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WO2015194671A1 - Dispersion aqueuse de résine de polyuréthane - Google Patents

Dispersion aqueuse de résine de polyuréthane Download PDF

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Publication number
WO2015194671A1
WO2015194671A1 PCT/JP2015/067800 JP2015067800W WO2015194671A1 WO 2015194671 A1 WO2015194671 A1 WO 2015194671A1 JP 2015067800 W JP2015067800 W JP 2015067800W WO 2015194671 A1 WO2015194671 A1 WO 2015194671A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane resin
resin dispersion
aqueous polyurethane
weight
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/067800
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English (en)
Japanese (ja)
Inventor
敦史 森上
山田　健史
昌弘 内貴
健太 三吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP2016529553A priority Critical patent/JP6805826B2/ja
Priority to CN201580030213.1A priority patent/CN106414536A/zh
Publication of WO2015194671A1 publication Critical patent/WO2015194671A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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

Definitions

  • the present invention relates to an aqueous polyurethane resin dispersion in which a polyurethane resin is dispersed in an aqueous medium.
  • the present invention also relates to a coating composition containing the aqueous polyurethane resin dispersion and a polyurethane resin film obtained by heating and drying the composition containing the polyurethane resin dispersion.
  • the water-based polyurethane resin dispersion is an environmentally friendly material that can provide a coating film having adhesiveness, abrasion resistance, rubber-like properties, and the like, and can reduce volatile organic substances compared to conventional organic solvent-based polyurethane. Therefore, it is a material that is being replaced by organic solvent-based polyurethane.
  • Polycarbonate polyol is a useful compound that can be used as a raw material for polyurethane resins. By reacting with isocyanate compounds, it produces durable polyurethane resins used for rigid foams, flexible foams, paints, adhesives, synthetic leather, ink binders, etc. can do.
  • Non-patent document 1 The characteristics of the polyurethane resin using polycarbonate polyol are expressed by the high cohesive strength of the carbonate group, and are described as being excellent in water resistance, heat resistance, oil resistance, elastic recovery, wear resistance, weather resistance, and the like. Also, it is known that a coating film obtained by applying an aqueous urethane resin dispersion using polycarbonate polyol as a raw material is excellent in light resistance, heat resistance, hydrolysis resistance, oil resistance, and the like (Patent Document 1). reference).
  • the aqueous polyurethane resin dispersion using the polycarbonate polyol exhibits good characteristics, but is not sufficient as compared with the organic solvent-based polyurethane. In particular, the solvent resistance and water resistance of the coating film are insufficient.
  • a crosslinked structure is introduced into a polyurethane resin, or a composition in which a crosslinking material such as an epoxy resin or a polyfunctional isocyanate is introduced is crosslinked at the time of curing.
  • the aqueous polyurethane resin dispersion having a blocked isocyanato group is stable at room temperature, and thus has a high utility value as a one-part crosslinking reactive dispersion having high storage stability (Patent Document 2 and Patent Document 3). reference). It is also known that an aqueous polyurethane resin dispersion using a polycarbonate polyol as a raw material has a feature of high adhesion to an electrodeposition coating film (see Patent Document 4).
  • the present inventors have controlled the film-forming speed after coating by an aqueous polyurethane resin dispersion having a specific amount of a blocked isocyanate group having a urethane bond, a urea bond, and a carbonate bond.
  • the film can be re-dispersed in water, and the coating obtained by applying and heat treatment is excellent in water resistance and solvent resistance, and is excellent in adhesion to the electrodeposition coating film. It has been found that since the breaking energy in tension is high, the impact resistance is also excellent (see Patent Document 5).
  • additives such as various pigments may be added to the aqueous polyurethane resin dispersion.
  • a water-insoluble organic solvent as a dispersant is added to the aqueous resin dispersion together with the pigment (see Patent Document 6).
  • the present inventors added a water-insoluble organic solvent to the aqueous polyurethane resin dispersion by creating a crosslinked structure using a polyamine compound having a total of 3 or more amino groups and / or imino groups in one molecule.
  • a polyamine compound having a total of 3 or more amino groups and / or imino groups in one molecule it has been found that the viscosity hardly increases (see Patent Document 7).
  • the aqueous polyurethane resin dispersion When used as a film, paint, or coating material, it is applied to a substrate or the like using an application device such as a bar coater, roll coater, or air spray. A coating film is formed on the substrate by heating and drying the applied aqueous polyurethane resin dispersion.
  • an application device such as a bar coater, roll coater, or air spray.
  • a coating film is formed on the substrate by heating and drying the applied aqueous polyurethane resin dispersion.
  • the water-insoluble organic solvent is added, the viscosity is remarkably increased, so that there is a problem in the storage stability as a paint or a coating material composition.
  • the subject of the present invention is that the viscosity does not increase remarkably even when a water-insoluble organic solvent is added, and when the film is formed on the substrate, a large breaking energy in tension and excellent adhesion to the substrate can be achieved.
  • An aqueous polyurethane resin dispersion is provided.
  • the subject of this invention is providing the water-based polyurethane resin dispersion which gives the coating film with the low water swelling rate and the high swelling rate to an aqueous cleaning liquid.
  • the present invention has been made to solve the above problems, and specifically has the following configuration.
  • [1] (a) a polyisocyanate compound, (b) a polyol compound, (c) an acidic group-containing polyol compound, (d) a hydroxyalkanoic acid, and (e) a blocking agent for an isocyanato group that dissociates at 80 to 180 ° C.
  • the polyurethane resin obtained by reacting (A) the polyurethane prepolymer obtained by the reaction with the (B) chain extender having reactivity with the isocyanate group of the polyurethane prepolymer is dispersed in an aqueous medium.
  • An aqueous polyurethane resin dispersion comprising:
  • the (b) polyol compound includes a polycarbonate polyol having a number average molecular weight of 800 to 3,500 and / or a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500,
  • the total content of urethane bonds and urea bonds is 6 to 20% by weight based on solid content
  • the content of carbonate bonds is 10 to 40% by weight based on solid content.
  • an aqueous polyurethane resin dispersion can be provided. Furthermore, the present invention can provide an aqueous polyurethane resin dispersion that provides a coating film having a low water swelling ratio and a high swelling ratio in an aqueous cleaning solution.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • the aqueous polyurethane resin dispersion comprises (a) a polyisocyanate compound, (b) a polyol compound, (c) an acidic group-containing polyol compound, (d) a hydroxyalkanoic acid, and (e) an isocyanato group that dissociates at 80 to 180 ° C.
  • a polyurethane resin obtained by reacting (A) a polyurethane prepolymer obtained by reacting a blocking agent with (B) a chain extender having reactivity with an isocyanato group of the polyurethane prepolymer is obtained in an aqueous medium.
  • An aqueous polyurethane resin dispersion dispersed in The (b) polyol compound includes a polycarbonate polyol having a number average molecular weight of 800 to 3,500 and / or a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500,
  • the total content of urethane bonds and urea bonds is 6 to 20% by weight based on solid content
  • the content of carbonate bonds is 10 to 40% by weight based on solid content.
  • the content ratio of the isocyanate group to which the blocking agent is bound is 0.2 to 2.0% by weight in terms of solid content and isocyanato group, and the weight average molecular weight is 20,000 to 150,000.
  • Some conventional water-based polyurethane resin dispersions can be applied to a substrate, etc., and then the paint layer or paint film can be washed or removed to remove the paint layer or paint film and reapply. There is also a thing. However, there has been a problem that, along with facilitating recoating, the breaking energy in tension becomes low and the coating film is easily broken. Furthermore, when stored as a paint or a coating material composition, there is a problem that the viscosity is remarkably increased by mixing with a water-insoluble organic solvent.
