WO2012026475A1 - Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor - Google Patents

Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor Download PDF

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Publication number
WO2012026475A1
WO2012026475A1 PCT/JP2011/068997 JP2011068997W WO2012026475A1 WO 2012026475 A1 WO2012026475 A1 WO 2012026475A1 JP 2011068997 W JP2011068997 W JP 2011068997W WO 2012026475 A1 WO2012026475 A1 WO 2012026475A1
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WO
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Prior art keywords
polyurethane resin
compound
group
polymerizable unsaturated
resin dispersion
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PCT/JP2011/068997
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French (fr)
Japanese (ja)
Inventor
山田　健史
藤井　輝昭
昌弘 内貴
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宇部興産株式会社
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Publication date
Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Priority to KR1020137007268A priority Critical patent/KR20130099070A/en
Priority to JP2012530683A priority patent/JP5821854B2/en
Priority to CN201180041102.2A priority patent/CN103080164B/en
Publication of WO2012026475A1 publication Critical patent/WO2012026475A1/en

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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/67—Unsaturated 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • 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
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the present invention relates to an aqueous urethane resin dispersion that can be cured by irradiation with active energy rays such as ultraviolet light, a method for producing the same, and use thereof.
  • Polycarbonate polyol is a useful compound to be a raw material of polyurethane resin, and can react with an isocyanate compound to produce polyurethane resin used for rigid foam, flexible foam, paint, adhesive, synthetic leather, ink binder, etc. .
  • coating the water-based polyurethane resin dispersion which used the polycarbonate polyol as a raw material is known to be excellent in light resistance, heat resistance, hydrolysis resistance, and oil resistance (refer patent document 1). .
  • a coating film obtained by applying an aqueous urethane resin dispersion using an aliphatic polycarbonate polyol is known to be used as an undercoat agent because the adhesion to a substrate and the blocking resistance are improved.
  • Patent Document 2 a coating film obtained by applying an aqueous urethane resin dispersion using an aliphatic polycarbonate polyol is known to be used as an undercoat agent because the adhesion to a substrate and the blocking resistance are improved.
  • Patent Document 3 the water-based polyurethane resin dispersion which used the polycarbonate polyol which has alicyclic structure is also proposed (refer patent document 3, 4 and 5).
  • the active energy ray-curable resin composition having a radically polymerizable compound is an active ingredient such as various coatings such as paints for metals, overcoats for various plastic films, paints for woodworking, printing inks, etc. It is used as.
  • an energy ray-curable aqueous resin composition in which a (meth) acrylate compound is dispersed in an aqueous polyurethane resin dispersion has been proposed (see Patent Document 6).
  • the (meth) acrylate compound is dispersed in the water-based polyurethane resin dispersion using a surfactant, and the surface activity is There is a problem in that the coating film performance is lowered by the agent remaining in the coating film. In this composition, if the amount of surfactant used is reduced or not used, there arises a problem that the storage stability is lowered.
  • the coating film obtained from the energy ray-curable water-based resin composition comprises various plastics ( In particular, there is a problem that the adhesion to ABS resin and acrylic resin) is not sufficient.
  • the present invention is an active energy ray (for example, ultraviolet light) -curable aqueous polyurethane resin dispersion, which has good dispersibility in an aqueous medium and storage stability, and an active energy ray (for example, ultraviolet light)
  • an active energy ray for example, ultraviolet light
  • this invention makes it a subject to obtain the aqueous
  • the present inventors disperse a polyurethane resin having a polymerizable unsaturated bond and a compound having a polymerizable unsaturated bond in an aqueous medium. It has been found that the problems can be solved by an aqueous polyurethane resin dispersion which is obtained by using a polycarbonate polyol having an alicyclic structure as a raw material of the polyurethane resin.
  • the present invention (1) is an aqueous polyurethane resin dispersion obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium.
  • the polyurethane resin (A) having a polymerizable unsaturated bond has at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one molecule.
  • An aqueous polyurethane resin dispersion characterized in that it is a polyurethane resin obtained by reacting a compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in It relates to the body.
  • the present invention (2) relates to the aqueous polyurethane resin dispersion of the present invention (1), wherein the compound (B) having a polymerizable unsaturated bond contains a compound having at least three (meth) acryloyl groups.
  • the aqueous polyurethane resin dispersion of the invention (1) or (2), wherein the compound (B) having a polymerizable unsaturated bond contains a compound having at least 5 (meth) acryloyl groups.
  • the compound (e) having a group capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule can react with one isocyanato group
  • the compound (e) having a group capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule can react with one isocyanato group
  • a compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule comprises two hydroxyl groups and two (two)
  • the present invention relates to the aqueous polyurethane resin dispersion of any of the present inventions (1) to (5), which comprises a compound having an acryloyl group.
  • a polyurethane resin having a polymerizable unsaturated bond comprises a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), and a polyisocyanate (d);
  • the invention is obtained by reacting a compound (e) having a group capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bond in the molecule with a chain extender (C) (
  • the present invention relates to the aqueous polyurethane resin dispersion of any one of 1) to (6).
  • the invention (8) relates to the aqueous polyurethane resin dispersion of the invention (7), wherein the chain extender (C) is a primary polyamine compound.
  • the present invention (9) comprises at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one or more isocyanato groups in one molecule.
  • the compound (e) having a group capable of reacting with the compound and one or more polymerizable unsaturated bonds is reacted to obtain a polyurethane resin (A),
  • the present invention (10) can react with at least a polycarbonate polyol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one or more isocyanato groups.
  • the present invention (7) comprising the step ( ⁇ ) of reacting the polyurethane prepolymer (A1) with a chain extender (C) having reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin ) Or the method for producing an aqueous polyurethane resin dispersion of (8).
  • the present invention (11) relates to the aqueous polyurethane resin dispersion of any of the present inventions (1) to (8), which further contains a photopolymerization initiator.
  • the present invention (12) relates to a paint composition containing the aqueous polyurethane resin dispersion of any of the present inventions (1) to (8) and (11).
  • the present invention (13) relates to a coating agent composition containing the aqueous polyurethane resin dispersion of any of the present inventions (1) to (8) and (11).
  • various plastics (ABS resin, acrylic resin, polycarbonate resin, etc.) have good dispersibility and storage stability in an aqueous medium, and have cured active energy ray (for example, ultraviolet light).
  • the aqueous polyurethane resin dispersion which is excellent in the adhesion nature to a.), And its manufacturing method are provided.
  • an aqueous polyurethane resin dispersion which provides a coating film having high hardness and a method for producing the same are provided.
  • the aqueous polyurethane resin dispersion of the present invention includes outer plates of aircrafts, automobiles, etc., interior materials of automobiles, cellular phone casings, home electric appliance casings, personal computer casings, flooring materials such as decorative films, optical films, floorings, etc. It can be used as a raw material for paints (including primers) of synthetic resin molded articles such as outer walls, inks, adhesives, coatings, paint compositions and the like, and can be used in a wide range of applications.
  • the present invention is an aqueous polyurethane resin dispersion obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium
  • the polyurethane resin (A) having a polymerizable unsaturated bond comprises at least one polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), and a polyisocyanate (d)
  • the present invention relates to an aqueous polyurethane resin dispersion obtained by reacting a group capable of reacting with an isocyanato group and a compound (e) having one or more polymerizable unsaturated bonds.
  • the polyurethane resin (A) having a polymerizable unsaturated bond is at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), and a polyisocyanate (d) It is obtained by reacting a group capable of reacting with one or more isocyanato groups with a compound (e) having one or more polymerizable unsaturated bonds.
  • Polycarbonate polyol having alicyclic structure in main chain (a)
  • the polycarbonate polyol used in the present invention is a polycarbonate polyol (a) having an alicyclic structure in its main chain from the viewpoint that a coating film excellent in storage stability of the aqueous polyurethane resin dispersion and excellent in adhesiveness is obtained Polycarbonate polyol (a))).
  • the polycarbonate polyol (a) is not particularly limited, and, for example, a polycarbonate polyol obtained by reacting a polyol having an alicyclic structure in the main chain and a carbonate ester, a polyol having an alicyclic structure in the main chain, and other polyols Copolymerized polycarbonate polyol etc. which are obtained by making and carbonic acid ester react, etc. are mentioned.
  • the alicyclic structure also includes one having a hetero atom such as an oxygen atom or a nitrogen atom in the ring.
  • the preferred number average molecular weight of the polycarbonate polyol (a) is 400 to 3,000. When the number average molecular weight is in this range, an appropriate viscosity and good handleability can be easily obtained. In addition, it is easy to ensure the performance as a soft segment, and when a coating film is formed using the obtained aqueous polyurethane resin dispersion, it is easy to suppress the occurrence of cracking, and furthermore, the reactivity with the polyisocyanate (d) Is sufficient, and the urethane prepolymer can be produced efficiently.
  • the number average molecular weight of the polycarbonate polyol (a) is more preferably 400 to 1,500, and particularly preferably 500 to 1300.
  • the number average molecular weight is a number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K 1557. Specifically, the hydroxyl value is measured, and it is calculated by (56.1 ⁇ 1000 ⁇ number of valence) / hydroxyl value [mg KOH / g] by an end group determination method.
  • the valence is the number of hydroxyl groups in one molecule, and when the polycarbonate polyol is a polycarbonate diol, the valence is two.
  • the polyol having an alicyclic structure in the main chain is not particularly limited.
  • 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1 4-Cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, tricyclo [5.2 1.0 2,6 !
  • Dichlorodimethanol represented by decanedimethanol, each structural isomer of dimer acid diol or a mixture thereof and the like, diol having alicyclic structure in the main chain, and the like can be mentioned.
  • 1,4-cyclohexanedimethanol is preferable because of easy availability.
  • the other polyols are not particularly limited, and examples thereof include aliphatic polyols, aromatic polyols, polyester polyols, polyether polyols and the like.
  • the aliphatic polyol is not particularly limited, and examples thereof include aliphatic polyols having 2 to 12 carbon atoms. Specifically, 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Linear aliphatic diols such as -octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentane Examples thereof include branched aliphatic diols such as diol and 2-methyl-1,9-nonanediol; and polyhydric alcohols having three or more functional groups such as 1,1,1-trimethylolpropane and pentaerythritol.
  • the aromatic polyol is not particularly limited and, for example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol, 3,4'- Naphthalene dimethanol etc. are mentioned.
  • polyester polyol is not particularly limited.
  • polyester polyol of hydroxycarboxylic acid and diol such as polyester polyol of 6-hydroxycaproic acid and hexanediol
  • dicarboxylic acid such as polyester polyol of adipic acid and hexanediol and diol
  • polyester polyols and the like polyester polyols and the like.
  • the polyether polyol is not particularly limited, and examples thereof include polyethylene glycol (for example, diethylene glycol, triethylene glycol, tetraethylene glycol and the like), and polyalkylene glycols such as polypropylene glycol and polytetramethylene glycol.
  • polyethylene glycol for example, diethylene glycol, triethylene glycol, tetraethylene glycol and the like
  • polyalkylene glycols such as polypropylene glycol and polytetramethylene glycol.
  • the carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, cyclic carbonates such as ethylene carbonate, and the like.
  • phosgene etc. which can produce polycarbonate polyol can also be used.
