a low stirring force, and from the viewpoint of preventing yellowing of the coating film.
- the phenolic compound is not particularly limited, and examples thereof include 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol (BHT).
- a hindered phenol compound is more preferable from the viewpoint of further improving the appearance of the coating film when stirred with a low stirring force.
- hindered phenol compounds 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol (BHT), 2,6-di-t-butyl-4-ethyl More preferably, it contains at least one selected from the group consisting of -phenol, 2,4,6-tri-t-butylphenol, and 2,6-di-t-butyl-4-s-butylphenol.
- the polyisocyanate composition contains a hindered phenol-based compound
- the content of the hindered phenol compound is 0.001% by mass or more, the smoothness of the coating film is increased, and the coating film appearance at the time of low stirring tends to be more excellent.
- the content of the hindered phenol compound is 0.1% by mass or less, bleeding out at the time of coating film formation can be prevented, and the coating film appearance at the time of low stirring tends to be more excellent.
- the content of the hindered phenol compound is measured by the method described in the examples.
- the content of the solvent is preferably 0% by mass or more and 90% by mass or less, more preferably 0% by mass or more and 50% by mass or less, with respect to the total amount (100% by mass) of the polyisocyanate composition. More preferably, it is 0 mass% or more and 30 mass% or less.
- the antioxidant, light stabilizer, polymerization inhibitor, and surfactant are preferably 0% by mass or more and 10% by mass or less, and 0% by mass with respect to the total amount (100% by mass) of the polyisocyanate composition. % To 5.0% by mass, more preferably 0% to 2.0% by mass.
- Method for producing polyisocyanate composition In the method for producing a polyisocyanate composition of the present embodiment, a polyisocyanate and a polyalkylene glycol alkyl ether represented by the following general formula (2) are reacted to obtain a polyisocyanate composition containing a modified polyisocyanate. Process. In the reaction step, the average number of isocyanate functional groups is 1.8 or more and 4.0 or less, and the portion derived from the polyalkylene glycol alkyl ether in the modified polyisocyanate with respect to the total amount (100% by mass) of the polyisocyanate composition.
- the dispersion ratio of the molecular weight distribution of the portion derived from the polyalkylene glycol alkyl ether is 1.05 or more and 2.00 or less. It is the process of making it react so that an isocyanate composition may be obtained. In the reaction step, it is preferable that polyisocyanate and polyalkylene glycol alkyl ether are mixed and reacted.
- R 1 is an alkylene group having 1 to 4 carbon atoms
- R 2 is an alkyl group having 1 to 4 carbon atoms.
- the average number of n is 5.0 or more and 20 or less.
- the dispersion ratio of the molecular weight distribution of the polyalkylene glycol alkyl ether used in the reaction step is 1.05 or more and 2.00 or less, and 1.06 or more and 1.50 from the viewpoint of water dispersion stability and coating film appearance.
- the following are preferable, 1.08 or more and 1.45 or less are more preferable, and 1.10 or more and 1.40 or less are more preferable.
- the dispersion ratio of the molecular weight distribution is 1.05 or more and 2.00 or less
- a component that maintains a distance between particles and a component that lowers the interaction between water molecules and a component that forms a thick hydrated layer are mixed appropriately. By doing so, it is speculated that the viscosity can be suppressed and the particles can be stably dispersed while improving the appearance of the coating film.
- the dispersion ratio of the molecular weight distribution is 1.05 or more and 2.00 or less, it is possible to achieve both suppression of increase in viscosity and water dispersion stability even in a state where the content of polyalkylene glycol alkyl ether is small. .
- R 1 of the polyalkylene glycol alkyl ether is an alkylene group having 1 to 4 carbon atoms from the viewpoint of imparting hydrophilicity.
- an ethylene group having 2 carbon atoms is preferable.
- R 2 is an alkyl group having 1 to 4 carbon atoms.
- a methyl group having 1 carbon atom is preferable.
- n is 5.0 or more, preferably 5.2 or more, and preferably 5.4 or more from the viewpoint of water dispersibility, water dispersion stability, and coating film appearance. Is more preferably 6.0 or more.
- the average number of n is 5.0 or more, the emulsifying power is increased, so that the dispersibility is improved and the dispersion can be easily performed. Therefore, the dispersibility to the main ingredient is further improved, and the appearance of the coating film is excellent.
- n is 20 or less, preferably 15 or less, more preferably 14 or less, and further preferably 11 or less, from the viewpoint of water dispersibility and coating film appearance. More preferably, it is 9.4 or less.
- n When the average number of n is 20 or less, an excessive increase in viscosity such as gelation can be further prevented and the dispersion can be easily performed. Therefore, the dispersibility to a main ingredient improves more and the external appearance of a coating film is more excellent.
- the polyalkylene glycol alkyl ether is a polyisocyanate having a different average number of n in order to make the molecular weight dispersion ratio of the portion derived from the polyalkylene glycol alkyl ether in the modified polyisocyanate 1.05 to 2.00. It is good also as what combined 2 or more types of alkylene glycol alkyl ether.
- two or more polyalkylene glycol alkyl ethers having different average numbers of n are combined, two or more polyalkylene glycol alkyl ethers may be mixed in advance and reacted with polyisocyanate.
- two or more polyalkylene glycol alkyl ethers having different average numbers of n may be reacted at the same time or mixed at different times.
- the average number of n as the first component is different from the group of 3.0 to 10 and the average number of n as the second component is 6.0 to 22 respectively.
- the ratio of the polyalkylene glycol alkyl ether and the polyisocyanate is reacted so as to be 10% by mass or more from the viewpoint of water dispersibility and water dispersion stability, and is 11% by mass or more. It is preferable to react so that it may become, and it is more preferable to react so that it may become 13 mass% or more. Since the part derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate is 10% by mass or more, the hydration layer is formed, so that dispersibility is improved.
- the reaction is performed so that the content is 18% by mass or less, and the reaction is preferably performed so that the content is 17.5% by mass or less. It is more preferable that the reaction is carried out. Since the portion derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate is 18% by mass or less, the contact between water and the isocyanate group is reduced, so that the retention rate of the isocyanate group is high, and the physical properties of the coating film (hardness, resistance) Solvent resistance and water resistance) are improved. The retention of isocyanate groups is measured by the method described in the examples.
- the reaction temperature and reaction time are appropriately determined according to the progress of the reaction, but the reaction temperature is preferably 0 ° C. or higher and 150 ° C. or lower, and the reaction time is 0.5 hour or longer and 48 hours or shorter. It is preferable.
- a known catalyst may be used in some cases.
- the catalyst include, but are not limited to, for example, tin octoate, tin 2-ethyl-1-hexanoate, tin ethylcaproate, tin laurate, tin palmitate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, Organotin compounds such as dibutyltin dimaleate, dibutyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate; zinc chloride, zinc octoate, zinc 2-ethyl-1-hexanoate, zinc 2-ethylcaproate, zinc stearate, naphthene Organic zinc compounds such as zinc acid and zinc acetylacetonate; Organic titanium compounds; Organic zirconium compounds; Tertiary amines such as triethylamine,
- a solvent may or may not be used.
- the solvent used in the method for producing the polyisocyanate composition of the present embodiment may be a hydrophilic solvent or a hydrophobic solvent.
- hydrophobic solvent examples include, but are not limited to, mineral spirits, solvent naphtha, LAWS (Low Aromatic White Spirit), HAWS (High Aromatic White Spirit), toluene, xylene, cyclohexane, etc .; ethyl acetate, butyl acetate Esters such as acetone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- hydrophilic solvent examples include, but are not limited to, alcohols such as methanol, ethanol, propanol, isopropanol, and 2-ethylhexanol; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, and the like.
- Ethers ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Esters of ether alcohols such as propylene glycol monomethyl ether acetate. These can be used individually by 1 type or in mixture of 2 or more types.
- the polyisocyanate composition of the present embodiment in addition to the polyalkylene glycol alkyl ether and the polyisocyanate, at least selected from the group consisting of an antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant.
- an antioxidant in addition to the polyalkylene glycol alkyl ether and the polyisocyanate, at least selected from the group consisting of an antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant.
- a surfactant one kind may be further added.
- the coating composition of this embodiment contains the above-mentioned polyisocyanate composition. Moreover, the water-based coating composition of this embodiment contains the coating composition and water. A coating composition will not be specifically limited if it contains the above-mentioned polyisocyanate composition, Furthermore, it is good also as an organic-solvent type coating composition besides the water-system coating composition containing water.
- the water-based coating composition is preferable to the coating composition containing no water from the viewpoint of reducing the amount of the organic solvent used because the resin as the coating film forming component is dissolved or dispersed in a medium mainly containing water. .
- coating compositions and water-based coating compositions include architectural paints, automotive paints, automotive repair paints, plastic paints, adhesives, adhesives, building materials, household water-based paints, other coating agents, sealing agents, It can be used in inks, casting materials, elastomers, foams, plastic raw materials, and fiber treatment agents.
- the main resins in the aqueous coating composition are not limited to the following, but examples include acrylic resins, polyester resins, polyether resins, epoxy resins, fluororesins, polyurethane resins, and polyvinylidene chloride.