  • the tensile energy at break is high, the swelling rate into an aqueous cleaning liquid (for example, an aqueous solution containing alcohol, amine, aminoalcohol, cellosolve, etc.) is high, and it can be repainted.
  • An aqueous polyurethane resin dispersion in which the viscosity does not increase remarkably by mixing the solvent can be obtained.
  • the coating film formed from the aqueous polyurethane resin dispersion of the present invention is useful as a protective coating for an electrodeposition coating film on steel sheets for building materials, electrical equipment, vehicles, industrial equipment, office machines and the like.
  • an aqueous coating material may be further applied on the aqueous coating film.
  • the surface smoothness of the laminated coating film may be lowered when the water resistance of the coating film is low.
  • the present invention it is possible to obtain an aqueous polyurethane resin dispersion that forms a coating film having high breaking energy in tension, low swelling rate in water, and high water resistance.
  • the coating film obtained using the water-based polyurethane resin dispersion of this invention has high adhesiveness to an electrodeposition coating film, it can be utilized as a protective film of a steel plate.
  • the polyurethane resin film of the present invention can also be used as a decorative film.
  • the polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups, and is an aromatic polyisocyanate compound, a linear or branched aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound. Any of these may be used.
  • Aromatic polyisocyanate compounds include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, metaxylylene diisocyanate (XDI), 4, 4'-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'- Examples include dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate.
  • Linear or branched aliphatic polyisocyanate compounds include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethyl.
  • the alicyclic polyisocyanate compound is not particularly limited as long as it is a compound having an alicyclic structure.
  • polyisocyanate compound may be used alone, or a plurality of types may be used in combination.
  • the polyisocyanate compound is preferably an alicyclic polyisocyanate compound, more preferably an alicyclic diisocyanate compound, and particularly preferably 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and isophorone diisocyanate (IPDI).
  • the polyisocyanate compound is an alicyclic polyisocyanate compound, preferably an alicyclic diisocyanate compound, it is possible to obtain a coating film that is less susceptible to yellowing, and the resulting coating film tends to have higher hardness. There is.
  • the polyisocyanate compound is 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) and / or isophorone diisocyanate (IPDI)
  • the reactivity can be controlled, and the elastic modulus of the resulting coating film Is high and the water swelling rate is low.
  • the polyol compound includes (b-1) one or more acidic compounds including a polycarbonate polyol having a number average molecular weight of 800 to 3,500 and / or a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500. It is a polyol compound containing no group. That is, (b) the polyol compound is a polyol other than a polycarbonate polyol having a number average molecular weight of 800 to 3,500 and a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500 and containing no acidic group. (Hereinafter also referred to as “(b-2) other polyol compounds”).
  • a polycarbonate polyol having a number average molecular weight of 800 to 3,500 and / or a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500 has a number average molecular weight. Is not particularly limited as long as it is a polycarbonate polyol having no acid group and 800 to 3,500, or a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500 and no acid group.
  • the number average molecular weight of the component (b-1) is more preferably from 1,500 to 3,200, and even more preferably from 2,000 to 3,000, from the viewpoint of breaking energy and film-forming property in the coating film tension.
  • the average molecular weight when the polycarbonate polyol and / or polyester polycarbonate polyol used in combination is mixed is preferably within this range.
  • the proportion of the component (b-1) in the total weight of the (b) polyol compound is preferably 50 to 100% by weight, preferably 70 to 100% by weight, from the viewpoint of breaking energy in the tension of the formed coating film. More preferably, it is 85 to 100% by weight.
  • the number average molecular weight (Mn) of polycarbonate polyol or polyester polycarbonate polyol is determined from the hydroxyl value according to the following formula.
  • Mn (56,100 ⁇ valence) / hydroxyl value
  • the valence is the number of hydroxyl groups in one molecule, and the hydroxyl value is a value measured in accordance with the method B of JIS K1557.
  • the polycarbonate polyol is a polycarbonate diol
  • the polyester polycarbonate polyol is a polyester polycarbonate diol
  • the valence is 2.
  • the polycarbonate polyol as the component (b-1) can be produced by a general production method such as a transesterification method or a phosgene method of polyol and carbonate ester.
  • the polyester polycarbonate polyol as the component (b-1) is, for example, a method of transesterifying a cyclic ester compound and / or a hydroxycarboxylic acid ester and a polycarbonate polyol, or a method of transesterifying a polyester polyol and a carbonate ester.
  • the polyester polyol and the polycarbonate polyol can be produced by a transesterification reaction.
  • polyol examples include linear aliphatic diols, branched aliphatic diols, alicyclic diols, aromatic diols, and polyfunctional polyols.
  • Linear aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-pentanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like.
  • the branched aliphatic diols include 1,3-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,6-diol, 2-methyl-1,3-pentanediol, neo Examples include pentyl glycol and 2-methyl-1,8-octanediol.
  • the alicyclic diol is a diol having an alicyclic structure, and is 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 1,3-cyclohexanedimethanol. 1,4-cyclohexanedimethanol and the like.
  • Examples of the aromatic diol include 1,4-benzenedimethanol.
  • Examples of the polyfunctional polyol include trimethylolpropane and pentaerythritol.
  • the polyol can be the polycarbonate polyol or the polyester polycarbonate polyol by using only one kind, or the polycarbonate polyol or the polyester polycarbonate polyol can be used in combination of two or more kinds.
  • Examples of the carbonate ester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; diaryl carbonates such as diphenyl carbonate; alkylaryl carbonates such as methyl phenyl carbonate and ethyl phenyl carbonate; It is done. These may be used individually by 1 type and may use multiple types together.
  • cyclic ester compound examples include aliphatic lactones such as ⁇ -acetolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • Hydroxycarboxylic acid esters include methyl glycolate, ethyl glycolate, methyl lactate, ethyl lactate, methyl tartronate, ethyl tartronate, methyl glycerate, ethyl glycerate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, 3- Examples include methyl hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl malate, ethyl malate, methyl tartrate, ethyl tartrate, methyl 6-hydroxycaproate, and ethyl 6-hydroxycaproate.
  • the cyclic ester compound and / or hydroxycarboxylic acid ester is preferably a cyclic ester compound, more preferably an aliphatic lactone having 2 to 10 carbon atoms, and an aliphatic having 4 to 6 carbon atoms in view of the breaking energy of the resulting coating film. Lactone is more preferred, and ⁇ -caprolactone is particularly preferred.
  • polyester polyol examples include a polyester polyol obtained by a transesterification reaction between a polyol and a polycarboxylic acid ester, and a polyester polyol obtained by condensation polymerization of a polycarboxylic acid or a derivative thereof and the polyol.
  • polycarboxylic acids or derivatives thereof include oxalic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and other saturated aliphatic polycarboxylic acids; maleic acid, fumaric acid, itaconic acid Unsaturated aliphatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid And aromatic polycarboxylic acids such as acid anhydrides and acid halogenoids thereof. These may be used individually by 1 type and may use multiple types together.
  • the polyester polyol can also be obtained by a transesterification reaction between a cyclic ester and / or a hydroxycarboxylic acid and a polyol.
  • the component (b-1) is obtained by using one or more selected from the group consisting of linear aliphatic diols, branched aliphatic diols, alicyclic diols, aromatic diols and polyfunctional polyols. It is more preferable to use a linear aliphatic diol and / or a branched aliphatic diol, and it is even more preferable to use a linear aliphatic diol. Further, the linear aliphatic diol and the branched aliphatic diol preferably have 2 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and 3 to 8 carbon atoms. More preferably.