  • aliphatic carbonates are preferable, and dimethyl carbonate is particularly preferable, in terms of easiness of production of polycarbonate polyol.
  • a carbonate ester and an excess number of polyols relative to the number of moles of the carbonate ester are added to a reactor, and the temperature 160 to 200 ° C., pressure
  • the reaction may be carried out at about 50 mmHg for 5 to 6 hours, and then at 200 to 220 ° C. for several hours at a pressure of several mmHg or less. It is preferable to make it react, extracting the byproduct alcohol out of the system in the said reaction.
  • the alicyclic structure content in the polycarbonate polyol (a) is preferably 20 to 65% by weight. If the alicyclic structure content is in this range, a coating film excellent in hardness is easily obtained due to the presence of the alicyclic structure, and the adhesion of the coating film to various plastics is also sufficient. On the other hand, it is easy to avoid a situation where the content of the alicyclic structure becomes too high and the viscosity of the prepolymer becomes high at the time of production of the aqueous polyurethane resin dispersion and handling becomes difficult, and good storage stability is easy Obtained.
  • the alicyclic structure content is more preferably 30 to 55% by weight.
  • the alicyclic structure content refers to the weight ratio of the alicyclic group in the polycarbonate polyol (a).
  • a cycloalkane residue such as a cyclohexane residue (in the case of 1,4-hexanedimethanol, a portion obtained by removing two hydrogen atoms from cyclohexane), or an unsaturated heterocyclic residue such as a tetrahydrofuran residue
  • tetrahydrofuran dimethanol the value calculated based on the part which remove
  • the polycarbonate polyol (a) is preferably a copolycarbonate polyol in which another polyol is used in combination.
  • other polyols aliphatic polyols, aromatic polyols, polyester polyols, polyether polyols can be used, and the above-mentioned specific examples apply.
  • a combination of a polyol having an alicyclic structure in the main chain and an aliphatic polyol is preferable, and in particular, a copolymerized polycarbonate polyol obtained by using 1,4-cyclohexanedimethanol and 1,6-hexanediol in combination is preferable. .
  • the polycarbonate polyol (a) may be used alone or in combination of two or more.
  • Acid group containing polyol (b) The acidic group-containing polyol (b) used in the present invention is not particularly limited as long as it contains two or more hydroxyl groups and one or more acidic groups in one molecule.
  • an acidic group a carboxy group, a sulfonic acid group, a phosphoric acid group, phenolic hydroxyl group etc. are mentioned.
  • the acidic group-containing polyol (b) one containing a compound having two hydroxyl groups and one carboxy group in one molecule is preferable.
  • the acidic group-containing polyol (b) may be used alone or in combination of two or more.
  • the acidic group-containing polyol (b) include dialkanolalkanoic acids such as dimethylolalkanoic acid such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid; N, N -Bishydroxyethyl glycine, N, N-bishydroxyethyl alanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acid group-containing polyether polyol, acid group-containing polyester polyol, etc. It can be mentioned.
  • dialkanolalkanoic acids such as dimethylolalkanoic acid such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid
  • N N -Bishydroxyethyl glycine
  • N N-bishydroxyethyl alanine
  • 3,4-dihydroxybutanesulfonic acid 3,6-dihydroxy-2-
  • a dialkanolalkanoic acid containing two alkanol groups is preferable, an alkanoic acid having 4 to 12 carbon atoms containing two methylol groups (dimethylolalkanoic acid) containing two alkanol groups is more preferable, and dimethylolol is more preferable.
  • alkanoic acids 2,2-dimethylol propionic acid is particularly preferred.
  • polys (c) Besides the polycarbonate polyol (a) and the acidic group-containing polyol (b), other polyols (c) (hereinafter sometimes referred to as "other polyols (c)") can be used.
  • Other polyols (c) include high molecular weight polyols such as polymer polyols and low molecular weight polyols. Examples of the high molecular weight polyol include those having a number average molecular weight of 400 to 6,000.
  • the polyol may be a diol or a trivalent or higher polyhydric alcohol.
  • Other polyols may be used alone or in combination of two or more. Low molecular weight polyols are preferred, and low molecular weight diols are particularly preferred, from the viewpoint that the hardness of the coating film is increased.
  • the polymer polymer polyol is not particularly limited, and polyester polyol, polyether polyol, acrylic polyol, polydiene polyol, and polycarbonate polyol having no alicyclic structure in the main chain can be suitably used.
  • the polyester polyol is not particularly limited.
  • the polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, random copolymer and block copolymer of ethylene oxide and butylene oxide, and the like. Furthermore, polyether polyester polyols having an ether bond and an ester bond can also be used.
  • the polydiene polyol is not particularly limited, and examples thereof include polydiene polyols containing units derived from butadiene, isoprene, 1,3-pentadiene, chloroprene, cyclopentadiene and the like.
  • Specific examples of the polydiene polyol include, for example, hydroxyl terminated liquid polybutadiene ("Poly bd” manufactured by Idemitsu Kosan Co., Ltd.), difunctional hydroxyl terminated liquid polybutadiene (“KRASOL” manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl terminated liquid polyisoprene ( Idemitsu Kosan Co., Ltd. "Poly ip”), a hydroxyl group terminal liquid polyolefin (Idemitsu Kosan Co., Ltd. "EPOL”), etc. are mentioned.
  • the polyacrylic polyol is not particularly limited.
  • acrylic acid ester having active hydrogen such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, or acrylic acid of glycerin Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, alone or in a mixture selected from the group consisting of monoesters or methacrylic acid monoesters, acrylic monoesters of trimethylolpropane or methacrylic monoesters; Acrylic acid esters such as 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, methacrylate Methacrylate with an active hydrogen such as 4-hydroxybutyl lactate, or methyl methacrylate, ethyl methacrylate, isopropyl methacrylate,
  • the polycarbonate polyol having no alicyclic structure in the main chain is not particularly limited, and examples thereof include aliphatic polycarbonate diols such as polytetramethylene carbonate diol, polypentamethylene carbonate diol, and polyhexamethylene carbonate diol; Aromatic polycarbonate diol such as xylylene carbonate diol; Copolycarbonate diol which is a reaction product of a plurality of aliphatic diols and a carbonate ester; co-reaction product of an aliphatic diol, an aromatic diol and a carbonate ester Copolymerized polycarbonate diols such as polymerized polycarbonate diols can be used.
  • aliphatic polycarbonate diols such as polytetramethylene carbonate diol, polypentamethylene carbonate diol, and polyhexamethylene carbonate diol
  • Aromatic polycarbonate diol such as xylylene carbon
  • copolymerized polycarbonate diol for example, copolymerized polycarbonate diol which is a reaction product of 1,3-propanediol, 1,4-butanediol and carbonate ester, 1,4-butanediol and 1,5-pentanediol Copolycarbonate diol which is a reaction product of esterification with carbonic acid ester, copolycarbonate diol which is a reaction product of 1,5-pentanediol, 1,6-hexanediol and carbonate ester, 1,4-butanediol, Copolymerized polycarbonate diol which is a reaction product of 1,6-hexanediol and carbonate ester, copolymerized polycarbonate diol which is a reaction product of 1,3-propanediol, 1,6-hexanediol and carbonate ester, etc. It can be mentioned.
  • the low molecular weight polyol is not particularly limited, and includes those having a number average molecular weight of 60 or more and less than 400.
  • Aliphatic diols having 2 to 9 carbon atoms such as diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane
  • the proportion of the other polyol (c) to the polycarbonate polyol (a) is preferably 40% by weight or less. If it is this range, it will be easy to avoid that the adhesiveness of the obtained coating film falls or it becomes difficult to manufacture aqueous polyurethane resin dispersion.
  • the proportion of the other polyol (c) is more preferably 20% by weight or less.
  • polyisocyanate (d) which can be used in the present invention is not particularly limited, and aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be mentioned.
  • aromatic polyisocyanate examples include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'- Diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 Examples thereof include '-diisocyanatodiphenylmethane, 1,5-naphthyl diisocyanate, 4,4 ′, 4 ′ ′-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate and the like.
  • aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecanetriisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexano And the like.
  • alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 And -isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.
  • IPDI isophorone diisocyanate
  • MDI 4,4'-dicyclohexylmethane diisocyanate
  • TDI methylcyclohexylene diisocyanate
  • bis (2 And -isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate 2,5-norbornane diisocyanate, 2,6-
  • These polyisocyanates may be used alone or in combination of two or more.
  • the number of isocyanato groups per one molecule of polyisocyanate is generally two, but polyisocyanates having three or more isocyanato groups such as triphenylmethane triisocyanate are also used to the extent that the polyurethane resin in the present invention does not gel. be able to.
  • polyisocyanates from the viewpoint of control of reactivity, high hardness, imparting of strength, etc., 4,4'-diphenylenemethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenation MDI) is preferred.
  • MDI 4,4'-diphenylenemethane diisocyanate
  • IPDI isophorone diisocyanate
  • hydrogenation MDI 4,4'-dicyclohexylmethane diisocyanate
  • V. Compounds having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule
  • e Polymerization in a compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule
  • the unsaturated bond includes, for example, a bond contained in an unsaturated group that can be polymerized by a radical or the like generated by a photopolymerization initiator.
  • Such unsaturated groups may be known ones, and include groups containing an ethylenically unsaturated bond, and from the viewpoint of easy availability and high reactivity, (meth) acryloyl group is preferable.
  • (meth) acryloyl group means acryloyl group and / or methacryloyl group
  • (meth) acrylate means acrylate or / and methacrylate
  • the unsaturated compound (e) has one or more polymerizable unsaturated bonds in the molecule.
  • Examples of the group capable of reacting with the isocyanato group in the unsaturated compound (e) include a hydroxyl group, an amino group, an isocyanato group, a thiol group and the like. Among them, a hydroxyl group is preferable from the viewpoint of the handling ease of the unsaturated compound (e).
  • the unsaturated compound (e) has one or more groups capable of reacting with the isocyanato group in the molecule.
  • the unsaturated compound (e) is preferably a compound (e ′) having at least one hydroxyl group and at least one polymerizable unsaturated bond from the viewpoint of easy handling.
  • the unsaturated compound (e ′) for example, an unsaturated compound (e′-1) having one hydroxyl group and one polymerizable unsaturated bond in one molecule, and one hydroxyl group in one molecule
  • Unsaturated compound (e'-2) having two or more polymerizable unsaturated groups
  • unsaturated compound (e'-3) having two or more hydroxyl groups and one polymerizable unsaturated group in one molecule
  • unsaturated compounds (e′-4) having two or more hydroxyl groups and two or more polymerizable unsaturated groups in one molecule.
  • an unsaturated compound (e'-1) having one hydroxyl group and one polymerizable unsaturated bond in one molecule for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate And 4-hydroxybutyl (meth) acrylate.
  • the unsaturated compound (e′-2) having one hydroxyl group and two or more polymerizable unsaturated bonds in one molecule for example, glycerin di (meth) acrylate, diglycerin tri (meth) acrylate, tri Examples include methylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, and (meth) acrylic acid adduct of glycidyl (meth) acrylate.
  • Examples of the unsaturated compound (e′-3) having two or more hydroxyl groups and one polymerizable unsaturated bond in one molecule include, for example, glycerin mono (meth) acrylate, diglycerin mono (meth) acrylate, penta Examples include erythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, and sorbitol mono (meth) acrylate.