- examples include copolymers, polyvinyl chloride copolymers, vinyl acetate copolymers, acrylonitrile butadiene copolymers, polybutadiene copolymers, and styrene butadiene copolymers.
- acrylic resins include, but are not limited to, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) (Meth) acrylic esters such as 2-ethylhexyl acrylate and lauryl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters having active hydrogen such as -2-hydroxybutyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl; acrylic acid, methacrylic acid, maleic acid, Unsaturated carboxylic acids such as itaconic acid; acrylamide, N-methylolacrylamide, diacetone Unsaturated amides such as acrylamide; glycidyl methacrylate, styl
- Examples thereof include acrylic resins obtained by polymerizing the mixture.
- the polymerization method is generally emulsion polymerization, but can also be produced by suspension polymerization, dispersion polymerization, or solution polymerization. In emulsion polymerization, it can also be polymerized stepwise.
- polyester resins include, but are not limited to, succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and the like.
- polyether resins examples include, but are not limited to, for example, hydroxides such as lithium, sodium, and potassium; strong basic catalysts such as alcoholates and alkylamines; Polyether polyols obtained by adding a single or mixture of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, etc .; reacting alkylene oxide with polyfunctional compounds such as ethylenediamine Polyether polyols obtained by the above; polyether polyols obtained by ring-opening polymerization of cyclic ethers such as tetrahydrofuran; so-called polymers obtained by polymerizing acrylamide or the like using these polyethers as a medium. Ma polyols, and the like.
- acrylic resins and polyester resins are preferable.
- resin such as a melamine type hardening
- These resins are preferably emulsified, dispersed or dissolved in water. Therefore, the carboxyl group, the sulfone group, etc. contained in the resins can be neutralized.
- the neutralizing agent for neutralizing the carboxyl group, the sulfone group and the like is not limited to the following, but examples include ammonia, water-soluble amino compounds such as monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, and propylamine. , Dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, 2-ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholine Can be used.
- the neutralizing agent is preferably a tertiary amine such as triethylamine or dimethylethanolamine.
- inorganic pigments organic pigments, extender pigments, silane coupling agents, titanium coupling agents, organic phosphates, organic phosphites, thickeners, leveling agents, thixotropic agents commonly added to paints Antifoaming agent, freezing stabilizer, matting agent, crosslinking reaction catalyst, anti-skinning agent, dispersant, wetting agent, filler, plasticizer, lubricant, reducing agent, preservative, antifungal agent, deodorant, You may combine a yellowing prevention agent, a ultraviolet absorber, an antistatic agent or a charge control agent, and an anti-settling agent.
- a surfactant may be added, and in order to improve the storage stability of the paint, an antioxidant, a light stabilizer, and a polymerization inhibitor may be added. Also good.
- the coating base material of this embodiment is a coating base material provided with a base material and the coating film coated with the above-mentioned coating composition or the above-mentioned aqueous coating composition.
- the substrate of the present embodiment is not limited to the following, but examples include metals, wood, glass, stones, ceramic materials, concrete, hard and flexible plastics, textile products, leather products, and paper.
- a normal primer may be provided before coating.
- Isocyanate group content rate Using the polyisocyanate composition as a sample, the isocyanate group content rate was measured according to the method described in JIS K7301-1995 (Testing method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer). did. Below, the more specific measuring method of isocyanate group content rate is shown.
- the isocyanate group content was calculated by the following calculation method from the sample titration and blank titration determined above.
- Isocyanate group content (mass%) (blank titration ⁇ sample titration) ⁇ 42 / [sample mass (g) ⁇ 1,000] ⁇ 100%.
- Nonvolatile Content (Physical Property 4) Nonvolatile Content
- the mass of the aluminum cup was precisely weighed, about 1 g of the sample was added, and the cup mass before heat drying was precisely weighed.
- the cup containing the sample was heated in a dryer at 105 ° C. for 3 hours. After the heated cup was cooled to room temperature, the mass of the cup was weighed again.
- the mass% of the dry residue in the sample was defined as the nonvolatile content.
- the calculation method of the nonvolatile content is as follows. In the case of no solvent dilution, the non-volatile content was treated as substantially 100%.
- Nonvolatile content (mass%) (cup weight after heat drying ⁇ aluminum cup weight) / (cup weight before heat drying ⁇ aluminum cup weight) ⁇ 100%.
- Microtrack Nanotrack UPA-EX150 Particle permeability transmission Particle shape: non-spherical Particle refractive index: 1.81 Solvent refractive index: 1.33 Analysis range: 0.95 nm to 6540 nm Sample measurement time: 120 seconds Background measurement time: 120 seconds
- the modification rate is the ratio of the polyalkylene glycol alkyl ether modified with respect to 100 equivalents of the isocyanate group of the starting polyisoisocyanate, and is not yet measured at 220 nm by liquid chromatography (LC). It was determined from the peak area ratio of the modified isocyanurate trimer, the 1 modified isocyanurate trimer, the 2 modified isocyanurate trimer, and the 3 modified isocyanurate trimer.
- the equipment and conditions used are as follows.
- LC device manufactured by Waters, UPLC (trade name), Column: manufactured by Waters, ACQUITY UPLC HSS T3 1.8 ⁇ m C18 inner diameter 2.1 mm ⁇ length 50 mm Flow rate: 0.3 mL / min
- B acetonitrile
- Detection method photodiode array detector, measurement wavelength is 220 nm
- polyalkylene glycol alkyl ether Isocyanate group content (% by mass) / 100% / 42 / (100-modification rate (%)) ⁇ modification rate (%) ⁇ molecular weight of polyalkylene glycol alkyl ether ⁇ 100%
- polyalkylene glycol alkyl ether used is polyethylene glycol (mono) methyl ether
- Molecular weight of polyethylene glycol (mono) methyl ether molecular weight of methyl group (15) + molecular weight of hydroxyl group (17) + (molecular weight of ethylene oxide (44) ⁇ n average number)
- the dispersion ratio (3) of the molecular weight distribution of the portion derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate in the polyisocyanate composition was assumed to be the same as the dispersion ratio (2) of the molecular weight distribution.
- the reactivity of the polyalkylene glycol alkyl ether was the same regardless of the molecular weight.
- the dispersion ratio (1) of the molecular weight distribution of the charged polyalkylene glycol alkyl ether used as the raw material and the molecular weight of the unreacted polyalkylene glycol alkyl ether detected in the polyisocyanate composition The distribution dispersion ratio (2) was consistent.
- the dispersion ratio (3) of the molecular weight distribution of the part derived from the polyalkylene glycol alkyl ether of the modified polyisocyanate obtained by reacting with the polyisocyanate is the dispersion ratio (1) and (2) of the molecular weight distribution. Judged to be identical.
- the difference in the dispersion ratios (1) and (2) of the molecular weight distribution is within the measurement error range.
- LC device manufactured by Waters, UPLC (trade name), Column: manufactured by Waters, ACQUITY UPLC HSS T3 1.8 ⁇ m C18 inner diameter 2.1 mm ⁇ length 50 mm Flow rate: 0.3 mL / min
- b acetonitrile
- Detection method 1 photodiode array detector, measurement wavelength is 220 nm
- Detection method 2 Mass spectrometer, manufactured by Waters, Synapt G2 (trade name)
- Ionization mode Electrospray ionization, positive ion detection Scan range: m / z 100 to 2000
- the measurement was performed using the above-described apparatus and conditions. After separating the components by liquid chromatography, in the ion derived from the polyalkylene glycol alkyl ether detected by mass spectrometry, the following formula is obtained from the molecular weight obtained from the mass-to-charge ratio (m / z) and the relative intensity of the ion. was used to calculate the dispersion ratio of the molecular weight distribution.
- TSKgelSuperH1000 (trade name) x 1
- TSKgel Super H2000 (trade name) x 1
- TSKgel SuperH3000 (trade name) x 1
- Carrier Tetrahydrofuran Detection method: Differential UV meter Calculation method: Polyisocyanate containing a hindered phenolic compound in a known ratio was measured, and a calibration curve was created by the area (mV ⁇ sec) of the hindered phenolic compound. . Then, the content rate of the hindered phenol-type compound was calculated
- Preparation Example 8 Polyethylene glycol monomethyl ether (10) 200 mass ppm of 2,6-di-t-butyl-p-cresol (BHT) was added to the polyethylene glycol monomethyl ether (6) obtained in Preparation Example 4, and the mixture was stirred at 40 ° C. for 2 hours and mixed. Polyethylene glycol monomethyl ether (10) was obtained.
- BHT 2,6-di-t-butyl-p-cresol
- Preparation Example 9 Polyethylene glycol monomethyl ether (11) 400 mass ppm of 2,6-di-t-butyl-p-cresol (BHT) was added to the polyethylene glycol monomethyl ether (6) obtained in Preparation Example 4, and the mixture was stirred for 2 hours at 40 ° C. and mixed. Polyethylene glycol monomethyl ether (11) was obtained.
- BHT 2,6-di-t-butyl-p-cresol
- Polyisocyanate composition (3) 500 mass ppm of 2,6-di-t-butyl-p-cresol (BHT) was added to a commercially available polyisocyanate composition (trade name “TPA-100”, manufactured by Asahi Kasei Chemicals Corporation), and 2 at 40 ° C. The mixture was stirred for a period of time to obtain a polyisocyanate composition (3).