  • Diols such as alicyclic diols and aromatic diols preferably have 2 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 8 carbon atoms.
  • component (b-1) a commercially available product can be used.
  • the (b-2) other polyol compound is not particularly limited as long as it is a polyol compound other than the component (b-1) and does not contain an acidic group.
  • (B-2) Other polyol compounds include, for example, polyester polyol, polyether polyol, polycarbonate polyol having a number average molecular weight other than 800 to 3,500, polyester polycarbonate polyol having a number average molecular weight other than 800 to 3,500, fat Aromatic diol, alicyclic diol, aromatic diol, polyfunctional polyol and the like.
  • polystyrene resin (B-2)
  • Other polyol compounds are preferably aliphatic diols, alicyclic diols, polycarbonate polyols having a number average molecular weight other than 800 to 3,500, and polyester polycarbonate polyols having a number average molecular weight other than 800 to 3,500.
  • the other polyol compound does not include the later-described (c) acidic group-containing polyol compound.
  • the acidic group-containing polyol compound is not particularly limited as long as it is a compound having at least one acidic group and two or more hydroxy groups. Examples of the acidic group include a carboxy group and a sulfo group.
  • the acidic group-containing polyol compound is preferably an acidic group-containing diol compound, and more preferably an acidic group-containing diol compound having 5 to 8 carbon atoms.
  • the acidic group-containing polyol compound examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3, Examples include 4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, and the like.
  • One type of acidic group-containing polyol compound may be used alone, or a plurality of types may be used in combination.
  • the acidic group-containing polyol compound is preferably a dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups from the viewpoint of availability and reactivity, and 2,2-dimethylolpropionic acid and More preferred is 2,2-dimethylolbutanoic acid.
  • Hydroxyalkanoic acid is not particularly limited as long as it is a compound having one carboxyl group and one hydroxyl group.
  • the hydroxyalkanoic acid preferably has 2 to 30 carbon atoms, more preferably 6 to 30 carbon atoms, and particularly preferably 10 to 26 carbon atoms.
  • the aqueous polyurethane resin dispersion has high storage stability, the water swelling rate of the resulting polyurethane film tends to be low, and the water resistance tends to be high.
  • (D) Hydroxyalkanoic acid is glycolic acid (2-hydroxyacetic acid), hydroxypivalic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 10-hydroxydecanoic acid, hydroxypivalic acid (2,2-dimethyl-3 -Hydroxypropionic acid), 12-hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, lactic acid, trichlorolactic acid, salicylic acid, hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxypropionic acid, 2-hydroxyoctanoic acid, Examples thereof include 3-hydroxyundecanoic acid, 12-hydroxystearic acid, 12-hydroxyoleic acid and the like, and glycolic acid, 4-hydroxybutyric acid, hydroxypivalic acid, and 12-hydroxystearic acid are preferable.
  • 12-hydroxystearic acid is particularly preferred as the (d) hydroxyalkanoic acid from the viewpoint that the water swelling rate of the resulting polyurethane film is lower.
  • (D) Hydroxyalkanoic acid may be used individually by 1 type, and may use multiple types together.
  • the blocking agent for the isocyanato group that dissociates at 80 to 180 ° C. is not particularly limited as long as it is a compound that dissociates from the isocyanato group at 80 to 180 ° C.
  • the “isocyanato group blocking agent” is a compound capable of reacting with an isocyanato group to convert the isocyanato group into another group, and capable of reversibly converting from another group to the isocyanato group by heat treatment. Means.
  • the blocking agent for the isocyanato group that dissociates at 80 to 180 ° C. is preferably at least one selected from the group consisting of oxime compounds, pyrazole compounds, and malonic ester compounds from the viewpoint of dissociation temperature.
  • the blocking agent for the isocyanato group that dissociates at 80 to 180 ° C. may be used alone or in combination of two or more.
  • the polyurethane prepolymer includes (a) a polyisocyanate compound, (b) a polycarbonate polyol having a number average molecular weight of 800 to 3,500 and / or a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500.
  • One or more polyol compounds hereinafter also simply referred to as “polyol compounds”
  • polyol compounds include acidic group-containing polyol compounds, (d) hydroxyalkanoic acids, and (e) blocking agents for isocyanato groups dissociating at 80 to 180 ° C.
  • it is a polyurethane prepolymer obtained by simply reacting with a “blocking agent”.
  • the production method of the polyurethane prepolymer is not particularly limited, and examples thereof include the following methods.
  • the first method performs a urethanization reaction by reacting (a) a polyisocyanate compound, (b) a polyol compound, and (c) an acidic group-containing polyol compound in the presence or absence of a urethanization catalyst. Then, (d) the hydroxyalkanoic acid is reacted, and finally (e) the blocking agent is reacted in the presence or absence of the blocking catalyst to perform the blocking reaction, and a part of the terminal isocyanate group is blocked.
  • A A method for synthesizing a polyurethane prepolymer.
  • a blocking reaction is performed by reacting (a) a polyisocyanate compound and (e) a blocking agent in the presence or absence of a blocking catalyst to block a part of the isocyanato group.
  • the polyisocyanate compound was synthesized and reacted with (b) a polyol compound and (c) an acidic group-containing polyol compound in the presence or absence of a urethanization catalyst.
  • a method of synthesizing A) a polyurethane prepolymer by reacting with a hydroxyalkanoic acid.
  • Urethane catalyst is not particularly limited, and salts of metals and organic and inorganic acids such as tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.), lead-based catalysts (lead octylate, etc.), organometallic derivatives, amines And catalyst based on triethylamine, N-ethylmorpholine, triethylenediamine and the like, and diazabicycloundecene based catalyst.
  • the urethanization catalyst is preferably dibutyltin dilaurate from the viewpoint of reactivity.
  • the blocking catalyst is not particularly limited, and examples thereof include alkali catalysts such as dibutyltin dilaurate and sodium methoxide.
  • the conditions for the urethanization reaction and the reaction conditions for the blocking reaction are not particularly limited, and can be appropriately selected according to the reactivity of the components used.
  • the reaction conditions for the urethanization reaction can be 3 to 15 hours at a temperature of 50 to 100 ° C.
  • the reaction conditions for the blocking reaction can be 1 to 5 hours at a temperature of 50 to 100 ° C.
  • the urethanization reaction and the blocking reaction may be performed independently or continuously.
  • Chain extender A chain extension agent will not be restrict
  • Chain extenders include, for example, hydrazine, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3 A diamine compound such as aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, adipodihydrazide; diethylenetriamine, bis ( Triamine compounds such as 2-aminopropyl) amine and bis (3-aminopropyl) amine; triethylenetetramine, tripropylenetetramine, N- (benzylenetetramine, N
  • the chain extender preferably contains a polyamine compound having a total of three or more amino groups and / or imino groups in one molecule.
  • the (B) chain extender contains a polyamine compound having a total of three or more amino groups and / or imino groups in one molecule, the resulting coating film has a higher breaking energy and a higher water swelling ratio. Tend to be lower.
  • the chain extender is more preferably a combination of a polyamine compound having a total of three or more amino groups and / or imino groups in one molecule and a diamine compound.
  • the proportion of the polyamine compound having 3 or more amino groups and / or imino groups in total in one molecule in the chain extender is preferably 10 to 100 mol%, and preferably 30 to 100 mol%. More preferably, it is particularly preferably 30 to 80 mol%.