  • Examples of the unsaturated compound (e′-4) having two or more hydroxyl groups and two or more polymerizable unsaturated bonds in one molecule include diglycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, and di Pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, 2 molecules Reaction product of (meth) acrylic acid with one molecule of 1,6-hexanediol diglycidyl (eg, "DA-212" manufactured by Nagase Chemtech Inc.), two molecules of epoxy (meth) acrylic acid and one molecule of neodymium Reaction with pentyl
  • a compound having an isocyanato group can also be used.
  • a (meth) acrylic compound having an isocyanato group 2-isocyanatoethyl acrylate (Kalens AOI manufactured by Showa Denko K. K.) 2-isocyanate Natoethyl methacrylate (Karenz MOI) and 1,1-bis (acryloyloxymethyl) ethyl isocyanate (Karenz BEI) may be mentioned.
  • As the unsaturated compound (e), N-isopropyl (meth) acrylamide and the like can also be used.
  • the unsaturated compounds (e) may be used alone or in combination of two or more.
  • only one type of unsaturated compounds (e′-1) to (e′-4) may be used, or two or more types may be used in combination.
  • the amount of the unsaturated compound (e) added is the solid content of the aqueous polyurethane resin dispersion (a compound having a polymerizable unsaturated bond (a compound (a polymerizable unsaturated bond ( When the total amount of B) is 100 parts by weight, it is preferably 2 to 50 parts by weight, more preferably 5 to 40 parts by weight.
  • the addition amount of the unsaturated compound (e) By setting the addition amount of the unsaturated compound (e) to 2 parts by weight or more, it is possible to suppress the decrease in the surface hardness of the obtained coating film.
  • By setting the addition amount of the unsaturated compound (e) to 50 parts by weight or less it is possible to suppress the decrease in the adhesion between the obtained coating film and the substrate.
  • the unsaturated compound (e) is preferably a compound having one hydroxyl group among the unsaturated compounds (e ′) from the viewpoint of improving the storage stability of the polyurethane water dispersion, and specifically, in a molecule, it is specifically An unsaturated compound (e'-1) having one hydroxyl group and one polymerizable unsaturated bond, and / or an unsaturated compound having one hydroxyl group and two or more polymerizable unsaturated bonds in one molecule It is preferred to contain the compound (e'-2).
  • an unsaturated compound (e'-2) having one hydroxyl group and two or more polymerizable unsaturated groups in one molecule from the viewpoint of improving the hardness of the obtained coating film, Among the unsaturated compounds (e′-2), compounds having one hydroxyl group and three (meth) acryloyl groups in one molecule are more preferable.
  • the amount of the unsaturated compound (e'-1) and / or the unsaturated compound (e'-2) used is the total solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond) Is preferably 2 to 50 parts by weight, and more preferably 5 to 40 parts by weight.
  • the unsaturated compound (e) is preferably a compound having two or more hydroxyl groups among the unsaturated compounds (e ′) from the viewpoint of the hardness of the obtained coating film, and specifically, two or more in one molecule.
  • Unsaturated compound (e'-3) having one hydroxyl group and one polymerizable unsaturated bond, and / or an unsaturated compound having two or more hydroxyl groups and two or more polymerizable unsaturated bonds in one molecule It is preferred to contain (e'-4).
  • an unsaturated compound (e'-4) having two or more hydroxyl groups and two or more polymerizable unsaturated groups in one molecule and an unsaturated compound (e Among '-4), compounds having two hydroxyl groups and two (meth) acryloyl groups in one molecule are more preferable.
  • the amount of the unsaturated compound (e'-3) and / or the unsaturated compound (e'-4) used is the total solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond) Is preferably 2 to 30 parts by weight, and more preferably 5 to 20 parts by weight.
  • the hydroxyl equivalent number of the polyol-containing component is preferably 100 to 500. If the number of hydroxyl group equivalents is in this range, the production of the aqueous polyurethane resin dispersion is easy, and a coating film excellent in storage stability and hardness of a good aqueous polyurethane resin dispersion is easily obtained. From the viewpoint of the hardness of the coating, it is preferably 120 to 300, more preferably 150 to 250.
  • the polyol-containing component is, in addition to the polycarbonate polyol (a), the acidic group-containing polyol (b), and any other polyol (c),
  • the unsaturated compound (e) is an unsaturated compound (e′-3) In the case of and / or (e'-4), these unsaturated compounds (e'-3) and / or (e'-4) are included.
  • the number of hydroxyl group equivalents can be calculated by the following formulas (1) and (2).
  • Number of hydroxyl group equivalents of each polyol molecular weight of each polyol / number of hydroxyl groups of each polyol (1)
  • Total number of hydroxyl group equivalents of total polyol M / total number of moles of polyol ...
  • M represents [[number of hydroxyl group equivalents of polycarbonate polyol (a) ⁇ number of moles of polycarbonate polyol (a)] + [number of hydroxyl group equivalents of acidic group-containing polyol (b) ⁇ acid group-containing polyol (b Number of hydroxyl groups of other polyol (c) ⁇ number of moles of other polyol (c) ⁇ + number of hydroxyl groups equivalent of (e′-3) ⁇ number of (e′-3) moles ]] + [Number of hydroxyl group equivalents of (e'-4) x number of moles of (e'-4)]] is shown.
  • the polyurethane resin (A) in the present invention is a polyurethane resin obtained by reacting at least a polycarbonate polyol (a), an acidic group-containing polyol (b), a polyisocyanate (d) and an unsaturated compound (e). Or a polycarbonate polyol (a), an acid group-containing polyol (b), a polyisocyanate (d), and an unsaturated compound (e) to obtain a polyurethane prepolymer (A1). Further, it is a polyurethane resin obtained by reacting with a chain extender (C).
  • the number of moles of all hydroxyl groups of the polycarbonate polyol (a), the acidic group-containing polyol (b), and the other polyols (c) and unsaturated compounds (e ') optionally present
  • the ratio of the number of moles of isocyanato groups of polyisocyanate (d) to is preferably 0.85 to 1.1.
  • the molecular weight of the polyurethane resin (A) may be small and the tack-free property may be inferior.
  • the ratio of the number of moles of isocyanato groups of polyisocyanate (d) to the number of moles of total hydroxyl groups of the component is preferably 0.90 to 1.05, and particularly preferably 0.95 to 1.01.
  • the polyurethane resin (A) and the polyurethane prepolymer (A1) are polycarbonate polyol (a), acid group-containing polyol (b), other polyols (c), polyisocyanate (d), unsaturated compound (e) Or an acid group-containing polyol (b), another polyol (c), a polyisocyanate (d), and an unsaturated compound (a). It may be a polyurethane resin obtained by reacting e) with the polyurethane prepolymer (A1) and further reacting it with a chain extender (C).
  • the temperature of the reaction between the polyurethane prepolymer (A1) and the chain extender (C) is, for example, 0 to 80. ° C., preferably 0 to 60 ° C.
  • the moles of all hydroxyl groups of the polycarbonate polyol (a), the acid group-containing polyol (b), and the other polyols (c) and unsaturated compounds (e ') optionally present
  • the ratio of the number of moles of isocyanato groups of polyisocyanate (d) to the number is preferably 1.01 to 2.5.
  • the ratio of the number of moles of isocyanato groups of polyisocyanate (d) to the number of moles of total hydroxyl groups of the component is preferably 1.2 to 2.2, and particularly preferably 1.3 to 2.0.
  • a polyurethane resin (A) or polyurethane prepolymer (A1) comprises polycarbonate polyol (a), acid group-containing polyol (b), optionally other polyol (c), and unsaturated compound (e)
  • the reaction of the component with the polyisocyanate (d) may be carried out by reacting (a), (b), optionally (c), (e) with (d) in a random order, and a plurality of types are mixed ((c) It may be reacted with d).
  • a catalyst can also be used.
  • the catalyst is not particularly limited.
  • salts of metals such as tin (tin) -based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead-based catalysts (lead acid octylate, etc.) and salts of organic and inorganic acids, and organometallics Derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine etc.), diazabicycloundecene catalysts, etc. may be mentioned.
  • dibutyltin dilaurate is preferable from the viewpoint of reactivity.
  • the reaction temperature in the reaction of the component with the polyisocyanate (d) is not particularly limited but is preferably 40 to 120.degree. Within this range, dissolution of the raw materials is sufficient, the viscosity of the resulting polyurethane (A) or urethane prepolymer (A1) is appropriate, stirring is easy, and polymerization in the unsaturated compound (e) It is easy to avoid problems such as the occurrence of polymerization reaction, gelation, and side reaction of the isocyanate group in the polyisocyanate (d).
  • the reaction temperature is more preferably 60 to 100 ° C.
  • a polymerization inhibitor is added to the reaction system to avoid unnecessary consumption of the polymerizable unsaturated bond of the unsaturated compound (e). Can also be added.
  • hydroquinone As a polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butyl hydroquinone, p-tert-butyl catechol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2, Quinone type polymerization inhibitors such as 5-bis (1,1-dimethylbutyl) hydroquinone; 2,6-bis (1,1-dimethylethyl) -4-methylphenol, 2,6-di-tert-butylphenol, 2 Such as 4, 4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol Alkylphenol polymerization inhibitors; aromatic amine polymerization inhibitors such as phenothiazine; Diphenylamine, N, N'-diphenyl-p-pheny
  • One of these may be used alone, or two or more of these may be used in combination.
  • a quinone type polymerization inhibitor and an alkylphenol type polymerization inhibitor in combination, the consumption by polymerization of the polymerizable unsaturated bond can be further reduced.
  • the amount of the polymerization inhibitor added can be 0.001 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of the polyurethane resin (A).
  • polycarbonate polyol (a), acidic group-containing polyol (b), optionally other polyol (c), and unsaturated compound (e) with polyisocyanate (d) can be carried out either without solvent or with an organic solvent You may do it.
  • organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, N-ethyl pyrrolidone, ethyl acetate and the like.
  • acetone, methyl ethyl ketone and ethyl acetate are preferable because they can be removed by heating and reducing pressure after dispersion of polyurethane prepolymer in water and chain elongation reaction.
  • N-methyl pyrrolidone and N-ethyl pyrrolidone are preferable because they function as a film forming aid when producing a coating film from the obtained aqueous polyurethane resin dispersion.
  • the addition amount of the organic solvent is preferably 0 to 5 by weight based on the total amount of polycarbonate polyol (a), acid group-containing polyol (b), optionally other polyol (c), and unsaturated compound (e).
  • the viscosity at the time of obtaining a polyurethane prepolymer (A1) can be made into a suitable range, and a favorable dispersion
  • the time taken to remove the organic solvent does not take too long, and the physical properties of the coating film may be deteriorated due to the organic solvent remaining in the coating film obtained using the aqueous polyurethane resin dispersion. It can be easily avoided.
  • the acid value of the polyurethane resin (A) or polyurethane prepolymer (A1) is preferably 20 to 50 mg KOH / g. Within this range, it is easy to ensure good dispersibility in an aqueous medium and water resistance of the coating film.
  • the acid value is more preferably 25 to 45 mg KOH / g, still more preferably 30 to 40 mg KOH / g.