- BHT 2,6-di-t-butyl-p-cresol
- Example 1 Polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Preparation Example 1 of 87 parts by mass of a commercially available polyisocyanate composition (trade name “TKA-100” manufactured by Asahi Kasei Chemicals Corporation) 13 parts by mass of (3) was added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition (trade name “TKA-100” manufactured by Asahi Kasei Chemicals Corporation) 13 parts by mass of (3) was added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the resulting polyisocyanate composition has a non-volatile content of 100%, a water-dispersed particle size of 180 nm, an isocyanate group content of 17.3% by mass, a number average molecular weight of 760, and an average number of isocyanate functional groups of 3.1. there were.
- the average number of ethylene oxide repeating units detected from NMR was 7.1, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.06.
- the modification rate in the obtained composition was 8.4%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 13.0%.
- Example 2 Polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Preparation Example 2 of 84 parts by mass of a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) (4) 16 parts by mass was added, and the reaction was performed by stirring at 90 ° C. for 8 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) (4) 16 parts by mass was added, and the reaction was performed by stirring at 90 ° C. for 8 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the obtained polyisocyanate composition has a non-volatile content of 100%, a water-dispersed particle size of 190 nm, an isocyanate group content of 16.5% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.8. there were.
- the average number of ethylene oxide repeating units detected from NMR was 5.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the resulting composition was 1.14.
- the modification rate in the obtained composition was 14.0%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 16.1%.
- Example 3 83 parts by mass of a commercially available polyisocyanate composition (trade name “24A-100” manufactured by Asahi Kasei Chemicals Corporation), average number of ethylene oxide repeating units obtained in Preparation Example 3: 15 polyethylene glycol monomethyl ether (5) 17 parts by mass were added, and the reaction was performed by stirring at 90 ° C. for 6 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition trade name “24A-100” manufactured by Asahi Kasei Chemicals Corporation
- the obtained polyisocyanate composition has a non-volatile content: 100%, a water-dispersed particle size: 80 nm, an isocyanate group content: 18.6% by mass, a number average molecular weight: 720, and an average isocyanate functional group number: 3.2. there were.
- the average number of ethylene oxide repeating units detected from NMR was 15.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.21.
- the modification rate in the obtained composition was 5.2%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 16.8%.
- Example 4 83 parts by mass of the polyisocyanate composition (1) obtained in Production Example 1 and 17 parts by mass of polyethylene glycol monomethyl ether (6) having an average number of ethylene oxide repeating units obtained in Preparation Example 4 of 6.0 Then, the reaction was carried out by stirring at 110 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the obtained polyisocyanate composition has a non-volatile content: 100%, a water-dispersed particle size: 50 nm, an isocyanate group content: 14.8% by mass, a number average molecular weight: 670, and an average isocyanate functional group number: 2.4. there were.
- the average number of ethylene oxide repeating units detected from NMR was 6.1, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 13.9%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 17.1%.
- Example 5 3 parts of 1,3-butanediol (indicated in the table as “1,3-BD”) are added to 84 parts by mass of a commercially available polyisocyanate composition (trade name “TKA-100” manufactured by Asahi Kasei Chemicals Corporation). The reaction was carried out by adding 2 parts by mass and stirring at 80 ° C. for 2 hours under nitrogen. Thereafter, 13 parts by mass of polyethylene glycol monomethyl ether (7) having an average number of ethylene oxide repeating units obtained in Preparation Example 5 of 9.0 was added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. It was. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition (trade name “TKA-100” manufactured by Asahi Kasei Chemicals Corporation).
- the resulting polyisocyanate composition has a non-volatile content of 100%, a water-dispersed particle size of 100 nm, an isocyanate group content of 14.0% by mass, a number average molecular weight of 1070, and an average number of isocyanate functional groups of 3.6. there were.
- the average number of ethylene oxide repeating units detected from NMR was 9.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.10.
- the modification rate in the obtained composition was 8.4%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 13.1%.
- Example 6 90 parts by mass of the polyisocyanate composition (1) obtained in Production Example 1 and 10 parts by mass of polyethylene glycol monomethyl ether (7) having an average number of ethylene oxide repeating units obtained in Preparation Example 5 of 9.0 Then, the reaction was carried out by stirring at 110 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the obtained polyisocyanate composition has a non-volatile content: 100%, a water-dispersed particle size: 160 nm, an isocyanate group content: 17.6% by mass, a number average molecular weight: 620, and an average isocyanate functional group number: 2.6. there were.
- the average number of ethylene oxide repeating units detected from NMR was 9.1.
- the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 5.3%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 10.0%.
- Example 7 24.7 parts by mass of a commercially available HDI polyisocyanate composition (Asahi Kasei Chemicals Corporation, trade name “TKA-100”), a commercially available IPDI polyisocyanate composition (Evonik Japan Co., Ltd., trade name “T1890 / 100”) ”)
- TKA-100 a commercially available HDI polyisocyanate composition
- IPDI polyisocyanate composition Evonik Japan Co., Ltd., trade name “T1890 / 100”
- a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the obtained polyisocyanate composition had a non-volatile content of 72.0%, a water-dispersed particle size of 50 nm, and an isocyanate group content calculated with the non-volatile content as 100% (the isocyanate group content was determined in a solvent-containing state).
- the value was calculated by dividing the value by the nonvolatile content ratio): 13.5% by mass, number average molecular weight: 880, average isocyanate functional group number: 2.8.
- the average number of ethylene oxide repeating units detected from NMR was 12.0.
- the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.12.
- the modification rate in the obtained composition was 9.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 17.8%.
- Example 8 26.5 parts by mass of a commercially available polyisocyanate composition (trade name “TPA-100”, manufactured by Asahi Kasei Chemicals Corporation), 43.0 parts by mass of the polyisocyanate composition obtained in Production Example 1 (number average molecular weight) Average number of ethylene oxide repeating units obtained in Preparation Example 2 in 10.0 parts by mass of 6400 polypropylene glycol (Asahi Glass Co., Ltd., trade name “Exenol 840”, “Ex840” in the table): 17.2 parts by mass of 5.0 polyethylene glycol monomethyl ether (4) was added, and the reaction was carried out by stirring at 120 ° C. for 6 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- TPA-100 commercially available polyisocyanate composition
- Example 1 number average molecular weight
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 80 nm, an isocyanate group content of 12.3 mass%, a number average molecular weight of 820, and an average number of isocyanate functional groups of 2.4. there were.
- the average number of ethylene oxide repeating units detected from NMR was 5.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the resulting composition was 1.13.
- the modification rate in the obtained composition was 19.5%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 17.9%.
- Example 9 59.5 parts by mass of a commercially available HDI-based polyisocyanate composition (trade name “TKA-100” manufactured by Asahi Kasei Chemicals Corporation), a commercially available IPDI-based polyisocyanate composition (trade name “T1890 / 100” manufactured by Evonik Japan Co., Ltd.) ]
- a commercially available HDI-based polyisocyanate composition (trade name “TKA-100” manufactured by Asahi Kasei Chemicals Corporation), a commercially available IPDI-based polyisocyanate composition (trade name “T1890 / 100” manufactured by Evonik Japan Co., Ltd.)
- the reaction was carried out by stirring at 100 ° C. for 6 hours under nitrogen. After completion of the reaction, a polyis
- the obtained polyisocyanate composition had a non-volatile content of 72.5% and a water-dispersed particle size of 80 nm, and an isocyanate group content calculated by setting the non-volatile content to 100% (determining the isocyanate group content in a solvent-containing state)
- the value was calculated by dividing the value by the non-volatile content ratio): 15.5% by mass, number average molecular weight: 810, and average number of isocyanate functional groups: 3.0.
- the average number of ethylene oxide repeating units detected from NMR was 9.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.09.
- the modification rate in the obtained composition was 8.7%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 15.1%.
- Example 10 Polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Preparation Example 4 of 84 parts by mass of a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) (6) 16.0 parts by mass were added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) (6) 16.0 parts by mass were added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 140 nm, an isocyanate group content of 16.9% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.8. there were.
- the average number of ethylene oxide repeating units detected from NMR was 6.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 11.8%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 15.9%.
- Example 11 The modified polyisocyanate was prepared in the same manner as in Example 10 except that the polyethylene glycol monomethyl ether (10) obtained in Preparation Example 8 was used instead of the polyethylene glycol monomethyl ether (6) obtained in Preparation Example 4. A polyisocyanate composition was obtained.
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 140 nm, an isocyanate group content of 16.9% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.8. there were.
- the average number of ethylene oxide repeating units detected from NMR was 6.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 11.8%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 15.9%.
- the content rate of BHT was 0.003%.
- Example 12 The modified polyisocyanate was prepared in the same manner as in Example 10 except that the polyethylene glycol monomethyl ether (11) obtained in Preparation Example 9 was used instead of the polyethylene glycol monomethyl ether (6) obtained in Preparation Example 4. A polyisocyanate composition was obtained.
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 140 nm, an isocyanate group content of 16.9% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.8. there were.