  • a polyamine compound having a total of three or more amino groups and / or imino groups in one molecule is diethylenetriamine, triethylenetetramine, bis (2-aminopropyl) amine, bis ( 3-aminopropyl) amine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, pentapropylenehexamine, and other polyamine compounds having two amino groups and one or more imino groups in one molecule Or a mixture thereof, triamine compounds such as diethylenetriamine, bis (2-aminopropyl) amine, bis (3-aminopropyl) amine are more preferred, and diethylenetriamine is more preferred.
  • the chain extender is more preferably a combination of a diamine compound and a polyamine compound having two amino groups and one or more imino groups in one molecule.
  • the chain extender is a combination of a diamine compound and a polyamine compound having two amino groups and one or more imino groups in one molecule, the water swelling rate of the resulting polyurethane resin is kept low, The swelling rate of the aqueous cleaning liquid can be increased.
  • the molar ratio of the diamine compound to the polyamine compound having two amino groups and one or more imino groups is 1/4.
  • the chain extender is a combination of a diamine compound and a polyamine compound having two amino groups and one or more imino groups in one molecule
  • the weight average molecular weight of the polyurethane resin is 20,000 to 150, 000
  • the content of blocked isocyanate groups in the polyurethane resin is 0.2 to 2.0% by weight
  • the acid value at the end of the polyurethane resin is easily adjusted to 3 to 30 mgKOH / g.
  • the molar ratio with the diamine compound (diamine compound / polyamine compound having two amino groups and one or more imino groups) is preferably 1/4 to 4/1, and preferably 1/3 to 3 / 1 is more preferable, and 1/2 to 2/1 is particularly preferable.
  • the amount of the (B) chain extender is preferably equal to or less than the equivalent of the unblocked isocyanato group that becomes the chain extension origin in the (A) polyurethane prepolymer, and more preferably the amount of the unblocked isocyanato group. 0.7 to 0.99 equivalents.
  • the amount of the chain extender is equal to or less than the equivalent of the unblocked isocyanato group, preferably 0.99 equivalent or less, the molecular weight of the chain-extended polyurethane resin tends to be suppressed.
  • the strength of the coating film obtained by applying the obtained aqueous polyurethane resin dispersion tends to be further improved.
  • An unrestricted method for producing an aqueous polyurethane resin dispersion comprises reacting (a) a polyisocyanate compound, (b) a polyol compound, (c) an acidic group-containing polyol compound, (d) a hydroxyalkanoic acid, and (e) a blocking agent.
  • the step of obtaining a polyurethane prepolymer is as described above in the method for producing a polyurethane prepolymer.
  • the step of neutralizing acidic groups and the step of dispersing the polyurethane prepolymer in an aqueous medium may be performed separately or together.
  • the step of reacting the polyurethane prepolymer with the (B) chain extender may be after the step of dispersing the polyurethane prepolymer in the aqueous medium, and the polyurethane prepolymer in the aqueous medium. You may carry out with the process to disperse
  • Each step in the method for producing an aqueous polyurethane resin dispersion may be performed in an inert gas atmosphere or in the air.
  • the total content of urethane bonds and urea bonds in the aqueous polyurethane resin dispersion is 6 to 20% by weight and 7 to 15% by weight based on the solid content. It is preferably 7.5 to 13.5% by weight, more preferably 8 to 13% by weight.
  • the urethane bond content means the urethane bond unit (-NHCOO-) content in the solid content of the polyurethane resin
  • the urea bond content means the urea bond unit (in the solid content of the polyurethane resin).
  • -NHCONH-) means the content ratio.
  • the coating film cannot be sufficiently formed, and the coating film surface becomes sticky after drying.
  • the total content of urethane bonds and urea bonds exceeds 20% by weight, when the aqueous polyurethane resin dispersion is applied to a substrate, the redispersibility of the paint or coating film in an aqueous solvent may be reduced. Since it is inferior, removal becomes difficult and repainting may not be possible.
  • the content of urethane bonds in the aqueous polyurethane resin dispersion is not particularly limited as long as the sum of the content of urea bonds and the content of urea bonds is 6 to 20% by weight based on the solid content.
  • the urethane bond content in the aqueous polyurethane resin dispersion is preferably 4 to 15% by weight, more preferably 5 to 12% by weight, and more preferably 6 to 10% by weight based on the solid content. Particularly preferred.
  • the urea bond content in the aqueous polyurethane resin dispersion is not particularly limited as long as the sum of the urethane bond content and the urethane bond content is 6 to 20 wt% based on the solid content.
  • the content of urea bonds in the aqueous polyurethane resin dispersion is preferably 1 to 6% by weight, more preferably 1.5 to 5% by weight, based on the solid content, and 2 to 4.5% by weight. It is particularly preferred that
  • the content ratio of the urethane bond and the content ratio of the urea bond in the aqueous polyurethane resin dispersion can be calculated from the charged amounts of the respective components when the aqueous polyurethane resin dispersion is prepared. It can also be calculated from the infrared absorption spectrum of the coating film.
  • the content ratio of the isocyanate group to which the blocking agent is bonded (also referred to as blocked isocyanate group) must be 0.2 to 2.0% by weight based on the solid content and converted to the isocyanate group. More preferably 0.3 to 1.5% by weight, still more preferably 0.3 to 1.2% by weight, particularly preferably 0.4 to 1.2% by weight.
  • the content ratio of the isocyanate group bonded to the blocking agent is the content ratio of the isocyanate group bonded to the blocking agent in the solid content of the polyurethane resin calculated as the content ratio of the isocyanate group (-NCO). means.
  • the content ratio of the isosinato group to which the blocking agent is bonded in the aqueous polyurethane resin dispersion can be calculated from the amount of each component charged when preparing the aqueous polyurethane resin dispersion.
  • the content ratio of the isocyanate group to which the blocking agent is bonded is less than 0.2% by weight, there is a problem that the adhesion of the obtained coating film to the surface of the electrodeposition coated plate is poor.
  • the content ratio of the isocyanate group to which the blocking agent is bonded exceeds 2.0% by weight, there is a problem that the elongation at break of the obtained coating film is small and only a coating film that is vulnerable to impact can be obtained.
  • the content of carbonate bonds in the aqueous polyurethane resin dispersion is 10 to 40% by weight, more preferably 15 to 40% by weight, more preferably 18 to 35% by weight based on the solid content. % Is more preferable, and 20 to 30% by weight is particularly preferable.
  • the content ratio of the carbonate bond means the content ratio of the carbonate bond unit (—OCOO—) in the solid content of the polyurethane resin.
  • the content of carbonate bonds in the aqueous polyurethane resin dispersion can be calculated from the amount of each component charged when preparing the aqueous polyurethane resin dispersion. Moreover, it can calculate from the infrared absorption spectrum of a coating film.
  • a polyester polycarbonate polyol having a number average molecular weight of 800 to 3,500 is used as the component (b-1), or when a polyol compound having an ester bond such as a polyester polyol is used as the component (b-2),
  • the resulting aqueous polyurethane resin dispersion will contain ester bonds.
  • the elongation at break tends to increase, but when too much is introduced, the water swelling rate increases.
  • the aqueous polyurethane resin dispersion contains an ester bond
  • the content of the ester bond is preferably 3 to 16% by weight, more preferably 4 to 14% by weight, and particularly preferably 4 to 12% by weight based on the solid content.
  • the weight average molecular weight of the polyurethane resin is 20,000 to 150,000, preferably 25,000 to 120,000, more preferably 30,000 to 110,000, and 35,000 to 100. Is particularly preferred.