  • the acid value of the polyurethane resin (A) or polyurethane prepolymer (A1) refers to the solvent used for producing the polyurethane resin (A) or polyurethane prepolymer (A1) and the polyurethane prepolymer (A1).
  • [Acid Value of Polyurethane Resin (A) or Polyurethane Prepolymer (A1)] [Mole number of acidic group of acidic group-containing polyol (b)] ⁇ 56.11 / [polycarbonate polyol (a), acidic group-containing polyol (b), optionally other polyol (c), unsaturated compound (e) And total weight of polyisocyanate (d)] (3)
  • dispersion in an aqueous solvent and chain extension with a chain extender (C) are carried out to obtain the aqueous polyurethane resin dispersion of the present invention, the acid value is polyurethane It is synonymous with the acid value of prepolymer (A1).
  • the total amount of solids (including the compound (B) having a polymerizable unsaturated bond) of the aqueous polyurethane resin dispersion is 100 parts by weight
  • the polycarbonate polyol (a) is preferably 2 to 50 parts by weight
  • the acid group-containing polyol (b) is preferably 2 to 15 parts by weight
  • the other polyol (c) is preferably 0 to 30 parts by weight, unsaturated.
  • the compound (e) is preferably 5 to 50 parts by weight.
  • the adhesion of the coating film obtained from the aqueous polyurethane resin dispersion is high, and the dispersibility of the polyurethane resin (A) in the aqueous medium is good and excellent.
  • Membrane properties are easily obtained.
  • the polycarbonate polyol (a) is more preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight. If the acidic group-containing polyol (b) is in the above range, the water resistance of the coating film obtained from the aqueous polyurethane resin dispersion is good, and the dispersibility of the polyurethane resin (A) in the aqueous medium is good.
  • the acidic group-containing polyol (b) is more preferably 3 to 10 parts by weight, particularly preferably 4 to 7 parts by weight.
  • the unsaturated compound (e) is in the above range, a film obtained from the aqueous polyurethane resin dispersion has excellent hardness and adhesion, and the storage stability of the aqueous polyurethane resin dispersion is also excellent.
  • the unsaturated compound (e) is more preferably 10 to 40 weight.
  • Chain extender (C) The polyurethane resin (A) having a polymerizable unsaturated bond in the present invention becomes less tacky to the dried coating before irradiation with active energy rays (for example, ultraviolet rays) by using the chain extender (C), and becomes tack free Therefore, it is preferable to use one prepared using a chain extender (C).
  • active energy rays for example, ultraviolet rays
  • the chain extender (C) for example, ethylene diamine, 1,4-tetramethylene diamine, 2-methyl-1,5-pentane diamine, 1,4-butane diamine, 1,6-hexamethylene diamine, 1,4 -Hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, hydrazine, adipoyl dihydrazide Amine compounds such as diethylenetriamine and triethylenetetramine, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol, polyalkylene glycols represented by polyethylene glycol, water and the like And above all
  • the chain extender (C) is preferably an organic compound, more preferably a polyamine compound, and more
  • the addition amount of the chain extender (C) is preferably not more than the equivalent of the isocyanato group as the chain extension origin in the polyurethane prepolymer (A1), and more preferably 0.7 to 0.99 equivalent of the isocyanato group. is there. Within this range, the molecular weight of the chain-extended polyurethane resin (A) can be made an appropriate range, and in turn, the strength of the coating film obtained by applying the aqueous polyurethane resin dispersion containing this can be improved. .
  • the chain extender (C) may be added after dispersing the polyurethane prepolymer (A1) in water, or may be added during the dispersion. Chain extension can also be performed with water. In this case, water as a dispersion medium also serves as a chain extender.
  • the compound (B) having a polymerizable unsaturated bond in the present invention is preferably a compound which is polymerized in the coexistence of a photo radical generator or in the coexistence of a heat radical generator, but a compound which does not react with the isocyanato group at 25 ° C. It is preferred to use
  • the compound which has ethylenic unsaturated bonds such as a vinyl group or an allyl group
  • the compound which has a (meth) acryloyl group is mentioned.
  • the compound (B) having a polymerizable unsaturated bond is a polyfunctional compound having a plurality of even a monofunctional compound having one group having a polymerizable unsaturated bond such as a (meth) acryloyl group. It may be a compound, and a compound having three or more (meth) acryloyl groups or a compound having five or more (meth) acryloyl groups can also be suitably used.
  • a (meth) acrylate compound As a compound (B) which has a polymerizable unsaturated bond, a (meth) acrylate compound is preferable.
  • (meth) acrylate compounds include (meth) acrylate compounds of monomers, polyurethane (meth) acrylate compounds, polyester (meth) acrylate compounds, and polyalkylene (meth) acrylate compounds.
  • Monomer (meth) acrylate compounds such as mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate and the like (mono) Meta) acrylates and poly (meth) acrylates can be used.
  • Examples of the mono (meth) acrylate include 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) 2.) Acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate and the like.
  • di (meth) acrylates examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Alkylene glycol di (meth) acrylates such as hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A di (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Polyether di (meth) acrylates such as acrylates; Bisphenol A ethylene oxide modified di (meth) acrylate, Bisphenol A propylene oxide modified di (meth) acrylate, Alkylene oxide modified di (meth) acrylates such as pentyl glycol ethylene oxide modified di (meth) acrylate, neopen
  • tri (meth) acrylates examples include trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate.
  • Examples of tetra (meth) acrylates include dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide (4 moles) modified pentaerythritol tetra (meth) acrylate (Dasel Cytech Co., Ltd. Ebecryl 40) And alkylene oxide-modified pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate and the like.
  • Examples of penta (meth) acrylates include dipentaerythritol penta (meth) acrylate and the like.
  • Examples of hexa (meth) acrylates include dipentaerythritol hexa (meth) acrylate and the like.
  • poly (di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate) Meta) acrylate is preferred. This is because, by having a plurality of (meth) acryloyl groups in the molecule, the molecular weight can be increased more easily than in the case of mono (meth) acrylates.
  • tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate are preferable in terms of hardness. More preferably, penta (meth) acrylate and hexa (meth) acrylate are used.
  • (meth) acrylates of polymers in addition to (meth) acrylates having a polyalkylene glycol structure, polyurethane (meth) acrylate compounds, polyester (meth) acrylate compounds, polyalkylene (meth) acrylate compounds, etc.
  • an acrylic polymer or the like having a polymerizable unsaturated bond in the molecule can be used, for example, polybutyl acrylate having a polymerizable double bond at the end of one molecule (manufactured by Soken Chemical Co., Ltd.) Actflow BGV-100T "), and polybutyl acrylate having polymerizable double bonds at both molecular ends (" Aktoflow "manufactured by Soken Chemical Co., Ltd.).
  • compounds having a vinyl group or an allyl group other than (meth) acrylate compounds such as acryloyl morpholine, styrene, N-vinyl-2-pyrrolidone and the like can also be used. .
  • the compound (B) having a polymerizable unsaturated bond a commercially available one may be used as it is.
  • the compound (B) having a polymerizable unsaturated bond may be used alone or in combination of two or more.
  • the total amount of solids (including the compound (B) having a polymerizable unsaturated bond) in the aqueous polyurethane resin dispersion is 100 parts by weight, preferably 2 to 50 parts by weight, and more preferably 5 to 40 parts by weight It is.
  • the compound (B) having a polymerizable unsaturated bond is preferably 10 to 60 parts by weight, based on 100 parts by weight of the total solid content of the aqueous polyurethane resin dispersion (including the polyurethane resin (A)). Within this range, the adhesion and hardness of the coating film obtained from the aqueous polyurethane resin dispersion can be easily improved, and good storage stability can be obtained for the aqueous polyurethane resin dispersion.
  • the compound (B) having a polymerizable unsaturated bond is more preferably 20 to 50 parts by weight, and particularly preferably 30 to 45 parts by weight.
  • Aqueous Medium the polyurethane resin (A) is dispersed in an aqueous medium.
  • the aqueous medium include water, a mixed medium of water and a hydrophilic organic solvent, and the like.
  • water examples include, for example, fresh water, ion-exchanged water, distilled water, ultrapure water and the like.
  • ion-exchanged water is preferable in consideration of easiness of obtaining and instability of particles due to the influence of salt and the like.
  • hydrophilic organic solvents examples include lower monohydric alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol and glycerol; aprotics such as N-methylmorpholine, dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone Hydrophilic organic solvents and the like.
  • the amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by weight.
  • the aqueous polyurethane resin of the present invention comprises at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one or more isocyanates in one molecule.
  • a polyurethane resin (A) is obtained by reacting a group (e) having a group capable of reacting with the group and a compound (e) having one or more polymerizable unsaturated bonds, It is obtained by dispersing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium.
  • the method for producing an aqueous polyurethane resin dispersion of the present invention comprises polycarbonate polyol (a), acidic group-containing polyol (b), polyisocyanate (d), and a group capable of reacting with one or more isocyanate groups.
  • a step ( ⁇ ) of reacting the polyurethane prepolymer (A1) with a chain extender (C) having reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin can be included.
  • the steps ( ⁇ 1) and ( ⁇ 2) for obtaining the polyurethane prepolymer (A1) are preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Moreover, it is desirable to add a polymerization inhibitor into the reaction system as needed.
  • the temperature of the steps ( ⁇ 1) and ( ⁇ 2) for obtaining the polyurethane prepolymer (A1) can be performed at 0 to 120 ° C. in order to avoid unnecessary polymerization of the polymerizable unsaturated bond. It is preferable to carry out at 0 to 100 ° C.
  • an acidic group neutralizer that can be used in the step ( ⁇ ) of neutralizing the acidic group of the polyurethane prepolymer (A1), trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N- Organic amines such as phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, and pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and ammonia. Among them, preferred is an organic amine, more preferred is a tertiary amine, and most preferred is triethylamine.
  • the acidic group of a polyurethane prepolymer (A1) means a carboxylic acid group, a sulfonic acid group, etc.
  • the amount of the acidic group neutralizer used is preferably such that the number of moles is from 0.8 to 1.5 with respect to the acidic group of the polyurethane prepolymer (A1). Within this range, the dispersibility of the polyurethane prepolymer (A1) in water is sufficient, and the storage stability of the resulting aqueous polyurethane resin dispersion does not decrease, and the odor of the aqueous polyurethane resin dispersion is reduced. It can easily be avoided that the situation becomes stronger.
  • the method and operation sequence thereof are not particularly limited, but, for example, a method of mixing (A1) with (B) and dispersing in an aqueous medium, or (B) mixing (A1) with an aqueous medium (A1) is dispersed in an aqueous medium, (B) is mixed and dispersed, (B) is dispersed in an aqueous medium, and (A1) is mixed and dispersed, , (A1) and (B) are each dispersed in an aqueous medium and then mixed.
  • a well-known stirring apparatus such as a homomixer or a homogenizer can be used for the above-mentioned mixing, stirring and dispersion.
  • a hydrophilic organic solvent, water, etc. are added in advance before mixing in order to adjust the viscosity, to improve the workability, and to improve the dispersibility. You can also
  • the step ( ⁇ ) of mixing the polyurethane prepolymer (A1) with the compound (B) having a polymerizable unsaturated bond is carried out in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond.
  • oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond.