- the average number of ethylene oxide repeating units detected from NMR was 6.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 11.8%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 15.9%.
- the content rate of BHT was 0.006%.
- Example 13 As in Example 10, except that the polyisocyanate composition (3) obtained in Preparation Example 10 was used instead of the commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation). Operation was performed to obtain a polyisocyanate composition containing the modified polyisocyanate.
- TPA-100 commercially available polyisocyanate composition
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 140 nm, an isocyanate group content of 16.9% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.8. there were.
- the average number of ethylene oxide repeating units detected from NMR was 6.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 11.8%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 15.9%.
- the content rate of BHT was 0.04%.
- Example 14 Polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Preparation Example 4 of 84 parts by mass of a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) (6) 16.0 parts by mass and 0.1 part by mass of BHT were added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) (6) 16.0 parts by mass and 0.1 part by mass of BHT were added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 140 nm, an isocyanate group content of 16.9% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.8. there were.
- the average number of ethylene oxide repeating units detected from NMR was 6.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 11.8%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 15.9%. Further, the content of BHT was 0.10%.
- Example 15 Polyethylene glycol having an average number of ethylene oxide repeating units obtained in Preparation Example 11 of 82.5 parts by mass of a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) 17.5 parts by mass of monomethyl ether (12) was added, and the reaction was carried out by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation
- the obtained polyisocyanate composition has a non-volatile content of 100%, a water-dispersed particle size of 150 nm, an isocyanate group content of 16.2% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.7. there were.
- the average number of ethylene oxide repeating units detected from NMR was 5.2, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.13.
- the modification rate in the obtained composition was 14.7%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 17.3%.
- Example 16 Polyethylene glycol having an average number of ethylene oxide repeating units obtained in Preparation Example 12 of 83.0 parts by mass of a commercially available polyisocyanate composition (trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation) 17.0 parts by mass of monomethyl ether (13) was added, and the reaction was carried out by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- a commercially available polyisocyanate composition trade name “TPA-100” manufactured by Asahi Kasei Chemicals Corporation 17.0 parts by mass of monomethyl ether (13) was added, and the reaction was carried out by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a polyisocyanate composition containing a modified polyisocyanate was obtained.
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 150 nm, an isocyanate group content of 16.4% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.7. there were.
- the average number of ethylene oxide repeating units detected from NMR was 5.4, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.12.
- the modification rate in the obtained composition was 13.8%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 16.9%.
- the resulting polyisocyanate composition has a non-volatile content of 100%, a water-dispersed particle size of 240 nm, an isocyanate group content of 17.4% by mass, a number average molecular weight of 760, and an average number of isocyanate functional groups of 3.1. there were.
- the average number of ethylene oxide repeating units detected from NMR was 7.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.03.
- the modification rate in the obtained composition was 8.4%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 12.9%.
- a commercially available HDI-based polyisocyanate composition trade name “TKA-100” manufactured by Asah
- the obtained polyisocyanate composition had a non-volatile content of 72.0% and a water-dispersed particle size of 200 nm, and an isocyanate group content calculated with the non-volatile content of 100% (the isocyanate group content was determined in a solvent-containing state).
- the value was calculated by dividing the value by the non-volatile content ratio): 15.6% by mass, number average molecular weight: 800, and average number of isocyanate functional groups: 3.0.
- the average number of ethylene oxide repeating units detected from NMR was 9.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.04.
- the modification rate in the obtained composition was 8.6%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 15.0%.
- the obtained polyisocyanate composition has a nonvolatile content of 100%, a water-dispersed particle size of 210 nm, an isocyanate group content of 16.9% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.8. there were.
- the average number of ethylene oxide repeating units detected from NMR was 6.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.04.
- the modification rate in the obtained composition was 12.0%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 16.2%.
- the resulting polyisocyanate composition has a non-volatile content of 100%, a water-dispersed particle size of 250 nm, an isocyanate group content of 16.3% by mass, a number average molecular weight of 700, and an average number of isocyanate functional groups of 2.7. there were.
- the average number of ethylene oxide repeating units detected from NMR was 4.8.
- the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.16.
- the modification rate in the obtained composition was 14.6%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 16.1%.
- the obtained polyisocyanate composition has a non-volatile content of 72.5%, a water-dispersed particle size of 500 nm or more, and an isocyanate group content calculated based on the non-volatile content of 100% (isocyanate group content in a solvent-containing state).
- the value was calculated by dividing the value by the non-volatile content ratio): 14.5% by mass, number average molecular weight: 1300, average number of isocyanate functional groups: 4.5.
- the average number of ethylene oxide repeating units detected from NMR was 8.9, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.10.
- the modification rate in the obtained composition was 9.2%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 14.8%.
- the obtained polyisocyanate composition has a non-volatile content: 100%, a water-dispersed particle size: 210 nm, an isocyanate group content: 18.0 mass%, a number average molecular weight: 620, and an average isocyanate functional group number: 2.7. there were.
- the average number of ethylene oxide repeating units detected from NMR was 9.0, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.11.
- the modification rate in the obtained composition was 4.6%, and thus the content of polyethylene glycol monomethyl ether was calculated to be 8.8%.
- the obtained polyisocyanate composition has a non-volatile content of 72.1%, a water-dispersed particle size of 500 nm or more, and an isocyanate group content calculated based on a non-volatile content of 100% (isocyanate group content in a solvent-containing state).
- the value was calculated by dividing the value by the non-volatile content ratio): 15.6% by mass, number average molecular weight: 1210, and average number of isocyanate functional groups: 4.5.
- the average number of ethylene oxide repeating units detected from NMR was 4.2, and the dispersion ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.01.
- the modification rate in the obtained composition was 10.0%, and therefore the content of polyethylene glycol monomethyl ether was calculated to be 8.9%.
- the judging method was as follows. A: 80% by mass or more B: 60% by mass or more and less than 80% by mass C: Less than 60% by mass
- the change in the concentration of the isocyanate group was determined by measuring the amount of isocyanate in the infrared absorption spectrum using FT / IR-4200typeA (trade name) manufactured by JASCO Corporation (detector: TGS, number of integrations: 16, decomposition: 4 cm ⁇ 1 ). It was calculated from an intensity ratio of an isocyanate absorption peak (near wave number 2271 cm ⁇ 1 ) to an absorption peak of nurate (near wave number 1686 cm ⁇ 1 ).
- Examples 17 to 32, Comparative Examples 8 to 14 Using the polyisocyanate compositions containing the modified polyisocyanates obtained in Examples 1 to 16 and Comparative Examples 1 to 7, coating compositions (1) and (2) were prepared as follows. The prepared coating composition (1) was used for the following (Evaluation 4) evaluation, and the coating composition (2) was used for the following (Evaluation 5) to (Evaluation 8).
- a coating composition was prepared in the same manner as in the preparation of the coating composition (1) except that the stirring for 3 minutes at 200 rpm was changed to 10 minutes at 600 rpm. Using the coating compositions thus prepared, the following coating film evaluations (Evaluation 5) to (Evaluation 8) were performed. However, the results of (Evaluation 6) to (Evaluation 8) were not evaluated if the coating film appearance was extremely bad. The evaluation results are shown in Table 2.