  • the weight average molecular weight of the polyurethane resin is less than 20,000, the breaking energy of the obtained coating film becomes low, and a coating film resistant to impact cannot be obtained.
  • the weight average molecular weight of the polyurethane resin is more than 150,000, it is difficult to remove the resulting aqueous polyurethane resin dispersion when applied to a substrate due to poor redispersibility of the paint or coating film in an aqueous solvent. It becomes difficult to repaint.
  • the weight average molecular weight of the polyurethane resin is from 35,000 to 100,000, the swelling rate in the aqueous cleaning liquid tends to be high, and there is a tendency to be more excellent in detergency. There is.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC), and is a conversion value obtained from a standard curve of standard polystyrene prepared in advance.
  • the acid value of the polyurethane resin is not particularly limited, but is preferably 10 to 40 mgKOH / g, more preferably 13 to 35 mgKOH / g, and particularly preferably 14 to 30 mgKOH / g.
  • the acid value derived from the molecular end of the polyurethane resin is not particularly limited, but is preferably 3 to 30 mgKOH / g, more preferably 4 to 25 mgKOH / g, and 5 to 20 mgKOH / g. Particularly preferred.
  • the acid value of the polyurethane resin is preferably 10 to 40 mgKOH / g, and the acid value derived from the molecular terminal of the polyurethane resin is preferably 3 to 30 mgKOH / g.
  • the breaking energy of the coating film is increased. be able to.
  • the acid value of the polyurethane resin is the sum of (c) the acid value derived from the acidic group-containing polyol and (d) the acid value derived from the hydroxyalkanoic acid.
  • the acid value derived from the molecular terminal of the polyurethane resin is the acid value derived from (d) hydroxyalkanoic acid.
  • the acid value of the polyurethane resin is a value measured according to the indicator titration method of JIS K1557.
  • the acid value derived from the molecular terminal of the polyurethane resin is calculated by calculating the molar concentration (mol / g) of hydroxyalkanoic acid on the basis of the solid content from the charged amount of each component when preparing the aqueous polyurethane resin dispersion. It is the value converted into the weight fraction (mgKOH / g) of potassium hydroxide required for the sum.
  • terminal carboxy group / blocked NCO group The molar ratio of the carboxy group to the isocyanate group bound to the blocking agent (hereinafter also referred to as “terminal carboxy group / blocked NCO group”) at the molecular terminal of the polyurethane resin is 10/90 to 70/30. Is preferable, 20/80 to 60/40 is more preferable, 30/70 to 60/40 is further preferable, and 30/70 to 49/51 is particularly preferable.
  • the terminal carboxy group / blocked NCO group by reducing the number of moles of the terminal carboxy group relative to the number of moles of the blocked NCO group, a coating film that does not break (provided high breaking energy) unless higher energy is applied. An aqueous polyurethane resin dispersion can be obtained.
  • the coating film can be made flexible (low elastic modulus), and the elongation at break of the coating film Can be high.
  • the terminal carboxy group / blocked NCO group is preferably 51/49 to 75/25, more preferably 55/45 to 70/30.
  • the content of the alicyclic structure in the aqueous polyurethane resin dispersion is not particularly limited, but is preferably 6 to 30% by weight, more preferably 7 to 25% by weight based on the solid content, and 7 to 22%. More preferably, it is 8% by weight, and particularly preferably 8 to 20% by weight.
  • the content of the alicyclic structure in the aqueous polyurethane resin dispersion is 6% by weight or more, the tensile strength of the coating film is increased and the breaking energy is increased.
  • the content of the alicyclic structure in the aqueous polyurethane resin dispersion is 30% by weight or less
  • the paint or coating film is reconstituted in an aqueous solvent. Since the dispersibility is high, removal is easy and repainting is easier.
  • the alicyclic structure is a cyclohexane ring
  • the content ratio of the alicyclic structure based on the solid content is a portion obtained by removing two hydrogen atoms from cyclohexane (the cyclohexane residue) in the solid content in the aqueous polyurethane resin dispersion. It shows how many groups are present.
  • the aqueous polyurethane resin dispersion preferably contains a neutralizing agent as an optional component.
  • the neutralizing agent is used to neutralize at least some of the acidic groups of the polyurethane prepolymer and disperse the polyurethane prepolymer in the aqueous medium.
  • the aqueous polyurethane resin dispersion containing a neutralizing agent is preferably obtained by reacting a polyurethane prepolymer dispersed in an aqueous medium with a chain extender.
  • Neutralizing agents are trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, aminomethylpropanol, aminomethylpropanediol, aminoethylpropanediol, trihydroxymethylaminomethane, monoethanolamine, N, N -Organic amines such as dimethylethanolamine and triisopropanolamine; inorganic alkali salts such as potassium hydroxide and sodium hydroxide; ammonia and the like.
  • a neutralizer may be used individually by 1 type and may use 2 or more types together.
  • the neutralizing agent is preferably an organic amine from the viewpoint of workability, and more preferably triethylamine.
  • the amount of the neutralizing agent is, for example, 0.4 to 1.2 equivalents, and preferably 0.6 to 1.0 equivalents per equivalent of acidic groups in the aqueous polyurethane resin dispersion.
  • the aqueous polyurethane resin dispersion may contain amino alcohol, monoalcohol and monoamine as further optional components.
  • a polyurethane prepolymer containing a hydroxyl group at the molecular end can be obtained by reacting the polyurethane prepolymer with amino alcohol in a state where the polyurethane prepolymer is dispersed in water.
  • the chain can be extended by a reaction with the isocyanate group that is generated by deblocking when the coating film is dried by heating.
  • it is effective to use amino alcohol.
  • amino alcohols examples include ethanolamine, butanolamine, hexanolamine and the like, and ethanolamine is preferred from the viewpoint of water dispersibility.
  • the amount of amino alcohol is preferably less than 2% by weight, more preferably less than 1% by weight, based on the solid content of the aqueous polyurethane resin dispersion.
  • (A) by reacting a polyurethane prepolymer with a monoalcohol or monoamine in a state where the polyurethane prepolymer is dispersed in water, a polyurethane prepolymer having a non-reactive molecular terminal can be obtained. Thereby, a crosslinking degree can be adjusted and it becomes possible to control the elasticity modulus of a coating film.
  • the monoalcohol include ethanol, n-propanol, isopropanol, n-butanol, hexanol, octanol and the like, and n-butanol is preferable from the viewpoint of ease of production.
  • Examples of the monoamine include ethylamine, n-propylamine, isopropylamine, n-butylamine, n-hexylamine and the like.
  • the amount of monoalcohol and monoamine added is preferably less than 2% by weight, more preferably less than 1% by weight, based on the solid content of the aqueous polyurethane resin.
  • monoalcohol is preferably used in the production of (A) polyurethane prepolymer.
  • the monoamine is preferably used after (A) the polyurethane prepolymer is dispersed in an aqueous medium, and is preferably used before (B) the chain extender is added.
  • (A) In the case of adding a monoalcohol during the production of the polyurethane prepolymer, it is preferable to carry out the reaction in a state heated to 60 ° C. or higher from the viewpoint of improving the reaction rate. When adding the said monoamine, it is preferable to make it react in the state of 60 degrees C or less from the point which suppresses a side reaction.
  • the polyurethane resin is dispersed in an aqueous medium.
  • the aqueous medium include water, a mixed medium of water and a hydrophilic organic solvent, and the like.
  • examples of the water include clean water, ion-exchanged water, distilled water, and ultrapure water.
  • ion-exchanged water is considered. Is preferred.