  • the temperature at which the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond are mixed can be performed at 0 to 100 ° C. in order to avoid unnecessary consumption of the polymerizable unsaturated bond. C., more preferably 0.degree. To 70.degree. C., and most preferably 50.degree. To 70.degree.
  • the step ( ⁇ ) of neutralizing the acidic group of the polyurethane prepolymer (A1), the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium may be carried out earlier or simultaneously.
  • the aqueous medium and the acidic group neutralizing agent may be mixed at one time, or the acidic group neutralizing agent is previously mixed in the aqueous medium or (B), And (A1) may be mixed.
  • (A1), (C), (B) and the aqueous medium may be mixed at one time, or (C) may be mixed in advance with the aqueous medium, and these may be mixed with (A1) or (B) And may be mixed.
  • a step ( ⁇ ) of neutralizing the acid group of the polyurethane prepolymer (A1), and a step ( ⁇ ) of dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium The step ( ⁇ ) of reacting the polyurethane prepolymer (A) with the chain extender (C) to obtain an aqueous polyurethane resin can also be carried out simultaneously.
  • the acidic group neutralizing agent and the aqueous medium may be mixed at one time, or (C) or the acidic group neutralizing agent may It may be mixed in B), and these may be mixed with (A1) or (B).
  • the reaction may be carried out slowly with cooling, and in some cases, heating up to 60 ° C. or less
  • the reaction may be promoted under conditions.
  • the reaction time under cooling can be about 0.5 to 24 hours, and the reaction time under heating conditions of 60 ° C. or less can be about 0.1 to 6 hours.
  • the polyurethane resin (A) is preferably 5 to 60 parts by weight, and more preferably Is 15 to 50 parts by weight, more preferably 25 to 40 parts by weight.
  • the number average molecular weight of the polyurethane resin (A) is preferably 1,000 to 1,000,000. From the viewpoint of tack-free property of the dried coating before light curing, it is more preferably 10,000 to 1,000,000.
  • Photopolymerization initiator can also be added to the aqueous polyurethane resin dispersion of the present invention.
  • the photopolymerization initiator is not particularly limited, and known ones can be used. Specifically, a photocleavage type or hydrogen abstraction type photopolymerization initiator capable of being easily cleaved to form two radicals by irradiation with active energy rays (for example, ultraviolet light) can be used. These can also be used together.
  • photopolymerization initiator examples include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, benzoin ethyl ether, benzoin n.
  • -Propyl ether benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl- ⁇ -hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl Ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl- - phenylpropan-1-one, 2,4,6, - trimethyl benzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenyl-ethanone, and the like.
  • hydroxycyclohexyl phenyl ketone is preferred.
  • a photoinitiator When adding a photoinitiator, it is preferable to add after the process ((delta)) which makes a polyurethane prepolymer (A1) and a chain extender (C) react, and obtains aqueous polyurethane resin (A).
  • the addition amount of the photopolymerization initiator is preferably 0.5 to 5 parts by weight with respect to the total solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond).
  • aqueous polyurethane resin dispersion of the present invention if necessary, a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoamer, a plasticizer, and a surface conditioner Additives such as anti-settling agents can also be added.
  • the additives may be used alone or in combination of two or more.
  • the aqueous polyurethane resin dispersion of the present invention is preferably substantially free of a protective colloid, an emulsifier and a surfactant from the viewpoint of the hardness and chemical resistance of the resulting coating film.
  • the present invention also relates to a coating composition and a coating composition comprising the aqueous polyurethane resin dispersion.
  • resins can also be added to the coating composition and the coating agent composition of the present invention in addition to the aqueous polyurethane resin dispersion.
  • resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins and the like. These may be used alone or in combination of two or more.
  • Other resins preferably have one or more hydrophilic groups.
  • the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, a polyethylene glycol group and the like.
  • the other resin is preferably at least one selected from the group consisting of polyester resin, acrylic resin, and polyolefin resin.
  • the polyester resin can be usually produced by an esterification reaction or transesterification reaction of an acid component and an alcohol component.
  • the acid component compounds which are usually used as an acid component in the production of polyester resins can be used.
  • an acid component an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid etc. can be used, for example.
  • the hydroxyl value of the polyester resin is preferably about 10 to 300 mg KOH / g, more preferably about 50 to 250 mg KOH / g, and still more preferably about 80 to 180 mg KOH / g.
  • the acid value of the polyester resin is preferably about 1 to 200 mg KOH / g, more preferably about 15 to 100 mg KOH / g, and still more preferably about 25 to 60 mg KOH / g.
  • the weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, and still more preferably 1,500 to 200,000.
  • a hydroxyl group-containing acrylic resin is preferable.
  • the hydroxyl group-containing acrylic resin comprises, for example, a solution polymerization method in an organic solvent, a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, in water It can manufacture by copolymerizing by well-known methods, such as the emulsion polymerization method of this.
  • the hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl group and one or more polymerizable unsaturated bond in one molecule.
  • (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like, and having 2 to 8 carbon atoms
  • Monoesters with dihydric alcohols; ⁇ -caprolactone modified products of these monoesters; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is a hydroxyl group Etc. can be mentioned.
  • the hydroxyl group-containing acrylic resin preferably has an anionic functional group.
  • the hydroxyl group-containing acrylic resin having an anionic functional group may be, for example, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group or a phosphoric acid group as one of the polymerizable unsaturated monomers. It can be manufactured by using.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mg KOH / g, and more preferably about 2 to 100 mg KOH / g, from the viewpoint of storage stability of the aqueous polyurethane resin dispersion and water resistance of the obtained coating film.
  • the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mg KOH / g, and preferably 2 to 150 mg KOH / g from the viewpoint of water resistance and the like of the obtained coating.
  • the degree is more preferable, and about 5 to 100 mg KOH / g is more preferable.
  • the weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably 3,000 to 50,000.
  • polyether resin examples include polymers or copolymers having an ether bond, and examples thereof include polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether, bisphenol A, bisphenol F and the like. And polyethers derived from group polyhydroxy compounds.
  • polycarbonate resin the polymer manufactured from the bisphenol compound is mentioned, For example, bisphenol A polycarbonate etc. are mentioned.
  • polyurethane resin resin which has a urethane bond obtained by reaction of various polyol components, such as an acryl, polyester, a polyether, and a polycarbonate, and polyisocyanate is mentioned.
  • the resin etc. which are obtained by reaction of a bisphenol compound and epichlorohydrin are mentioned.
  • bisphenols include bisphenol A and bisphenol F.
  • alkyd resins include polybasic acids such as phthalic acid, terephthalic acid and succinic acid and polyhydric alcohols, as well as fats and oils / fat fatty acids (soybean oil, linseed oil, coconut oil, stearic acid etc.), natural resins (rosin, succinic acid)
  • Alkyd resins obtained by reacting modifiers such as e.g.
  • a polyolefin resin a polyolefin resin obtained by polymerizing or copolymerizing an olefin monomer with another monomer appropriately according to a general polymerization method is dispersed in water using an emulsifying agent, or an olefin monomer is suitably used with another monomer And resins obtained by emulsion polymerization.
  • olefin monomers examples include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1- ⁇ -olefins such as decene and 1-dodecene; conjugated dienes and non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and styrenes, etc. may be mentioned, and these monomers may be used alone You may use together and may use multiple types.
  • Examples of other monomers copolymerizable with olefin monomers include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, etc., and these monomers These may be used alone or in combination of two or more.
  • the coating composition and the coating agent composition of the present invention improve the water resistance and the like of the coating film or multilayer coating film, coating film using the coating composition or the coating agent composition, by containing a curing agent. be able to.
  • curing agent for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like can be used.
  • the curing agent may be used alone or in combination of two or more.
  • the amino resin includes, for example, partially or completely methylated amino resin obtained by the reaction of an amino component and an aldehyde component.
  • the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiloganamine, dicyandiamide and the like.
  • the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
  • polyisocyanate examples include compounds having two or more isocyanato groups in one molecule, and examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
  • blocked polyisocyanates include those obtained by adding a blocking agent to the polyisocyanate group of the aforementioned polyisocyanate, and examples of blocking agents include phenols such as phenol and cresol, etc., methanol, ethanol and the like.
  • Aliphatic alcohols such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetic acid amide, lactams such as ⁇ -caprolactam and ⁇ -valerolactam, and amber Blocking agents such as acid imides such as acid imides and maleimides, oximes such as acetoaldoxime, acetone oxime and methyl ethyl ketoxime, and amines such as diphenyl aniline, aniline and ethylene imine; Be
  • melamine resins include methylolmelamines such as dimethylolmelamine and trimethylolmelamine; alkyl ethers or condensates of these methylolmelamines; and condensates of alkylolates of methylolmelamine.
  • a color pigment, an extender pigment and a bright pigment can be added to the coating composition and the coating agent composition of the present invention.
  • color pigments include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, graphene pigments, perylene pigments and the like. These may be used alone or in combination of two or more. In particular, it is preferable to use titanium oxide and / or carbon black as a color pigment.
  • the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white and the like.
  • barium sulfate and / or talc as an extender pigment, and it is more preferable to use barium sulfate.
  • the bright pigment for example, aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, etc. may be used. it can.
  • the coating composition and the coating agent composition of the present invention may optionally contain a thickener, a curing catalyst, an ultraviolet light absorber, a light stabilizer, an antifoamer, a plasticizer, a surface conditioner, an antisettling agent, etc.
  • Conventional paint additives can be included. These may be used alone or in combination of two or more.
  • the method for producing the coating composition and the coating agent composition of the present invention is not particularly limited, but any known production method can be used. Generally, a coating composition and a coating agent composition are produced by mixing the aqueous polyurethane resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the coating method. Ru.
  • to-be-coated material of a coating composition or to-be-coated material of a coating agent composition a metal, a plastics, an inorganic substance, a wood etc. are mentioned.
  • the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, dip coating and the like.
  • the aqueous polyurethane resin dispersion, the aqueous polyurethane resin dispersion composition, the coating composition, and the coating composition of the present invention are applied to or coated or coated on a desired substrate, and then an aqueous medium with or without heating. After evaporating at least a part of the compound, it is preferable to cure by irradiating active energy rays.
  • active energy ray ionizing radiation such as electron beam, ultraviolet ray or ⁇ ray may be mentioned, and among them, ultraviolet ray is preferable.
  • the light source of ultraviolet light is not particularly limited as long as it emits light in the ultraviolet region, and for example, a xenon lamp, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc lamp, tungsten lamp and the like can be used.
  • the irradiation time can be appropriately varied depending on conditions such as the type of the compound having a polymerizable unsaturated bond, the type of the photopolymerization initiator, the film thickness, the ultraviolet light source and the like. It is preferable to irradiate for 1 to 60 seconds from the viewpoint of workability. Furthermore, in order to complete the curing reaction, it can also be subjected to heat treatment after ultraviolet irradiation.
  • the irradiation amount of the ultraviolet light used when curing the aqueous polyurethane resin dispersion, the coating composition, the coating composition and the like of the present invention is 300 to 3,000 mJ / cm 2 from the viewpoint of fast curing and workability. Is preferred.
  • electron beams and the like can also be used for curing.
  • a photopolymerization initiator may not be added, and it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.
  • ETERACOLL registered trademark
  • UM90 3
  • the reaction mixture was cooled to 70 ° C., to which dipentaerythritol hexaacrylate (DPHA, 79.9 g) and triethylamine (8.9 g) were added and mixed.