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Abstract
Description
[1]
ポリイソシアネートと、下記一般式(1)で表されるポリアルキレングリコールアルキルエーテルと、の反応により得られる変性ポリイソシアネートを含む、ポリイソシアネート組成物であって、
平均イソシアネート官能基数が、1.8以上4.0以下であり、
前記ポリイソシアネート組成物の総量に対して、前記変性ポリイソシアネートにおける前記ポリアルキレングリコールアルキルエーテルに由来する部分を、10質量%以上18質量%以下含み、
前記変性ポリイソシアネートにおいて、前記ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比が、1.05以上2.00以下である、ポリイソシアネート組成物。
[2]
前記分子量分布の分散比は、1.05以上1.50以下である、[1]に記載のポリイソシアネート組成物。
[3]
前記式(1)中、R1はエチレン基であり、nの平均数は5.0以上15以下である、[1]又は[2]に記載のポリイソシアネート組成物。
[4]
前記ポリアルキレングリコールアルキルエーテルは、前記式(1)中、nの平均数が異なる二種以上のポリアルキレングリコールアルキルエーテルを含む、[1]~[3]のいずれかに記載のポリイソシアネート組成物。
[5]
ヒンダードフェノール系化合物をさらに含む、[1]~[4]のいずれかに記載のポリイソシアネート組成物。
[6]
ポリイソシアネートと、下記一般式(2)で表されるポリアルキレングリコールアルキルエーテルと、を反応させ、変性ポリイソシアネートを含むポリイソシアネート組成物を得る反応工程を含み、
前記反応工程は、平均イソシアネート官能基数が、1.8以上4.0以下であり、前記ポリイソシアネート組成物の総量に対して、前記変性ポリイソシアネートにおける前記ポリアルキレングリコールアルキルエーテルに由来する部分を、10質量%以上18質量%以下含み、かつ、前記変性ポリイソシアネートにおいて、前記ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比が、1.05以上2.00以下である、前記ポリイソシアネート組成物を得るように反応させる工程である、ポリイソシアネート組成物の製造方法。
[7]
前記分子量分布の分散比は、1.05以上1.50以下である、[6]に記載のポリイソシアネート組成物の製造方法。
[8]
前記式(2)中、R1はエチレン基であり、nの平均数は5.0以上15以下である、[6]又は[7]に記載のポリイソシアネート組成物の製造方法。
[9]
前記ポリアルキレングリコールアルキルエーテルは、前記式(2)中、nの平均数が異なる二種以上のポリアルキレングリコールアルキルエーテルを含む、[6]~[8]のいずれかに記載のポリイソシアネート組成物の製造方法。
[10]
[1]~[5]のいずれかに記載のポリイソシアネート組成物を含む、コーティング組成物。
[11]
[10]に記載のコーティング組成物と、水と、を含む、水系コーティング組成物。
[12]
基材と、[10]に記載のコーティング組成物又は[11]に記載の水系コーティング組成物によってコーティングされたコーティング膜と、を備える、コーティング基材。
本実施形態のポリイソシアネート組成物は、ポリイソシアネートと、下記一般式(1)で表されるポリアルキレングリコールアルキルエーテルと、の反応により得られる変性ポリイソシアネートを含む。また、上記ポリイソシアネート組成物は、平均イソシアネート官能基数が、1.8以上4.0以下であり、該ポリイソシアネート組成物の総量(100質量%)に対して、上記変性ポリイソシアネートにおける上記ポリアルキレングリコールアルキルエーテルに由来する部分を、10質量%以上18質量%以下含む。さらに、上記変性ポリイソシアネートにおいて、上記ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比が、1.05以上2.00以下である。
本実施形態のポリイソシアネートとしては、以下のものに限定されないが、例えば、脂肪族ジイソシアネート、脂環族ジイソシアネート、及び芳香族ジイソシアネートから選ばれる少なくとも1種のジイソシアネート化合物、これらジイソシアネート化合物から誘導されるポリイソシアネート化合物が挙げられる。本実施形態に用いるポリイソシアネートは、工業的に入手しやすいという観点から、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、及び芳香族ポリイソシアネートからなる群より選ばれる少なくとも一種のジイソシアネート化合物であることが好ましい。
本実施形態に用いるポリアルキレングリコールアルキルエーテルは、下記一般式(1)で表される構造を有する。
分子量分布の分散比=B/A
A=ΣMiIi/ΣIi
B=ΣMi 2Ii/ΣMiIi
(Miは各成分の質量電荷比(m/z)から求めた分子量、Iiは各成分のイオンの相対強度を示す。)
本実施形態のポリイソシアネート組成物の製造方法は、ポリイソシアネートと、下記一般式(2)で表されるポリアルキレングリコールアルキルエーテルとを、反応させ、変性ポリイソシアネートを含むポリイソシアネート組成物を得る反応工程を含む。反応工程は、平均イソシアネート官能基数が1.8以上4.0以下であり、上記ポリイソシアネート組成物の総量(100質量%)に対して上記変性ポリイソシアネートにおける上記ポリアルキレングリコールアルキルエーテルに由来する部分を10質量%以上18質量%以下含み、かつ、上記変性ポリイソシアネートにおいて、上記ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比が、1.05以上2.00以下である、上記ポリイソシアネート組成物を得るように反応させる工程である。また、反応工程において、ポリイソシアネートとポリアルキレングリコールアルキルエーテルとを、混合させて反応させることが好ましい。
本実施形態のコーティング組成物は、上述のポリイソシアネート組成物を含む。また、本実施形態の水系コーティング組成物は、そのコーティング組成物と水とを含む。コーティング組成物は、上述のポリイソシアネート組成物を含むものであれば特に限定されず、さらに水を含む水系コーティング組成物以外にも、有機溶剤系のコーティング組成物としてもよい。水系コーティング組成物は、水を主とする媒体中に塗膜形成成分である樹脂類が溶解又は分散しており、有機溶剤の使用量低減の観点から、水を含まないコーティング組成物よりも好ましい。
本実施形態のコーティング基材は、基材と、上述のコーティング組成物又は上述の水系コーティング組成物によってコーティングされたコーティング膜と、を備えるコーティング基材である。
ポリイソシアネート組成物を試料として、イソシアネート基含有率の測定は、JIS K7301-1995(熱硬化性ウレタンエラストマー用トリレンジイソシアネート型プレポリマー試験方法)に記載の方法に従って実施した。以下に、より具体的なイソシアネート基含有率の測定方法を示す。
(2)その後、上記フラスコに2.0Nのジ-n-ブチルアミン・トルエン溶液20mLを添加し、15分間静置した。
(3)上記フラスコに2-プロパノール70mLを添加し、溶解させて溶液を得た。
(4)上記(3)で得られた溶液について、1mol/L塩酸を用いて滴定を行い、試料滴定量を求めた。
(5)試料を添加しない場合にも、上記(1)~(3)と同様の方法で測定を実施し、ブランク滴定量を求めた。
上記で求めた試料滴定量及びブランク滴定量から、イソシアネート基含有率を以下の計算方法により算出した。
イソシアネート基含有率(質量%)=(ブランク滴定量-試料滴定量)×42/[試料質量(g)×1,000]×100%。
ポリイソシアネート組成物を試料として、ポリイソシアネート組成物中の変性ポリイソシアネートと未反応ポリイソシアネートとを含むポリイソシアネートの数平均分子量は、以下の装置及び条件を用いてゲルパーミエーションクロマトグラフ(GPC)によりポリスチレン基準の数平均分子量を測定した。
装置:東ソー(株)製 HLC-8120GPC(商品名)
カラム:東ソー(株)製 TSKgelSuperH1000(商品名)×1本、TSKgelSuperH2000(商品名)×1本、TSKgelSuperH3000(商品名)×1本、
キャリアー:テトラヒドロフラン
検出方法:示差屈折計
ポリイソシアネート組成物を試料として、平均イソシアネート官能基数は、ポリイソシアネート1分子が統計的に有するイソシアネート官能基の数であり、(物性2)で測定したポリイソシアネートの数平均分子量と(物性1)で測定したイソシアネート基含有率とから以下のとおり算出した。
平均官能基数=ポリイソシアネートの数平均分子量×イソシアネート基含有率(質量%)/100%/42
ポリイソシアネート組成物を試料として、溶剤希釈をした場合には、アルミニウム製カップの質量を精秤し、試料約1gを入れて、加熱乾燥前のカップ質量を精秤した。上記試料を入れたカップを105℃の乾燥機中で3時間加熱した。上記加熱後のカップを室温まで冷却した後、再度カップの質量を精秤した。試料中の乾燥残分の質量%を不揮発分とした。不揮発分の計算方法は以下のとおりである。なお、溶剤希釈なしの場合には、不揮発分は実質的に100%であるとして扱った。
不揮発分(質量%)=(加熱乾燥後のカップ質量-アルミニウム製カップ質量)/(加熱乾燥前のカップ質量-アルミニウム製カップ質量)×100%。
ポリイソシアネート組成物を試料として、ポリイソシアネート組成物中の変性ポリイソシアネートと未反応ポリイソシアネートとを含むポリイソシアネートの水分散粒子径は、レーザー回折・散乱式粒子径分布測定装置を用いて積算分布曲線より、50%径(d50)の値を測定した。
装置:日機装株式会社製 マイクロトラック ナノトラック UPA-EX150
粒子透過性:透過
粒子形状:非球形
粒子屈折率:1.81
溶媒屈折率:1.33
解析範囲:0.95nmから6540nm
サンプル測定時間:120秒
バックグラウンド測定時間:120秒
ポリイソシアネート組成物を試料として、nの平均数は、以下の装置及び条件を用いてプロトン核磁気共鳴(NMR)により求めた。ここでは、アルキレン基に対応する相対強度の積分値とアルキル基に対応する相対強度の積分値を対応させることにより、ポリイソシアネート組成物中のポリアルキレングリコールアルキルエーテルのnの平均数を求めた。
NMR装置:Bruker Biospin Avance600(商品名)
観測核:1H
周波数:600MHz
溶媒:CDCl3
積算回数:256回
原料のポリアルキレングリコールアルキルエーテルを試料として、nの平均数は、下記の水酸基価から算出した。
水酸基価の測定は、JIS K 0070-1992(化学製品の酸価,けん化価,エステル価,よう素価,水酸基価及び不けん化物の試験方法)及び、JIS K 1557-1(プラスチック?ポリウレタン原料ポリオール試験方法?第1部:水酸基価の求め方)に記載の方法に従って実施した。
上記で求めた水酸基価から、ポリアルキレングリコールアルキルエーテルの分子量を求め、その値を用いてnの平均数を以下の計算方法により算出した。