  • Hydrophilic organic solvents include lower monohydric alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as ethylene glycol and glycerin; N-methylmorpholine, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone. And aprotic hydrophilic organic solvents such as dipropylene glycol dimethyl ether (DMM) and ⁇ -alkoxypropionic acid amide.
  • the amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by weight, and more preferably 0 to 10% by weight.
  • the coating film obtained by applying the aqueous polyurethane resin dispersion is excellent in water resistance and solvent resistance, and is excellent in adhesion to the electrodeposition coating film.
  • the cationic type uses a modified epoxy resin as a base resin and is crosslinked with isocyanate, whereas the anionic type is crosslinked by oxidative polymerization. Since the secondary hydroxyl group produced by ring opening of the epoxy group remains in the cationic type and the carboxyl group is introduced in the anionic type, the blocking agent is used in the heat drying step of the aqueous polyurethane resin dispersion of the present invention.
  • Electrodeposition coatings are used in industrial machinery such as heavy machinery and agricultural machinery, vehicles such as automobiles and bicycles, prefabricated steel frames, fire doors, building materials such as sashes, electrical equipment such as switchboards, elevators, and microwave ovens. Yes.
  • the aqueous polyurethane resin dispersion can be applied, for example, on a base material on which the electrodeposition coating film is formed using an application device and baked at a temperature of 80 to 250 ° C.
  • a drying step can be provided before the baking step, or baking can be performed at a time after the aqueous polyurethane resin dispersion is applied and dried, and another coating material is applied and dried.
  • the blocking agent of the blocked isocyanate group is dissociated to form a cross-linked structure with an acidic group or other isocyanate group.
  • a coating film having high hardness can be formed.
  • a general method can be used for the baking step and the drying step.
  • the coating material composition includes an aqueous polyurethane resin dispersion and optionally an additive.
  • the coating material composition consists only of an aqueous polyurethane resin dispersion.
  • Additives include plasticizers, antifoaming agents, leveling agents, fungicides, rust inhibitors, matting agents, flame retardants, tackifiers, thixotropic agents, lubricants, antistatic agents, thickeners, thickeners , Diluents, pigments, dyes, ultraviolet absorbers, light stabilizers, antioxidants, fillers and the like.
  • the coating material composition can be applied to coating (film formation) on various substrates such as metal, ceramic, synthetic resin, nonwoven fabric, woven fabric, knitted fabric, and paper.
  • a polyurethane resin film (hereinafter also referred to as “polyurethane film”) is produced by heating and drying a composition containing an aqueous polyurethane resin dispersion.
  • the composition comprising the aqueous polyurethane resin dispersion comprises an aqueous polyurethane resin dispersion and optionally an additive.
  • the composition containing the aqueous polyurethane resin dispersion does not contain an additive
  • the composition containing the aqueous polyurethane resin dispersion consists only of the aqueous polyurethane resin dispersion.
  • the additive in the composition containing the aqueous polyurethane resin dispersion is as described above in the coating composition.
  • the method for producing the polyurethane resin film is not particularly limited.
  • a step of applying a composition containing an aqueous polyurethane resin dispersion on a releasable substrate, and drying the composition containing the aqueous polyurethane resin dispersion examples thereof include a method including a step of forming a polyurethane resin film and a step of peeling the releasable substrate and the polyurethane resin film.
  • the peelable substrate is not particularly limited, and examples thereof include a glass substrate; a plastic substrate such as polyethylene terephthalate or polytetrafluoroethylene; a metal substrate; The peelable substrate is obtained by treating the surface of each substrate with a release agent.
  • the coating device for applying the composition containing the aqueous polyurethane resin dispersion is not particularly limited, and examples thereof include a bar coater, a roll coater, a gravure roll coater, and an air spray.
  • the thickness of the polyurethane resin film is not particularly limited, but is preferably 0.01 mm to 0.5 mm.
  • the acid value was measured according to the indicator titration method of JIS K 1557.
  • the content ratio (urethane bond content) based on solid content of urethane bonds and the content ratio (urea bond content) based on solid content of urea bonds are determined based on the proportions of the raw materials of the aqueous polyurethane resin dispersion,
  • the molar concentration (mole / g) of the urea bond was calculated and expressed as a weight fraction.
  • the weight fraction was based on the solid content of the aqueous polyurethane resin dispersion.
  • aqueous polyurethane resin dispersion (0.3 g) was applied to a glass substrate with a thickness of 0.2 mm, and the weight remaining after heating and drying at 140 ° C. for 4 hours was measured. The partial concentration was used. The weight fraction was calculated using the product of the total weight of the aqueous polyurethane resin dispersion and the solid content concentration as the solid content weight.
  • ester bond solid content content (ester bond content)
  • the molar concentration (mol / g) of the ester bond is calculated from the charge ratio of each raw material of the aqueous polyurethane resin dispersion, and converted to a weight fraction. I wrote what I did.
  • the weight fraction was calculated based on the solid content of the aqueous polyurethane resin dispersion by the same method as the content of the urethane bond based on the solid content.
  • the carbonate bond molar concentration (mol / g) is calculated from the charge ratio of each raw material of the aqueous polyurethane resin dispersion, and converted to the weight fraction. I wrote what I did.
  • the weight fraction was calculated based on the solid content of the aqueous polyurethane resin dispersion by the same method as the content of the urethane bond based on the solid content.
  • the molar concentration (mol / g) of hydroxyalkanoic acid is calculated based on the solid content based on the charge ratio of each raw material of the aqueous polyurethane resin dispersion. Is converted to the weight fraction of potassium hydroxide required for neutralization (mgKOH / g).
  • the content ratio (alicyclic structure content) based on the solid content of the alicyclic structure represents the weight fraction of the alicyclic structure calculated from the charging ratio of each raw material of the aqueous polyurethane resin dispersion.
  • the weight fraction was calculated based on the solid content of the aqueous polyurethane resin dispersion by the same method as the content of the urethane bond based on the solid content.
  • the weight average molecular weight of the polyurethane resin in the aqueous polyurethane resin dispersion was measured by gel permeation chromatography (GPC), and a conversion value obtained from a standard polystyrene calibration curve prepared in advance was described.
  • GPC gel permeation chromatography
  • the content ratio of the isocyanate group to which the blocking agent based on the solid content in the aqueous polyurethane resin dispersion is bonded is the weight of the isocyanate group charged in the charged molar amount of the blocking agent.
  • the ratio divided by the solid content weight of the aqueous polyurethane resin dispersion was expressed.
  • the solid content weight of the aqueous polyurethane resin dispersion was calculated by the same method as the content based on the solid content of the urethane bond.
  • (Swelling ratio) [(weight of coating film after water immersion) ⁇ (weight of coating film before water immersion)] / (weight of coating film before water immersion) ⁇ 100 (12) Swelling ratio of dry coating film to aqueous cleaning solution: Aqueous cleaning solutions containing 5%, 4%, 1% and 90% of butyl cellosolve, isopropanol, dimethylethanolamine and ion-exchanged water on a weight basis were prepared. . An aqueous polyurethane resin dispersion (0.3 mL) was coated on a glass plate at a thickness of 72 ⁇ m (bar coater # 36), and dried by heating at 50 ° C. until the solid content concentration of the coating film reached 90%.
  • This coating film was immersed in an aqueous cleaning solution at 28 ° C. for 3 minutes, and the coating film weight before and after immersion was measured.
  • the swelling ratio of the coating film into the aqueous cleaning solution was calculated by the following formula.
  • the solid content concentration of the dried coating film was calculated by the same method as the content ratio of the urethane bond based on the solid content.