  • DPHA dipentaerythritol hexaacrylate
  • triethylamine 8.9 g
  • the reaction mixture (226 g) was added into water (386 g) under vigorous stirring.
  • 35% by weight of an aqueous 2-methyl-1,5-pentanediamine solution (MPMD, 20.1 g) was added to obtain an aqueous polyurethane resin dispersion.
  • ETERACOLL registered trademark
  • UM90 3
  • ETERACOLL registered trademark
  • UM90 3: 1 polycarbonate mixture obtained by reacting a
  • the reaction mixture was cooled to 70 ° C., to which dipentaerythritol hexaacrylate (DPHA, 178 g) and triethylamine (19.5 g) were added and mixed.
  • DPHA dipentaerythritol hexaacrylate
  • triethylamine (19.5 g) were added and mixed.
  • the reaction mixture (251 g) was added into water (423 g) under vigorous stirring. Then, 35 wt% aqueous diethylenetriamine solution (DETA, 13.3 g) was added to obtain an aqueous polyurethane resin dispersion.
  • DETA 35 wt% aqueous diethylenetriamine solution
  • ETERACOLL registered trademark
  • UM90 3
  • polycarbonate mixture obtained by reacting a
  • the reaction mixture was cooled to 70 ° C., to which dipentaerythritol hexaacrylate (DPHA, 178 g) and triethylamine (19.5 g) were added and mixed.
  • the reaction mixture (232 g) was added into water (391 g) under vigorous stirring.
  • a 35 wt% aqueous solution of diethylenetriamine (DETA, 6.1 g) and a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 10.4 g) are added to obtain an aqueous polyurethane resin dispersion. Obtained.
  • ETERACOLL registered trademark
  • UM90 3
  • reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 79.1 g) and triethylamine (8.6 g) were added and mixed.
  • TMPTA trimethylolpropane triacrylate
  • 8.6 g triethylamine
  • ETERACOLL registered trademark
  • UM90 3
  • ETERACOLL registered trademark
  • UM90 3
  • ETERACOLL registered trademark
  • UM90 3
  • ETERACOLL registered trademark
  • UM90 3
  • ETERACOLL registered trademark
  • UM90
  • reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 78.7 g) and triethylamine (5.6 g) were added and mixed.
  • TMPTA trimethylolpropane triacrylate
  • 5.6 g triethylamine
  • the reaction mixture (241 g) was added into water (390 g) under vigorous stirring.
  • 35% by weight of a 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 29.1 g) was added to obtain an aqueous polyurethane resin dispersion.
  • reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 75.0 g) and triethylamine (6.8 g) were added and mixed.
  • TMPTA trimethylolpropane triacrylate
  • the reaction mixture (222 g) was added into water (375 g) under vigorous stirring. Then, 35% by weight of an aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 16.5 g) was added to obtain an aqueous polyurethane resin dispersion.
  • MPMD 2-methyl-1,5-pentanediamine
  • ETERACOLL registered trademark
  • reaction mixture (241 g) was added into water (334 g) under vigorous stirring. Then, 35% by weight of an aqueous 2-methyl-1,5-pentanediamine solution (MPMD, 29.5 g) was added to obtain an aqueous polyurethane resin dispersion.
  • MPMD 2-methyl-1,5-pentanediamine solution
  • Example preparation of pencil hardness and adhesion To each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4, 3% by weight / solid content of a polymerization initiator (IRGACURE 500, manufactured by Ciba Specialty Chemical Co., Ltd.) is added, and the coating agent is Obtained. This was uniformly applied on ABS resin, acrylic resin and PC resin so that the film thickness after drying was about 20 ⁇ m. Subsequently, the coating film (before ultraviolet irradiation) was obtained by drying at 60 degreeC for 30 minutes. The obtained coating film was passed under a high pressure mercury lamp (single irradiation, ultraviolet irradiation amount 1000 mJ / cm 2 ). The obtained polyurethane resin coating film was subjected to pencil hardness measurement and adhesion evaluation.
  • a polymerization initiator IRGACURE 500, manufactured by Ciba Specialty Chemical Co., Ltd.
  • the polyurethane resin coating film on the ABS resin, acrylic resin, and PC resin obtained above was evaluated by the cross-cut peeling method. That is, 25 square grids of 4 mm 2 were prepared on a test piece with a cutter, and peelability was examined using a cellophane tape.
  • the parts by weight in the table represent the parts by weight of each compound when the total solid content (including the acrylic compound) in the resin is 100 parts by weight.
  • the pencil hardness in the table for example, “H” indicates that the pencil of H does not scratch at all.
  • “" 2H-3H indicates that a 3H pencil is scratched or not, and 2H is not scratched at all.
  • the adhesion in the table indicates the result of the peeling test.
  • “25/25" indicates that 25 cells in 25 cells are in close contact with each other after the test.
  • the aqueous polyurethane resin dispersion of the example was able to form a coating film having excellent adhesion and was excellent in storage stability.
  • the storage stability was inferior.
  • the aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for paints and coatings.

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Abstract

Provided are: an aqueous polyurethane resin dispersion that exhibits good storage stability, and after being cured by actinic radiation (such as UV radiation) and formed into a coating, adheres well to various plastics (ABS resins, acrylic resins, polycarbonate resins); and an aqueous polyurethane resin dispersion that yields a high-hardness coating. The present invention pertains to an aqueous polyurethane resin dispersion that comprises at least the following dispersed in an aqueous medium: a polyurethane resin (A) that has polymerizable unsaturated bonds; and a compound (B) that has polymerizable unsaturated bonds. Said polyurethane resin (A) that has polymerizable unsaturated bonds comprises: a polycarbonate diol (a) that has an alicyclic structure in the main chain thereof; an acid-group-containing polyol (b); a polyisocyanate (d); and a compound (e), each molecule of which has at least one group that can react with an isocyanate group and at least one polymerizable unsaturated bond. The present invention also pertains to a paint composition and coating composition that contain the abovementioned aqueous polyurethane resin dispersion and a manufacturing method therefor.

Description

水性ポリウレタン樹脂分散体及びその製造方法、並びにその使用Aqueous polyurethane resin dispersion, method for producing the same, and use thereof
　本発明は、紫外線をはじめとする活性エネルギー線照射により硬化可能な水性ウレタン樹脂分散体及びその製造方法、並びにその使用に関するものである。 The present invention relates to an aqueous urethane resin dispersion that can be cured by irradiation with active energy rays such as ultraviolet light, a method for producing the same, and use thereof.
　ポリカーボネートポリオールはポリウレタン樹脂の原料となる有用な化合物であり、イソシアネート化合物との反応により、硬質フォーム、軟質フォーム、塗料、接着剤、合成皮革、インキバインダー等に用いられるポリウレタン樹脂を製造することができる。また、ポリカーボネートポリオールを原料とした水性ポリウレタン樹脂分散体を塗布して得られる塗膜は、耐光性、耐熱性、耐加水分解性、耐油性に優れることが知られている（特許文献１参照）。 Polycarbonate polyol is a useful compound to be a raw material of polyurethane resin, and can react with an isocyanate compound to produce polyurethane resin used for rigid foam, flexible foam, paint, adhesive, synthetic leather, ink binder, etc. . Moreover, the coating film obtained by apply | coating the water-based polyurethane resin dispersion which used the polycarbonate polyol as a raw material is known to be excellent in light resistance, heat resistance, hydrolysis resistance, and oil resistance (refer patent document 1). .
　中でも、脂肪族ポリカーボネートポリオールを用いた水性ウレタン樹脂分散体を塗布して得られる塗膜は、基材への密着性や耐ブロッキング性が向上することからアンダーコート剤として用いられることが知られている（特許文献２参照）。また、塗膜の硬度、耐久性を向上させるために、脂環構造を有するポリカーボネートポリオールを用いた水性ポリウレタン樹脂分散体も提案されている（特許文献３、４及び５参照）。 Above all, a coating film obtained by applying an aqueous urethane resin dispersion using an aliphatic polycarbonate polyol is known to be used as an undercoat agent because the adhesion to a substrate and the blocking resistance are improved. (See Patent Document 2). Moreover, in order to improve the hardness of a coating film, and durability, the water-based polyurethane resin dispersion which used the polycarbonate polyol which has alicyclic structure is also proposed (refer patent document 3, 4 and 5).
　一方、ラジカル重合性化合物は、加熱以外の方法によっても硬化性に優れるため、生産性、省エネルギーの観点からも特長を有するものとして一般に認識されている。ラジカル重合性化合物を有する活性エネルギー線硬化性樹脂組成物は、かかる特長に照らし、金属用塗料、各種プラスチックフィルム用オーバーコート剤、木工用塗料、印刷インキ等の各種コーティングや接着剤等の有効成分として使用されている。例えば、水性ポリウレタン樹脂分散体に対し、（メタ）アクリレート系化合物を分散させたエネルギー線硬化型水系樹脂組成物が提案されている（特許文献６参照）。 On the other hand, since radically polymerizable compounds are excellent in curability by methods other than heating, they are generally recognized as having characteristics from the viewpoint of productivity and energy saving. The active energy ray-curable resin composition having a radically polymerizable compound, in view of such features, is an active ingredient such as various coatings such as paints for metals, overcoats for various plastic films, paints for woodworking, printing inks, etc. It is used as. For example, an energy ray-curable aqueous resin composition in which a (meth) acrylate compound is dispersed in an aqueous polyurethane resin dispersion has been proposed (see Patent Document 6).
　また、（メタ）アクリル化ポリウレタンと、（メタ）アクリル化合物を水系媒体中に分散してなるエネルギー線硬化型水系樹脂組成物も提案されている（特許文献７参照）。 In addition, an energy ray-curable aqueous resin composition in which a (meth) acrylated polyurethane and a (meth) acrylic compound are dispersed in an aqueous medium has also been proposed (see Patent Document 7).
特開平１０－１２０７５７号公報Unexamined-Japanese-Patent No. 10-120757 特開２００５－２８１５４４号公報JP 2005-281544 A 特開平６－２４８０４６号公報Japanese Patent Application Laid-Open No. 6-248046 ＷＯ２００９／１４５２４２公報WO2009 / 145242 ＷＯ２０１０／００４９５１公報WO 2010/004951 特開２００８－２４８０１４号公報JP 2008-248014 A 特表２００９－５３３５０４号公報Japanese Patent Publication No. 2009-533504
　しかしながら、ポリカーボネートポリオールを原料とした水性ポリウレタン樹脂分散体において、ポリカーボネートポリオールとして脂肪族ポリカーボネートポリオールのみを用いると、水性ポリウレタン樹脂分散体を塗布して得られる塗膜の密着性、硬度は、例えば航空機・自動車等の外板、住宅の外壁面及び床材等の塗料分野やコーティング剤の分野において充分ではないという問題があった。一方、脂環構造を有するポリカーボネートポリオールを用いると、水系媒体中への分散性が悪くなり、水性ポリウレタン樹脂分散体の取り扱い性及び安定性に問題が出てくるという問題があり、また、密着性、硬度についても満足いくものが得られることは確認されていない。 However, in the aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material, when only aliphatic polycarbonate polyol is used as the polycarbonate polyol, the adhesion and hardness of the coating film obtained by applying the aqueous polyurethane resin dispersion are, for example, aircraft, There has been a problem that it is not sufficient in the fields of paints such as outer panels of automobiles and the like, outer wall surfaces of houses and floorings such as floorings, and coatings. On the other hand, when a polycarbonate polyol having an alicyclic structure is used, there is a problem that the dispersibility in the aqueous medium is deteriorated, and problems occur in the handling property and stability of the aqueous polyurethane resin dispersion. It has not been confirmed that satisfactory results can be obtained for hardness.