nの平均数=(ポリアルキレングリコールアルキルエーテルの分子量-アルキル基の分子量-水酸基の分子量)/(アルキレンオキサイドの分子量)
ポリアルキレングリコールアルキルエーテルの分子量=56.1×1000/[水酸基価(mgKOH/g)]
例えば、使用したポリアルキレングリコールアルキルエーテルがポリエチレングリコール(モノ)メチルエーテルだった場合、以下のように求められる。
nの平均数=(ポリエチレングリコール(モノ)メチルエーテルの分子量-メチル基の分子量(15)-水酸基の分子量(17))/(エチレンオキサイドの分子量(44))
ポリイソシアネート組成物を試料として、変性率は、原料のポリイソイソシアネートのイソシアネート基100当量に対して、ポリアルキレングリコールアルキルエーテルが変性された割合であり、液体クロマトグラフィー(LC)の220nmにおける、未変性イソシアヌレート3量体、1変性イソシアヌレート3量体、2変性イソシアヌレート3量体、及び3変性イソシアヌレート3量体のピーク面積比から求めた。用いた装置及び条件は以下のとおりである。
LC装置:Waters社製、UPLC(商品名)、
カラム:Waters社製、ACQUITY UPLC HSS T3 1.8μm C18 内径2.1mm×長さ50mm
流速:0.3mL/min
移動相:A=10mM酢酸アンモニウム水溶液、B=アセトニトリル
グラジェント条件:初期の移動相組成はA/B=98/2で、試料注入後Bの比率を直線的に上昇させ、10分後にA/B=0/100とした。
検出方法:フォトダイオードアレイ検出器、測定波長は220nm
ポリイソシアネート組成物を試料として、ポリイソシアネート組成物中の、変性ポリイソシアネートのポリアルキレングリコールアルキルエーテルに由来する部分の含有率は、(物性1)で測定したイソシアネート基含有率と、(物性6)で求めたポリアルキレングリコールアルキルエーテルのnの平均数から算出されるポリアルキレングリコールアルキルエーテルの分子量と、(物性8)で求めた変性率とから以下のとおり算出した。
含有率(%)=イソシアネート基含有率(質量%)/100%/42/(100-変性率(%))×変性率(%)×ポリアルキレングリコールアルキルエーテルの分子量×100%
例えば、使用したポリアルキレングリコールアルキルエーテルがポリエチレングリコール(モノ)メチルエーテルだった場合、以下のように求められる。
ポリエチレングリコール(モノ)メチルエーテルの分子量=メチル基の分子量(15)+水酸基の分子量(17)+(エチレンオキサイドの分子量(44)×nの平均数)
原料のポリアルキレングリコールアルキルエーテルを試料として、ポリアルキレングリコールアルキルエーテルの分子量分布の分散比(1)を求めた。また、ポリイソシアネート組成物を試料として、未反応のポリアルキレングリコールアルキルエーテルの分子量分布の分散比(2)を求めた。ポリイソシアネート組成物中の変性ポリイソシアネートの、ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比(3)は、分子量分布の分散比(2)と同一であるとした。
原料のポリアルキレングリコールアルキルエーテルを試料としたとき、ポリアルキレングリコールアルキルエーテルの反応性は、分子量に依存せず同等であった。よって、表1に記載の通り、原料として用いた仕込みのポリアルキレングリコールアルキルエーテルの分子量分布の分散比(1)と、ポリイソシアネート組成物中から検出される未反応のポリアルキレングリコールアルキルエーテルの分子量分布の分散比(2)は一致した。このため、ポリイソシアネートと反応して得られた変性ポリイソシアネートの、ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比(3)は、分子量分布の分散比(1)及び(2)と同一であると判断した。なお、表1における、分子量分布の分散比(1)及び(2)における差分は、測定誤差の範囲内のものである。
用いた装置及び条件は以下のとおりである。
LC装置:Waters社製、UPLC(商品名)、
カラム:Waters社製、ACQUITY UPLC HSS T3 1.8μm C18 内径2.1mm×長さ50mm
流速:0.3mL/min
移動相:a=10mM酢酸アンモニウム水溶液、b=アセトニトリル
グラジェント条件:初期の移動相組成比はa/b=98/2で、試料注入後bの比率を直線的に上昇させ、10分後にa/b=0/100とした。
検出方法1:フォトダイオードアレイ検出器、測定波長は220nm
検出方法2:質量分析装置、Waters社製、Synapt G2(商品名)
イオン化モード:エレクトロスプレーイオン化、正イオン検出
スキャンレンジ:m/z 100から2000
分子量分布の分散比=B/A
A=ΣMiIi/ΣIi
B=ΣMi 2Ii/ΣMiIi
(Miは各成分の質量電荷比(m/z)から求めた分子量、Iiは各成分のイオンの相対強度を示す)
ポリイソシアネート組成物を試料として、ポリイソシアネート組成物中のヒンダードフェノール系化合物の含有率は、以下の装置及び条件を用いてゲルパーミエーションクロマトグラフ(GPC)により、紫外線(UV)波長280nmで検出されるヒンダードフェノール系化合物のピーク面積から算出した。
装置:東ソー(株)製 HLC-8120GPC(商品名)
カラム:東ソー(株)製 TSKgelSuperH1000(商品名)×1本、TSKgelSuperH2000(商品名)×1本、TSKgelSuperH3000(商品名)×1本、
キャリアー:テトラヒドロフラン
検出方法:示差UV計
算出方法:ヒンダードフェノール系化合物が既知の割合で含有されているポリイソシアネートを測定し、ヒンダードフェノール系化合物の面積(mV×秒)で検量線を作成した。その後、実施例及び比較例のポリイソシアネート組成物から検出された面積(mV×秒)からヒンダードフェノール系化合物の含有率を求めた。
攪拌機、温度計、還流冷却管、窒素吹き込み管、滴下ロートを取り付けた四つ口フラスコの内部を窒素置換し、HDI1000部と2-エチルヘキサノール30部を仕込み、攪拌下80℃で2時間ウレタン化反応を行った。イソシアヌレート化及びアロファネート化触媒としてテトラメチルアンモニウムカプリエートを0.04部添加し、約3時間反応させ、リン酸の固形分85%水溶液0.075部を加えて反応を停止した。反応液をろ過した後、薄膜蒸発缶を用いて未反応のHDIを除去し、ポリイソシアネート組成物(1)を得た。
撹拌機、温度計、還流冷却管、窒素吹き込み管、滴下ロートを取り付けた四つ口フラスコ内を窒素雰囲気にし、HDIを600部、3価アルコールである分子量300のポリカプロラクトン系ポリエステルポリオール(ダイセル化学株式会社製、商品名「プラクセル303」)30部を仕込み、撹拌下反応器内温度を90℃1時間保持しウレタン化反応を行った。その後反応器内温度を60℃に保持し、イソシアヌレート化触媒としてテトラメチルアンモニウムカプリエートを加え、収率が48%になった時点で燐酸を添加し反応を停止した。反応液をろ過した後、薄膜蒸発缶を用いて未反応のHDIを除去し、ポリイソシアネート組成物(2)を得た。
1000mLオートクレーブの反応器内を窒素置換した後、メタノール128g(4.0mol)及び水酸化カリウム0.56g(10.0mmol)を仕込んだ。110℃に昇温した後、この温度を保ちながらエチレンオキサイド880g(28.0mol)を加圧下で2.5時間かけて反応させ、さらに1時間熟成を行った。得られた反応混合物に、85質量%のリン酸1.16g(10.0mmol)を加え中和し、析出したリン酸のカリウム塩を濾過で除き、エチレンオキサイド繰返単位の平均数:7.0のポリエチレングリコールモノメチルエーテル(1)を得た。分散比を測定したところ、1.03であった。
1000mLオートクレーブの反応器内を窒素置換した後、メタノール128g(4.0mol)及び水酸化カリウム0.56g(10.0mmol)を仕込んだ。110℃に昇温した後、この温度を保ちながらエチレンオキサイド1056g(24.0mol)を加圧下で2.5時間かけて反応させ、さらに1時間熟成を行った。得られた反応混合物に、85質量%のリン酸1.16g(10.0mmol)を加え中和し、析出したリン酸のカリウム塩を濾過で除き、エチレンオキサイド繰返単位の平均数:6.0のポリエチレングリコールモノメチルエーテル(2)を得た。分散比を測定したところ、1.04であった。
エチレンオキサイド繰返単位の平均数:3.0のトリエチレングリコールモノメチルエーテルと、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」)を、質量比で2.1:10.9になるように混合し、エチレンオキサイド繰返単位の平均数:7.0のポリエチレングリコールモノメチルエーテル(3)を得た。分散比を測定したところ、1.06であった。
エチレンオキサイド繰返単位の平均数:4.2のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG」)と、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」)を、質量比で130:55になるように混合し、エチレンオキサイド繰返単位の平均数:5.0のポリエチレングリコールモノメチルエーテル(4)を得た。分散比を測定したところ、1.13であった。
エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」)と、平均分子量1000のポリエチレングリコールモノメチルエーテル(日本油脂株式会社製、商品名「ユニオックスM-1000(エチレンオキサイド繰返単位の平均数:22)」)を、質量比で5.7:11.3になるように混合し、エチレンオキサイド繰返単位の平均数:15.0のポリエチレングリコールモノメチルエーテル(5)を得た。分散比を測定したところ、1.20であった。
エチレンオキサイド繰返単位の平均数:4.2のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG」)と、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」)を、質量比で16:19になるように混合し、エチレンオキサイド繰返単位の平均数:6.0のポリエチレングリコールモノメチルエーテル(6)を得た。分散比を測定したところ、1.11であった。
製造例4で得られたエチレンオキサイド繰返単位の平均数:6.0のポリエチレングリコールモノメチルエーテル(2)と、平均分子量550のポリエチレングリコールモノメチルエーテル(日本油脂株式会社製、商品名「ユニオックスM-550(エチレンオキサイド繰返単位の平均数:11.8)」)を、質量比で1:2になるように混合し、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(7)を得た。分散比を測定したところ、1.10であった。
エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」)と、エチレンオキサイド繰返単位の平均数:15のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-081」)を、質量比で6.8:11.0になるように混合し、エチレンオキサイド繰返単位の平均数:12.0のポリエチレングリコールモノメチルエーテル(8)を得た。分散比を測定したところ、1.12であった。
エチレンオキサイド繰返単位の平均数:4.2のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG」と、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」を、質量比で12.5:3.5になるように混合し、エチレンオキサイド繰返単位の平均数:4.8のポリエチレングリコールモノメチルエーテル(9)を得た。分散比を測定したところ、1.17であった。
調製例4で得られたポリエチレングリコールモノメチルエーテル(6)に、2,6-ジ-t-ブチル-p-クレゾール(BHT)を200質量ppm添加し、40℃で2時間撹拌して混合し、ポリエチレングリコールモノメチルエーテル(10)を得た。
調製例4で得られたポリエチレングリコールモノメチルエーテル(6)に、2,6-ジ-t-ブチル-p-クレゾール(BHT)を400質量ppm添加し、40℃で2時間撹拌して混合し、ポリエチレングリコールモノメチルエーテル(11)を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)に、2,6-ジ-t-ブチル-p-クレゾール(BHT)を500質量ppm添加し、40℃で2時間撹拌して混合し、ポリイソシアネート組成物(3)を得た。
エチレンオキサイド繰返単位の平均数:4.2のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG」)と、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」)を、質量比で46:27になるように混合し、エチレンオキサイド繰返単位の平均数:5.3のポリエチレングリコールモノメチルエーテル(12)を得た。分散比を測定したところ、1.13であった。
エチレンオキサイド繰返単位の平均数:4.2のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG」)と、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」)を、質量比で30:22になるように混合し、エチレンオキサイド繰返単位の平均数:5.5のポリエチレングリコールモノメチルエーテル(13)を得た。分散比を測定したところ、1.12であった。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TKA-100」)87質量部に、調製例1で得られたエチレンオキサイド繰返単位の平均数:7.0のポリエチレングリコールモノメチルエーテル(3)を13質量部添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)84質量部に、調製例2で得られたエチレンオキサイド繰返単位の平均数:5.0のポリエチレングリコールモノメチルエーテル(4)16質量部を添加し、窒素下、90℃で8時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「24A-100」)83質量部、調製例3で得られたエチレンオキサイド繰返単位の平均数:15のポリエチレングリコールモノメチルエーテル(5)17質量部を添加し、窒素下、90℃で6時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
製造例1で得られたポリイソシアネート組成物(1)83質量部、調製例4で得られたエチレンオキサイド繰返単位の平均数:6.0のポリエチレングリコールモノメチルエーテル(6)17質量部を添加し、窒素下、110℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TKA-100」)84質量部に、1,3-ブタンジオール(表中、「1,3-BD」と表記する。)を3質量部添加し、窒素下、80℃2時間撹拌して反応を行った。その後、調製例5で得られたエチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(7)を13質量部添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
製造例1で得られたポリイソシアネート組成物(1)90質量部、調製例5で得られたエチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(7)10質量部を添加し、窒素下、110℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のHDI系ポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TKA-100」)24.7質量部、市販のIPDI系ポリイソシアネート組成物(エボニックジャパン株式会社製、商品名「T1890/100」)57.5質量部に、調製例6で得られたエチレンオキサイド繰返単位の平均数:12.0のポリエチレングリコールモノメチルエーテル(8)17.8質量部、プロピレングリコールモノメチルエーテルアセテート40質量部を添加し、窒素下、100℃で6時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)26.5質量部、製造例1で得られたポリイソシアネート組成物(1)43.0質量部、数平均分子量6400のポリプロピレングリコール(旭硝子株式会社製、商品名「エクセノール840」、表中「Ex840」と表記する。)10.0質量部に、調製例2で得られたエチレンオキサイド繰返単位の平均数:5.0のポリエチレングリコールモノメチルエーテル(4)17.2質量部を添加し、窒素下、120℃で6時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のHDI系ポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TKA-100」)59.5質量部、市販のIPDI系ポリイソシアネート組成物(エボニックジャパン株式会社製、商品名「T1890/100」)25.5質量部に、調製例5で得られたエチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(7)15.0質量部、酢酸ブチル40質量部を添加し、窒素下、100℃で6時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)84質量部に、調製例4で得られたエチレンオキサイド繰返単位の平均数:6.0のポリエチレングリコールモノメチルエーテル(6)16.0質量部を添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
調製例4で得られたポリエチレングリコールモノメチルエーテル(6)の代わりに、調製例8で得られたポリエチレングリコールモノメチルエーテル(10)を用いた以外は実施例10と同様に操作し、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
調製例4で得られたポリエチレングリコールモノメチルエーテル(6)の代わりに、調製例9で得られたポリエチレングリコールモノメチルエーテル(11)を用いた以外は実施例10と同様に操作し、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)の代わりに、調製例10で得られたポリイソシアネート組成物(3)を用いた以外は実施例10と同様に操作し、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)84質量部に、調製例4で得られたエチレンオキサイド繰返単位の平均数:6.0のポリエチレングリコールモノメチルエーテル(6)16.0質量部、BHT0.1質量部を添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)82.5質量部に、調製例11で得られたエチレンオキサイド繰返単位の平均数:5.3のポリエチレングリコールモノメチルエーテル(12)17.5質量部を添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)83.0質量部に、調製例12で得られたエチレンオキサイド繰返単位の平均数:5.5のポリエチレングリコールモノメチルエーテル(13)17.0質量部を添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TKA-100」)87質量部に、製造例3で得られたエチレンオキサイド繰返単位の平均数:7.0のポリエチレングリコールモノメチルエーテル(1)13.0質量部を添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のHDI系ポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TKA-100」)59.5質量部、市販のIPDI系ポリイソシアネート組成物(エボニックジャパン株式会社製、商品名「T1890/100」)25.5質量部に、エチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG-130」、分子量分布の分散比:1.04)15.0質量部、酢酸ブチル40質量部を添加し、窒素下、100℃で6時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)84質量部に、製造例4で得られたエチレンオキサイド繰返単位の平均数:6.0のポリエチレングリコールモノメチルエーテル(2)16.0質量部を添加し、窒素下、120℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
市販のポリイソシアネート組成物(旭化成ケミカルズ株式会社製、商品名「TPA-100」)84質量部に、調製例7で得られたエチレンオキサイド繰返単位の平均数:4.8のポリエチレングリコールモノメチルエーテル(9)16.0質量部を添加し、窒素下、90℃で8時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
製造例2で得られたポリイソシアネート組成物(2)85質量部に、調製例5で得られたエチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(7)15質量部、酢酸ブチル40質量部を添加し、窒素下、120℃で4時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