  • the adhesion with the electrodeposited surface was evaluated as follows. An aqueous polyurethane resin dispersion was applied to an automotive steel plate cationic electrodeposition coating plate (manufactured by Nippon Test Panel Co., Ltd.) with a thickness of 40 ⁇ m (bar coater # 20), dried by heating at 140 ° C. for 30 minutes, and the resulting coating film was used. A cross-cut peel test was conducted. The coating film was cut at an interval of 1 mm vertically and horizontally in an area of 10 mm ⁇ 10 mm, and after sticking an adhesive tape, the number of cells remaining on the surface of the electrodeposition layer when peeled off was visually evaluated. For example, the case where 60 out of 100 remained was described as 60/100.
  • the viscosity increase rate when 2-ethylhexanol was added was evaluated as follows. To 100 g of the aqueous polyurethane resin dispersion, 3 g of 2-ethylhexanol was added and stirred at 20 ° C. for 5 minutes. The viscosity was measured after standing at the same temperature for 10 minutes, and the increase rate (%) of the viscosity before and after the addition of 2-ethylhexanol was calculated.
  • Example 1 [Production of aqueous polyurethane resin dispersion (1)]
  • ETERNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 1,993; hydroxyl value 56.3 mgKOH / g; 1,6-hexane) 230 g of polycarbonate diol obtained by reacting diol and dimethyl carbonate
  • 10.6 g of 2,2-dimethylolpropionic acid (DMPA) and 115 g of N-ethylpyrrolidone (NEP) were charged under a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • the aqueous polyurethane resin dispersion (1) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer.
  • the obtained coating layer was peeled off to produce a polyurethane film (A).
  • the film thickness of the obtained polyurethane film (A) was 0.10 mm.
  • Example 2 [Production of aqueous polyurethane resin dispersion (2)]
  • ETERRNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,029; hydroxyl value 55.3 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol obtained in this manner, 7.93 g of 2,2-dimethylolpropionic acid (DMPA) and 113 g of N-ethylpyrrolidone (NEP) were charged under a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • polyurethane film (B) The aqueous polyurethane resin dispersion (2) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (B). The film thickness of the obtained polyurethane film (B) was 0.10 mm.
  • Example 3 [Production of aqueous polyurethane resin dispersion (3)]
  • ETERRNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,029; hydroxyl value 55.3 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol) 240 g obtained, 2,2-dimethylolpropionic acid (DMPA) 5.33 g, and N-ethylpyrrolidone (NEP) 110 g were charged under a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • the aqueous polyurethane resin dispersion (3) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and at 140 ° C. for 30 minutes to obtain a good coating layer.
  • the obtained coating layer was peeled off to produce a polyurethane film (C).
  • the film thickness of the obtained polyurethane film (C) was 0.10 mm.
  • Example 4 [Production of aqueous polyurethane resin dispersion (4)]
  • ETERRNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,007; hydroxyl value 55.9 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol obtained in this manner, 2,2-dimethylolpropionic acid (DMPA) 14.1 g, and N-ethylpyrrolidone (NEP) 137 g were charged in a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • IPDI isophorone diisocyanate
  • Catalyst dibutyltin dilaurate
  • DMPZ 3,5-dimethylpyrazole
  • polyurethane film (D) The aqueous polyurethane resin dispersion (4) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (D). The film thickness of the obtained polyurethane film (D) was 0.10 mm.
  • Example 5 [Production of aqueous polyurethane resin dispersion (5)]
  • ETERNACOLL UHC50-200 registered trademark; polyester polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,040; hydroxyl value 55.0 mgKOH / g; 1,6-hexanediol, ⁇ -caprolactone
  • 239 g of a polyester polycarbonate diol obtained by reacting dimethyl carbonate 10.8 g of 2,2-dimethylolpropionic acid (DMPA) and 108 g of N-ethylpyrrolidone (NEP) were charged under a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • polyurethane film (E) The aqueous polyurethane resin dispersion (5) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (E). The film thickness of the obtained polyurethane film (E) was 0.10 mm.
  • Example 6 [Production of aqueous polyurethane resin dispersion (6)]
  • ETERRNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,007; hydroxyl value 55.9 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol) 286 g, 2,2-dimethylolpropionic acid (DMPA) 12.5 g and N-ethylpyrrolidone (NEP) 129 g were charged under a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • polyurethane film (F) The aqueous polyurethane resin dispersion (6) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (F). The film thickness of the obtained polyurethane film (F) was 0.10 mm.
  • Example 7 [Production of aqueous polyurethane resin dispersion (7)]
  • ETERNACOLL UHC50-200 registered trademark; polyester polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,014; hydroxyl value 55.7 mgKOH / g; 1,6-hexanediol, ⁇ -caprolactone
  • 251 g of polyester polycarbonate diol obtained by reacting dimethyl carbonate 17.4 g of 2,2-dimethylolpropionic acid (DMPA) and 129 g of N-methylpyrrolidone (NMP) were charged in a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NMP N-methylpyrrolidone
  • polyurethane film (G) The aqueous polyurethane resin dispersion (7) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (G). The film thickness of the obtained polyurethane film (G) was 0.10 mm.
  • Example 8 [Production of aqueous polyurethane resin dispersion (8)]
  • ETERRNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,004; hydroxyl value 56.0 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol 145 g, polytetramethylene ether glycol (PTMG) 70.5 g having a number average molecular weight of 2,000, 10.1 g 2,2-dimethylolpropionic acid (DMPA) and N-ethylpyrrolidone (NEP) ) 108 g was charged under a nitrogen stream.
  • PTMG polytetramethylene ether glycol
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • the aqueous polyurethane resin dispersion (8) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (H). The film thickness of the obtained polyurethane film (H) was 0.10 mm.
  • Example 9 [Production of aqueous polyurethane resin dispersion (9)]
  • ETERNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,036; hydroxyl value 55.1 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol obtained in this manner) 2,2-dimethylolpropionic acid (DMPA) 17.7 g and N-ethylpyrrolidone (NEP) 196 g were charged under a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • polyurethane film (I) The aqueous polyurethane resin dispersion (9) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (I). The film thickness of the obtained polyurethane film (I) was 0.10 mm.
  • Example 10 [Production of aqueous polyurethane resin dispersion (10)]
  • ETERRNACOLL UH-200 registered trademark; polycarbonate diol manufactured by Ube Industries; number average molecular weight 2,029; hydroxyl value 55.3 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol obtained in this manner, 252 g of 2,2-dimethylolpropionic acid (DMPA) and 8.0 g of N-ethylpyrrolidone (NEP) were charged in a nitrogen stream.
  • DMPA 2,2-dimethylolpropionic acid
  • NEP N-ethylpyrrolidone
  • polyurethane film (J) The aqueous polyurethane resin dispersion (10) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (J). The film thickness of the obtained polyurethane film (J) was 0.10 mm.
  • Example 11 [Production of aqueous polyurethane resin dispersion (11)]
  • ETERNACOLL UH-200 registered trademark; polycarbonate diol produced by Ube Industries; number average molecular weight 1,968; hydroxyl value 57.0 mgKOH / g; 1,6-hexanediol and dimethyl carbonate were reacted.
  • Polycarbonate diol) 243 g, 2,2-dimethylolpropionic acid (DMPA) 8.23 g, and Idemitsu Kosan Ecamide M-100 122 g were charged under a nitrogen stream.
  • the aqueous polyurethane resin dispersion (11) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer.
  • the obtained coating layer was peeled off to produce a polyurethane film (K).
  • the film thickness of the obtained polyurethane film (K) was 0.10 mm.