　一方、エネルギー線硬化型水系樹脂組成物については、前記で指摘した特許文献６においては、界面活性剤を用いて（メタ）アクリレート系化合物を水性ポリウレタン樹脂分散体に対し分散させており、界面活性剤が塗膜中に残存することで、塗膜性能を低下させるという問題点があった。この組成物において、界面活性剤の使用量を少なくするか、あるいは使用しないこととすると、貯蔵安定性が低下するという問題が発生する。
　また、特許文献７においては、具体的に開示される（メタ）アクリル化ポリウレタンポリオールと（メタ）アクリル化合物との組み合わせでは、エネルギー線硬化型水系樹脂組成物から得られる塗膜は、各種プラスチック（特にＡＢＳ樹脂、アクリル樹脂）に対する密着性が十分ではないという問題点があった。 On the other hand, in the energy beam-curable water-based resin composition, in Patent Document 6 pointed out above, the (meth) acrylate compound is dispersed in the water-based polyurethane resin dispersion using a surfactant, and the surface activity is There is a problem in that the coating film performance is lowered by the agent remaining in the coating film. In this composition, if the amount of surfactant used is reduced or not used, there arises a problem that the storage stability is lowered.
Further, in Patent Document 7, in the combination of a (meth) acrylated polyurethane polyol and a (meth) acrylic compound specifically disclosed, the coating film obtained from the energy ray-curable water-based resin composition comprises various plastics ( In particular, there is a problem that the adhesion to ABS resin and acrylic resin) is not sufficient.
　本発明は、活性エネルギー線（例えば、紫外線）硬化型の水性ポリウレタン樹脂分散体であって、良好な水系媒体中への分散性及び貯蔵安定性を有し、かつ活性エネルギー線（例えば、紫外線）硬化後の塗膜の各種プラスチック（ＡＢＳ樹脂、アクリル樹脂、ポリカーボネート樹脂等）への密着性に優れる水性ポリウレタン樹脂分散体を得ることを課題とする。また、本発明は、活性エネルギー線（例えば、紫外線）硬化後の塗膜が高い硬度を有する水性ポリウレタン樹脂分散体を得ることを課題とする。 The present invention is an active energy ray (for example, ultraviolet light) -curable aqueous polyurethane resin dispersion, which has good dispersibility in an aqueous medium and storage stability, and an active energy ray (for example, ultraviolet light) It is an object of the present invention to obtain an aqueous polyurethane resin dispersion which is excellent in adhesion to various plastics (ABS resin, acrylic resin, polycarbonate resin and the like) of a coating film after curing. Moreover, this invention makes it a subject to obtain the aqueous | water-based polyurethane resin dispersion to which the coating film after active energy ray (for example, ultraviolet-ray) hardening has high hardness.
　本発明者らは、前記の従来技術の問題点を克服すべく種々の検討を行った結果、重合性不飽和結合を有するポリウレタン樹脂と重合性不飽和結合を有する化合物を水系媒体中に分散してなる水性ポリウレタン樹脂分散体であって、ポリウレタン樹脂の原料として脂環構造を有するポリカーボネートポリオールを用いたものによって、問題点が解決できることを見出した。 As a result of various investigations to overcome the problems of the prior art described above, the present inventors disperse a polyurethane resin having a polymerizable unsaturated bond and a compound having a polymerizable unsaturated bond in an aqueous medium. It has been found that the problems can be solved by an aqueous polyurethane resin dispersion which is obtained by using a polycarbonate polyol having an alicyclic structure as a raw material of the polyurethane resin.
　本発明（１）は、少なくとも、重合性不飽和結合を有するポリウレタン樹脂（Ａ）と重合性不飽和結合を有する化合物（Ｂ）を水系媒体中に分散してなる水性ポリウレタン樹脂分散体であって、
　重合性不飽和結合を有するポリウレタン樹脂（Ａ）が、少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）とを反応させて得られるポリウレタン樹脂であることを特徴とする、水性ポリウレタン樹脂分散体に関する。
　本発明（２）は、重合性不飽和結合を有する化合物（Ｂ）が、少なくとも３個の（メタ）アクリロイル基を有する化合物を含む、本発明（１）の水性ポリウレタン樹脂分散体に関する。
　本発明（３）は、重合性不飽和結合を有する化合物（Ｂ）が、少なくとも５個の（メタ）アクリロイル基を有する化合物を含む、本発明（１）又は（２）の水性ポリウレタン樹脂分散体に関する。
　本発明（４）は、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）が、１個のイソシアナト基と反応し得る基と１個以上の（メタ）アクリロイル基を有する化合物を含む、本発明（１）～（３）のいずれかの水性ポリウレタン樹脂分散体に関する。
　本発明（５）は、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）が、１個のイソシアナト基と反応し得る基と３個以上の（メタ）アクリロイル基を有する化合物を含む、本発明（１）～（４）のいずれかの水性ポリウレタン樹脂分散体に関する。
　本発明（６）は、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）が、２個の水酸基と２個の（メタ）アクリロイル基を有する化合物を含む、本発明（１）～（５）のいずれかの水性ポリウレタン樹脂分散体に関する。
　本発明（７）は、重合性不飽和結合を有するポリウレタン樹脂が、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）と、鎖延長剤（Ｃ）とを反応させて得られる、本発明（１）～（６）のいずれかの水性ポリウレタン樹脂分散体に関する。
　本発明（８）は、鎖延長剤（Ｃ）が、１級ポリアミン化合物である、本発明（７）の水性ポリウレタン樹脂分散体に関する。
　本発明（９）は、少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）とを反応させてポリウレタン樹脂（Ａ）を得て、
　ポリウレタン樹脂（Ａ）及び重合性不飽和結合を有する化合物（Ｂ）を水系媒体に分散させることを含む、本発明（１）～（６）のいずれかの水性ポリウレタン樹脂分散体の製造方法に関する。
　本発明（１０）は、少なくとも、主鎖に脂環構造を有するポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）とを反応させてポリウレタンプレポリマー（Ａ１）を得る工程（α１）と、
　ポリウレタンプレポリマー（Ａ１）の酸性基を中和する工程（β）と、
　ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）と、
　ポリウレタンプレポリマー（Ａ１）と、ポリウレタンプレポリマー（Ａ１）のイソシアナト基と反応性を有する鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂を得る工程（δ）とを含む、本発明（７）又は（８）の水性ポリウレタン樹脂分散体の製造方法に関する。
　本発明（１１）は、さらに光重合開始剤を含有する、本発明（１）～（８）のいずれかの水性ポリウレタン樹脂分散体に関する。
　本発明（１２）は、本発明（１）～（８）及び（１１）のいずれかの水性ポリウレタン樹脂分散体を含有する塗料組成物に関する。
　本発明（１３）は、本発明（１）～（８）及び（１１）のいずれかの水性ポリウレタン樹脂分散体を含有するコーティング剤組成物に関する。 The present invention (1) is an aqueous polyurethane resin dispersion obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium. ,
The polyurethane resin (A) having a polymerizable unsaturated bond has at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one molecule. An aqueous polyurethane resin dispersion characterized in that it is a polyurethane resin obtained by reacting a compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in It relates to the body.
The present invention (2) relates to the aqueous polyurethane resin dispersion of the present invention (1), wherein the compound (B) having a polymerizable unsaturated bond contains a compound having at least three (meth) acryloyl groups.
In the invention (3), the aqueous polyurethane resin dispersion of the invention (1) or (2), wherein the compound (B) having a polymerizable unsaturated bond contains a compound having at least 5 (meth) acryloyl groups. About.
In the present invention (4), the compound (e) having a group capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule can react with one isocyanato group The aqueous polyurethane resin dispersion according to any one of the inventions (1) to (3), which comprises a compound having a group and one or more (meth) acryloyl groups.
In the present invention (5), the compound (e) having a group capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule can react with one isocyanato group The aqueous polyurethane resin dispersion according to any one of the inventions (1) to (4), comprising a compound having a group and three or more (meth) acryloyl groups.
In the present invention (6), a compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule comprises two hydroxyl groups and two (two) The present invention relates to the aqueous polyurethane resin dispersion of any of the present inventions (1) to (5), which comprises a compound having an acryloyl group.
According to the invention (7), a polyurethane resin having a polymerizable unsaturated bond comprises a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), and a polyisocyanate (d); The invention is obtained by reacting a compound (e) having a group capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bond in the molecule with a chain extender (C) ( The present invention relates to the aqueous polyurethane resin dispersion of any one of 1) to (6).
The invention (8) relates to the aqueous polyurethane resin dispersion of the invention (7), wherein the chain extender (C) is a primary polyamine compound.
The present invention (9) comprises at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one or more isocyanato groups in one molecule. The compound (e) having a group capable of reacting with the compound and one or more polymerizable unsaturated bonds is reacted to obtain a polyurethane resin (A),
The method for producing an aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (6), which comprises dispersing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium.
The present invention (10) can react with at least a polycarbonate polyol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one or more isocyanato groups. A step (α1) of reacting a group with a compound (e) having one or more polymerizable unsaturated bonds to obtain a polyurethane prepolymer (A1);
Neutralizing the acid group of the polyurethane prepolymer (A1) (β);
Dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium (γ);
The present invention (7) comprising the step (δ) of reacting the polyurethane prepolymer (A1) with a chain extender (C) having reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin ) Or the method for producing an aqueous polyurethane resin dispersion of (8).
The present invention (11) relates to the aqueous polyurethane resin dispersion of any of the present inventions (1) to (8), which further contains a photopolymerization initiator.
The present invention (12) relates to a paint composition containing the aqueous polyurethane resin dispersion of any of the present inventions (1) to (8) and (11).
The present invention (13) relates to a coating agent composition containing the aqueous polyurethane resin dispersion of any of the present inventions (1) to (8) and (11).
　本発明によれば、良好な水系媒体中への分散性及び貯蔵安定性を有し、かつ活性エネルギー線（例えば、紫外線）硬化後の塗膜の各種プラスチック（ＡＢＳ樹脂、アクリル樹脂、ポリカーボネート樹脂等）への密着性に優れる水性ポリウレタン樹脂分散体及びその製造方法が提供される。また、本発明によれば、高い硬度を有する塗膜を与える水性ポリウレタン樹脂分散体及びその製造方法が提供される。本発明の水性ポリウレタン樹脂分散体は、航空機・自動車等の外板、自動車の内装材、携帯電話筐体、家電製品筐体、パーソナルコンピュータ筐体、加飾フィルム、光学フィルム、フローリング等の床材、外壁等の合成樹脂成形体の塗料（プライマーを含む）、インキ、接着剤、コーティング剤、塗料組成物等の原料とすることができ、幅広い用途に使用することができる。 According to the present invention, various plastics (ABS resin, acrylic resin, polycarbonate resin, etc.) have good dispersibility and storage stability in an aqueous medium, and have cured active energy ray (for example, ultraviolet light). The aqueous polyurethane resin dispersion which is excellent in the adhesion nature to a.), And its manufacturing method are provided. Further, according to the present invention, an aqueous polyurethane resin dispersion which provides a coating film having high hardness and a method for producing the same are provided. The aqueous polyurethane resin dispersion of the present invention includes outer plates of aircrafts, automobiles, etc., interior materials of automobiles, cellular phone casings, home electric appliance casings, personal computer casings, flooring materials such as decorative films, optical films, floorings, etc. It can be used as a raw material for paints (including primers) of synthetic resin molded articles such as outer walls, inks, adhesives, coatings, paint compositions and the like, and can be used in a wide range of applications.