製造例1で得られたポリイソシアネート組成物(1)91質量部、調製例5で得られたエチレンオキサイド繰返単位の平均数:9.0のポリエチレングリコールモノメチルエーテル(7)9質量部を添加し、窒素下、110℃で3時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
製造例2で得られたポリイソシアネート組成物(2)91質量部に、エチレンオキサイド繰返単位の平均数:4.2のポリエチレングリコールモノメチルエーテル(日本乳化剤株式会社製、商品名「MPG」、分子量分布の分散比:1.01)9質量部、酢酸ブチル40質量部を添加し、窒素下、120℃で4時間攪拌して反応を行った。反応終了後、変性ポリイソシアネートを含むポリイソシアネート組成物を得た。
(1)100mLフラスコと、吉野紙との質量を測定した。
(2)変性ポリイソシアネートを含むポリイソシアネート組成物を、固形分換算で16gとなるように100mLフラスコに採取し、脱イオン水24gを添加した。
(3)プロペラ羽を使用し、200rpmで3分間、100mLフラスコ内の溶液を撹拌した後、(1)で秤量した吉野紙で濾過した。
(4)吉野紙に残った濾過残渣と、100mLフラスコに残った残渣とを合わせて105℃の乾燥機中で1時間加熱し、質量(g)を求めた。
(5)以下の計算方法で、変性ポリイソシアネートを含む組成物が水へ分散した割合を求めた。
水へ分散した割合(質量%)=100%-((4)で求めた残渣を含む100mLフラスコと吉野紙との合計質量(g)-(1)で測定した100mLフラスコと吉野紙との合計質量(g))/((2)で採取した変性ポリイソシアネートを含むポリイソシアネート組成物の質量(g)×不揮発分(質量%))×100%
判定方法は以下のとおりとした。
A:80質量%以上
B:60質量%以上80質量%未満
C:60質量%未満
200mLフラスコに、変性ポリイソシアネートを含むポリイソシアネート組成物0.1gと、脱イオン水100gを量り取り、プロペラ羽を使用し、600rpmで5分間、200mLフラスコ内の溶液を撹拌し、水分散液を得た。その後、50mLのガラス瓶に移し替え、分散状態を肉眼で観察した。
判定方法は以下のとおりとした。
A:3時間経過後も変化が見られなかった。
B:3時間経過後にわずかに沈殿又は分離が見られた。
C:3時間以内に沈殿又は分離が見られた。
100mLフラスコに、変性ポリイソシアネートを含むポリイソシアネート組成物15gと、脱イオン水45gを量り取り、プロペラ羽を使用し、600rpmで10分間、100mLフラスコ内の溶液を撹拌し、水分散液を得た。この水分散液におけるイソシアネート基の保持率を、以下のように評価した。
A:80%以上
C:80%未満
反応器として、撹拌機、温度計、還流冷却管、窒素吹き込み管、滴下ロートを取り付けた4ツ口のセパラブルフラスコを用いた。水675gとエマノールNC(アニオン界面活性剤、35%水溶液、花王株式会社製)4.3gを入れ、80℃に加熱し、開始剤として過硫酸アンモニウム(2%水溶液)8gを入れた。次に、フラスコ内に下記の混合物を4時間かけて滴下し、滴下終了後1時間80℃に保った。
2-ヒドロキシメチルメタクリレート 25g(3.5質量%)
アクリル酸 10g(1.4質量%)
アクリルアミド 2g(0.3質量%)
グリシジルメタアクリレート 27g(3.8質量%)
メチルメタアクリレート 353g(49.0質量%)
ブチルアクリレート 293g(40.7質量%)
スチレン 9g(1.3質量%)
水 400g
過硫酸アンモニウム(2%水溶液) 31g
エレミノールJS-2(注1) 38g
エマルゲン920(注2) 9g
(注1)反応性乳化剤、39%水溶液、三洋化成株式会社製
(注2)ノニオン界面活性剤、25%水溶液、花王株式会社
得られた水性エマルジョンは乳白色、不揮発分38%の安定な分散液であり、粒子径は100nmであった。計算から求められた水酸価15.0mgKOH/g、酸価10.8m
gKOH/g、ガラス転移点温度15.7℃であった。
実施例1~16、及び比較例1~7で得られた変性ポリイソシアネートを含むポリイソシアネート組成物を用いて、下記のようにコーティング組成物(1)及び(2)をそれぞれ作製した。作製したコーティング組成物(1)は、下記の(評価4)の評価に用い、コーティング組成物(2)は、下記の(評価5)~(評価8)の評価に用いた。
製造例6で作製したポリオール水分散体40g容器に計り取り、変性ポリイソシアネートを含むポリイソシアネート組成物中のイソシアネート基とポリオール水分散体中のヒドロキシル基とのモル比が、NCO/OH=1.25になるように、変性ポリイソシアネートを含むポリイソシアネート組成物を加えて混合物を得た。更に上記混合物に、コーティング組成物の固形分が38質量%となるように脱イオン水を加え、プロペラ羽を使用し、200rpmで3分間撹拌し、コーティング組成物を作製した。作製したコーティング組成物を用いて、以下の(評価4)の塗膜評価を行った。評価結果を表2に示す。
上記のコーティング組成物(1)を用いて、ガラス板上に、厚さ40μmの塗膜を塗装し、23℃/50%RHの雰囲気下で7日間乾燥させた。得られた塗膜をBYK Garder社製、商品名「haze-gloss version3.40」を用いて、屈折率が1.567の黒色ガラス標準板での測定結果を100グロスユニットとして、20°の光沢値を測定した。なお、塗装に用いたガラス板単体の20°の光沢値は174であった。判定方法は以下のとおりとした。
AAA:160以上
AA:150以上160未満
A:130以上150未満
B:100以上130未満
C:100未満
200rpmで3分間の撹拌を600rpmで10分間に変更した以外はコーティング組成物(1)の作製と同様に行い、コーティング組成物を作製した。作製したコーティング組成物を用いて、以下の(評価5)~(評価8)の塗膜評価を行った。ただし、塗膜外観が著しく悪いものは、(評価6)~(評価8)の結果を評価不可とした。評価結果を表2に示す。
上記のコーティング組成物(2)を用いて、PP板上に、厚さ40μmの塗膜を塗装し、23℃/50%RHの雰囲気下で24時間乾燥させた。得られた塗膜をアセトンに23℃で24時間浸漬させた後に取り出し、塗膜を乾燥させた。塗膜の架橋性を以下の計算方法により算出した。
塗膜の架橋性(%)=(溶解せずに残った塗膜の質量)/(アセトン浸漬前の塗膜の質量)×100%
判定方法は以下のとおりとした。
A:85%以上
B:80%以上85%未満
C:80%未満
上記のコーティング組成物(2)を用いて、ガラス板上に、厚さ40μmの塗膜を塗装し、23℃/50%RHの雰囲気下で7日間乾燥させた。得られた塗膜をケーニッヒ硬度計(BYK Garder社製、商品名「Pendulum hardness tester」)を用いて測定した。判定方法は以下のとおりとした。
A:100以上
C:100未満
上記のコーティング組成物(2)を用いて、ガラス板上に、厚さ40μmの塗膜を塗装し、23℃/50%RHの雰囲気下で7日間乾燥させた。得られた塗膜上にキシレンを1g含ませた直径10mmのコットンボールを10分間置き、表面に残ったキシレンを除いた後の塗膜の様子を観察した。判定方法は以下のとおりとした。
ただし、塗膜外観が悪いものは目視評価が不可能のため、測定不可とした。
A:透明、凹みなし
B:やや白濁、又はやや凹みあり
C:白濁、又は凹みあり
上記のコーティング組成物(2)を用いて、PP板上に、厚さ40μmの塗膜を塗装し、23℃/50%RHの雰囲気下で7日間乾燥させた。得られた塗膜を40℃の水に4時間浸漬させた後に取り出し、塗膜の様子を観察した。判定方法は以下のとおりとした。
ただし、塗膜外観が悪いものは目視評価が不可能のため、測定不可とした。
A:変化なし
B:やや白濁が発生
C:白濁が発生、又は塗膜が溶解
Claims (12)
- ポリイソシアネートと、下記一般式(1)で表されるポリアルキレングリコールアルキルエーテルと、の反応により得られる変性ポリイソシアネートを含む、ポリイソシアネート組成物であって、
平均イソシアネート官能基数が、1.8以上4.0以下であり、
前記ポリイソシアネート組成物の総量に対して、前記変性ポリイソシアネートにおける前記ポリアルキレングリコールアルキルエーテルに由来する部分を、10質量%以上18質量%以下含み、
前記変性ポリイソシアネートにおいて、前記ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比が、1.05以上2.00以下である、ポリイソシアネート組成物。
- 前記分子量分布の分散比は、1.05以上1.50以下である、請求項1に記載のポリイソシアネート組成物。
- 前記式(1)中、R1はエチレン基であり、nの平均数は5.0以上15以下である、請求項1又は2に記載のポリイソシアネート組成物。
- 前記ポリアルキレングリコールアルキルエーテルは、前記式(1)中、nの平均数が異なる二種以上のポリアルキレングリコールアルキルエーテルを含む、請求項1~3のいずれか一項に記載のポリイソシアネート組成物。
- ヒンダードフェノール系化合物をさらに含む、請求項1~4のいずれか一項に記載のポリイソシアネート組成物。
- ポリイソシアネートと、下記一般式(2)で表されるポリアルキレングリコールアルキルエーテルと、を反応させ、変性ポリイソシアネートを含むポリイソシアネート組成物を得る反応工程を含み、
前記反応工程は、平均イソシアネート官能基数が、1.8以上4.0以下であり、前記ポリイソシアネート組成物の総量に対して、前記変性ポリイソシアネートにおける前記ポリアルキレングリコールアルキルエーテルに由来する部分を、10質量%以上18質量%以下含み、かつ、前記変性ポリイソシアネートにおいて、前記ポリアルキレングリコールアルキルエーテルに由来する部分の分子量分布の分散比が、1.05以上2.00以下である、前記ポリイソシアネート組成物を得るように反応させる工程である、ポリイソシアネート組成物の製造方法。
- 前記分子量分布の分散比は、1.05以上1.50以下である、請求項6に記載のポリイソシアネート組成物の製造方法。
- 前記式(2)中、R1はエチレン基であり、nの平均数は5.0以上15以下である、請求項6又は7に記載のポリイソシアネート組成物の製造方法。
- 前記ポリアルキレングリコールアルキルエーテルは、前記式(2)中、nの平均数が異なる二種以上のポリアルキレングリコールアルキルエーテルを含む、請求項6~8のいずれか一項に記載のポリイソシアネート組成物の製造方法。
- 請求項1~5のいずれか一項に記載のポリイソシアネート組成物を含む、コーティング組成物。
- 請求項10に記載のコーティング組成物と、水と、を含む、水系コーティング組成物。
- 基材と、請求項10に記載のコーティング組成物又は請求項11に記載の水系コーティング組成物によってコーティングされたコーティング膜と、を備える、コーティング基材。
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CN110520456A (zh) * | 2017-03-30 | 2019-11-29 | 旭化成株式会社 | 多异氰酸酯固化剂、水性涂料组合物、涂膜以及涂装物 |
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