  • reaction mixture was cooled to 80 ° C., 584 g was extracted from the mixture obtained by adding and mixing 15.4 g of triethylamine, and added to 838 g of water under strong stirring. Subsequently, 58.3 g of a 35% by weight 2-methyl-1,5-diaminopentane aqueous solution was added to carry out chain extension reaction to obtain an aqueous polyurethane resin dispersion (12).
  • polyurethane film (L) The aqueous polyurethane resin dispersion (12) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (L). The film thickness of the obtained polyurethane film (L) was 0.10 mm.
  • polyurethane film (M) The aqueous polyurethane resin dispersion (13) was applied as a coating material composition on a glass plate, and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (M). The film thickness of the obtained polyurethane film (M) was 0.10 mm.
  • reaction mixture was cooled to 80 ° C., 475 g was extracted from the mixture obtained by adding and mixing 12.0 g of triethylamine, and added to 713 g of water under strong stirring. Subsequently, 25.1 g of 35% by weight diethylenetriamine aqueous solution was added to carry out chain extension reaction to obtain an aqueous polyurethane resin dispersion (14).
  • polyurethane film (N) The aqueous polyurethane resin dispersion (14) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (N). The film thickness of the obtained polyurethane film (N) was 0.10 mm.
  • polyurethane film (P) The aqueous polyurethane resin dispersion (16) was applied as a coating material composition on a glass plate and dried at 120 ° C. for 3 hours and 140 ° C. for 30 minutes to obtain a good coating layer. The obtained coating layer was peeled off to produce a polyurethane film (P). The film thickness of the obtained polyurethane film (P) was 0.10 mm.
  • H12-MDI 4,4'-dicyclohexylmethane diisocyanate
  • IPDI is isophorone diisocyanate
  • UH-200 is Ube Industries 'ETERNACOLL UH-200
  • UHC50-200 is Ube Industries' ETERNACOLL UHC50-200
  • PTMG is a number Polytetramethylene ether glycol having an average molecular weight of 2,000
  • HS is 12-hydroxystearic acid
  • GA is glycolic acid
  • HP hydroxypivalic acid
  • DMPZ 3,5-dimethylpyrazole
  • MEKO is methyl ethyl ketoxime
  • MPMD represents 2-methyl-1,5-pentanediamine
  • DETA represents diethylenetriamine.
  • the aqueous polyurethane resin dispersion of the present invention has a high swelling ratio of the coating film to the cleaning liquid, a low water swelling ratio, a high breaking energy, and a high adhesion to the electrodeposited surface.
  • the viscosity increase rate when adding a hydrophobic solvent is low.
  • Comparative Example 1 when the hydroxyalkanoic acid and the isocyanato group blocking agent are not contained, the swelling ratio to the cleaning liquid is lowered.
  • Comparative Example 2 if no hydroxyalkanoic acid is contained, the viscosity increase rate when a hydrophobic solvent is added increases.
  • the aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for paints and coating materials.

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

Abstract

　La présente invention se rapporte à une dispersion aqueuse de résine de polyuréthane dans laquelle une résine de polyuréthane, obtenue en faisant réagir un allongeur de chaîne avec un prépolymère de polyuréthane, le prépolymère de polyuréthane étant obtenu en faisant réagir un polyisocyanate, un polyol, un polyol contenant un groupe acide, un acide hydroxyalcanoïque et un agent de blocage de groupe isocyanate, est dispersée dans un vecteur aqueux, le polyol comprenant un polyol de polycarbonate et/ou un polyol de polycarbonate polyester ayant une masse moléculaire moyenne en nombre allant de 800 à 3500, et, dans la résine de polyuréthane, le total de liaisons uréthane et de liaisons urée constitue de 6 à 20 % en poids en se basant sur la teneur en matières solides, les liaisons carbonates constituent de 10 à 40 % en poids en se basant sur la teneur en matières solides, les groupes isocyanate bloqués constituent de 0,2 à 2,0 % en poids en se basant sur la teneur en matières solides, et la masse moléculaire moyenne en poids est de 20 000 à 150 000.
PCT/JP2015/067800 2014-06-20 2015-06-19 Dispersion aqueuse de résine de polyuréthane Ceased WO2015194671A1 (fr)

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JP2017218565A (ja) * 2016-06-10 2017-12-14 宇部興産株式会社 水性ポリウレタン樹脂分散体
CN108250397A (zh) * 2018-01-11 2018-07-06 重庆文理学院 一种水性四氢枞酸封端聚氨酯树脂、制备方法、及其应用
JP2019536849A (ja) * 2016-10-18 2019-12-19 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ ブロックトポリイソシアネートの触媒架橋によるプラスチックの製造
KR20200015250A (ko) * 2018-08-03 2020-02-12 주식회사 케이씨씨 블록 폴리이소시아네이트 및 이를 포함하는 수성 도료 조성물
JP2020506256A (ja) * 2017-01-13 2020-02-27 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 織物用の低溶剤コーティング系
WO2021065324A1 (fr) * 2019-09-30 2021-04-08 第一工業製薬株式会社 Agent de revêtement de film
US12305075B2 (en) 2019-11-20 2025-05-20 Akzo Nobel Coatings International B.V. Aqueous fire-retardant composition and aqueous coating composition comprising such fire-retardant composition

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EP4174039A4 (fr) * 2020-06-24 2024-03-13 Sumitomo Electric Industries, Ltd. Composition de résine, fibre optique et procédé de production de fibre optique
CN116157437A (zh) * 2020-07-17 2023-05-23 台湾日华化学工业股份有限公司 水性聚氨酯树脂组合物及聚氨酯薄膜
CN118530577B (zh) * 2024-02-05 2025-03-25 蓝帆医疗股份有限公司 聚氨酯-聚脲水分散体及其制备方法、用途与浆料，聚氨酯手套制备方法及聚氨酯手套

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JP2016084463A (ja) * 2014-10-24 2016-05-19 三洋化成工業株式会社 ポリウレタン樹脂水性分散体
JP2017218565A (ja) * 2016-06-10 2017-12-14 宇部興産株式会社 水性ポリウレタン樹脂分散体
JP2019536849A (ja) * 2016-10-18 2019-12-19 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ ブロックトポリイソシアネートの触媒架橋によるプラスチックの製造
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CN108250397A (zh) * 2018-01-11 2018-07-06 重庆文理学院 一种水性四氢枞酸封端聚氨酯树脂、制备方法、及其应用
CN108250397B (zh) * 2018-01-11 2020-08-11 重庆文理学院 一种水性四氢枞酸封端聚氨酯树脂、制备方法、及其应用
KR20200015250A (ko) * 2018-08-03 2020-02-12 주식회사 케이씨씨 블록 폴리이소시아네이트 및 이를 포함하는 수성 도료 조성물
KR102076608B1 (ko) 2018-08-03 2020-02-13 주식회사 케이씨씨 블록 폴리이소시아네이트 및 이를 포함하는 수성 도료 조성물
WO2021065324A1 (fr) * 2019-09-30 2021-04-08 第一工業製薬株式会社 Agent de revêtement de film
JP2021054940A (ja) * 2019-09-30 2021-04-08 第一工業製薬株式会社 フィルムコーティング剤
JP7393173B2 (ja) 2019-09-30 2023-12-06 第一工業製薬株式会社 フィルムコーティング剤
US12305075B2 (en) 2019-11-20 2025-05-20 Akzo Nobel Coatings International B.V. Aqueous fire-retardant composition and aqueous coating composition comprising such fire-retardant composition

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