　本発明は、少なくとも、重合性不飽和結合を有するポリウレタン樹脂（Ａ）と重合性不飽和結合を有する化合物（Ｂ）を水系媒体中に分散してなる水性ポリウレタン樹脂分散体であって、
　重合性不飽和結合を有するポリウレタン樹脂（Ａ）が、少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）を反応させて得られるものである、水性ポリウレタン樹脂分散体に関する。 The present invention is an aqueous polyurethane resin dispersion obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium,
The polyurethane resin (A) having a polymerizable unsaturated bond comprises at least one polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), and a polyisocyanate (d) The present invention relates to an aqueous polyurethane resin dispersion obtained by reacting a group capable of reacting with an isocyanato group and a compound (e) having one or more polymerizable unsaturated bonds.
<重合性不飽和結合を有するポリウレタン樹脂（Ａ）>
　本発明において、重合性不飽和結合を有するポリウレタン樹脂（Ａ）は、少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）を反応させて得られるものである。 <Polyurethane resin having a polymerizable unsaturated bond (A)>
In the present invention, the polyurethane resin (A) having a polymerizable unsaturated bond is at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), and a polyisocyanate (d) It is obtained by reacting a group capable of reacting with one or more isocyanato groups with a compound (e) having one or more polymerizable unsaturated bonds.
Ｉ．主鎖に脂環構造を有するポリカーボネートポリオール（ａ）
　本発明で使用するポリカーボネートポリオールは、水性ポリウレタン樹脂分散体の貯蔵安定性に優れ、密着性に優れる塗膜が得られる点から、主鎖に脂環構造を有するポリカーボネートポリオール（ａ）（以下、「ポリカーボネートポリオール（ａ）」ということがある）である。 I. Polycarbonate polyol having alicyclic structure in main chain (a)
The polycarbonate polyol used in the present invention is a polycarbonate polyol (a) having an alicyclic structure in its main chain from the viewpoint that a coating film excellent in storage stability of the aqueous polyurethane resin dispersion and excellent in adhesiveness is obtained Polycarbonate polyol (a))).
　ポリカーボネートポリオール（ａ）は、特に限定されず、例えば、主鎖に脂環構造を有するポリオールと炭酸エステルとを反応させて得られるポリカーボネートポリオールや、主鎖に脂環構造を有するポリオールと他のポリオールと炭酸エステルとを反応させて得られる共重合ポリカーボネートポリオール等が挙げられる。本明細書において、脂環構造には、環内に酸素原子や窒素原子等のヘテロ原子を有するものも含む。 The polycarbonate polyol (a) is not particularly limited, and, for example, a polycarbonate polyol obtained by reacting a polyol having an alicyclic structure in the main chain and a carbonate ester, a polyol having an alicyclic structure in the main chain, and other polyols Copolymerized polycarbonate polyol etc. which are obtained by making and carbonic acid ester react, etc. are mentioned. In the present specification, the alicyclic structure also includes one having a hetero atom such as an oxygen atom or a nitrogen atom in the ring.
　ポリカーボネートポリオール（ａ）の好ましい数平均分子量は、４００～３０００である。数平均分子量がこの範囲であると、適切な粘度及び良好な取り扱い性が容易に得られる。また、ソフトセグメントとしての性能の確保が容易であり、得られた水性ポリウレタン樹脂分散体を用いて塗膜を形成した場合に割れの発生を抑制し易く、さらにポリイソシアネート（ｄ）との反応性が充分で、ウレタンプレポリマーの製造を効率的に行うことができる。ポリカーボネートポリオール（ａ）は、数平均分子量が４００～１５００であることがより好ましく、５００～１３００であることが特に好ましい。 The preferred number average molecular weight of the polycarbonate polyol (a) is 400 to 3,000. When the number average molecular weight is in this range, an appropriate viscosity and good handleability can be easily obtained. In addition, it is easy to ensure the performance as a soft segment, and when a coating film is formed using the obtained aqueous polyurethane resin dispersion, it is easy to suppress the occurrence of cracking, and furthermore, the reactivity with the polyisocyanate (d) Is sufficient, and the urethane prepolymer can be produced efficiently. The number average molecular weight of the polycarbonate polyol (a) is more preferably 400 to 1,500, and particularly preferably 500 to 1300.
　本発明において、数平均分子量は、ＪＩＳ　Ｋ　１５５７に準拠して測定した水酸基価に基づいて算出した数平均分子量とする。具体的には、水酸基価を測定し、末端基定量法により、（５６．１×１０００×価数）／水酸基価　［ｍｇＫＯＨ／ｇ］で算出する。前記式中において、価数は１分子中の水酸基の数であり、ポリカーボネートポリオールがポリカーボネートジオールの場合は価数が２となる。 In the present invention, the number average molecular weight is a number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K 1557. Specifically, the hydroxyl value is measured, and it is calculated by (56.1 × 1000 × number of valence) / hydroxyl value [mg KOH / g] by an end group determination method. In the above formula, the valence is the number of hydroxyl groups in one molecule, and when the polycarbonate polyol is a polycarbonate diol, the valence is two.
　主鎖に脂環構造を有するポリオールは、特に制限されず、例えば、１，４－シクロヘキサンジメタノール、１,３－シクロヘキサンジメタノール、１,４－シクロヘキサンジオール、１，３－シクロペンタンジオール、１，４－シクロヘプタンジオール、２，５‐ビス（ヒドロキシメチル）－１，４－ジオキサン、２，７－ノルボルナンジオール、テトラヒドロフランジメタノール、１，４‐ビス（ヒドロキシエトキシ）シクロヘキサン、トリシクロ［５．２．１．０２，６］デカンジメタノールに代表されるトリシクロデカンジメタノール、ダイマー酸ダイオールの各構造異性体又はその混合物等の主鎖に脂環構造を有するジオールなどが挙げられる。中でも入手の容易さから１，４－シクロヘキサンジメタノールが好ましい。 The polyol having an alicyclic structure in the main chain is not particularly limited. For example, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1 , 4-Cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, tricyclo [5.2 1.0 2,6 ! Dichlorodimethanol represented by decanedimethanol, each structural isomer of dimer acid diol or a mixture thereof and the like, diol having alicyclic structure in the main chain, and the like can be mentioned. Among these, 1,4-cyclohexanedimethanol is preferable because of easy availability.
　他のポリオールを併用する場合、前記他のポリオールは、特に制限されず、例えば、脂肪族ポリオール、芳香族ポリオール、ポリエステルポリオール、ポリエーテルポリオール等が挙げられる。 When other polyols are used in combination, the other polyols are not particularly limited, and examples thereof include aliphatic polyols, aromatic polyols, polyester polyols, polyether polyols and the like.
　脂肪族ポリオールは、特に制限されず、例えば、炭素数２～１２の脂肪族ポリオール等が挙げられる。具体的には、１，２－エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール等の直鎖状脂肪族ジオール；２－メチル－１，３－プロパンジオール、２－メチル－１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、２－メチル－１，９－ノナンジオール等の分岐鎖状脂肪族ジオール；１，１，１－トリメチロールプロパン、ペンタエリスリトール等の３官能以上の多価アルコール等が挙げられる。 The aliphatic polyol is not particularly limited, and examples thereof include aliphatic polyols having 2 to 12 carbon atoms. Specifically, 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Linear aliphatic diols such as -octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentane Examples thereof include branched aliphatic diols such as diol and 2-methyl-1,9-nonanediol; and polyhydric alcohols having three or more functional groups such as 1,1,1-trimethylolpropane and pentaerythritol.
　芳香族ポリオールは、特に制限されず、例えば、１，４－ベンゼンジメタノール、１，３－ベンゼンジメタノール、１，２－ベンゼンジメタノール、４，４’－ナフタレンジメタノール、３，４’－ナフタレンジメタノール等が挙げられる。 The aromatic polyol is not particularly limited and, for example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol, 3,4'- Naphthalene dimethanol etc. are mentioned.
　ポリエステルポリオールは、特に制限されず、例えば、６－ヒドロキシカプロン酸とヘキサンジオールとのポリエステルポリオール等のヒドロキシカルボン酸とジオールとのポリエステルポリオール、アジピン酸とヘキサンジオールとのポリエステルポリオール等のジカルボン酸とジオールとのポリエステルポリオール等が挙げられる。 The polyester polyol is not particularly limited. For example, polyester polyol of hydroxycarboxylic acid and diol such as polyester polyol of 6-hydroxycaproic acid and hexanediol, and dicarboxylic acid such as polyester polyol of adipic acid and hexanediol and diol And polyester polyols and the like.
　ポリエーテルポリオールは、特に制限されず、例えば、ポリエチレングリコール（例えば、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等）やポリプロピレングリコールやポリテトラメチレングリコール等のポリアルキレングリコール等が挙げられる。 The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol (for example, diethylene glycol, triethylene glycol, tetraethylene glycol and the like), and polyalkylene glycols such as polypropylene glycol and polytetramethylene glycol.
　炭酸エステルは、特に制限されず、例えば、ジメチルカーボネート、ジエチルカーボネート等の脂肪族炭酸エステル、ジフェニルカーボネート等の芳香族炭酸エステル、エチレンカーボネート等の環状炭酸エステル等が挙げられる。その他に、ポリカーボネートポリオールを生成することができるホスゲン等も使用できる。中でも、ポリカーボネートポリオールの製造のし易さから、脂肪族炭酸エステルが好ましく、ジメチルカーボネートが特に好ましい。 The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, cyclic carbonates such as ethylene carbonate, and the like. In addition, phosgene etc. which can produce polycarbonate polyol can also be used. Among them, aliphatic carbonates are preferable, and dimethyl carbonate is particularly preferable, in terms of easiness of production of polycarbonate polyol.
　ポリオール及び炭酸エステルからポリカーボネートポリオールを製造する方法としては、例えば、反応器中に炭酸エステルと、この炭酸エステルのモル数に対して過剰のモル数のポリオールとを加え、温度１６０～２００℃、圧力５０ｍｍＨｇ程度で５～６時間反応させた後、さらに数ｍｍＨｇ以下の圧力において２００～２２０℃で数時間反応させる方法が挙げられる。前記反応においては副生するアルコールを系外に抜き出しながら反応させることが好ましい。その際、炭酸エステルが副生するアルコールと共沸することにより系外へ抜け出る場合には、過剰量の炭酸エステルを加えてもよい。また、前記反応において、チタニウムテトラブトキシド等の触媒を使用してもよい。 As a method for producing a polycarbonate polyol from a polyol and a carbonate ester, for example, a carbonate ester and an excess number of polyols relative to the number of moles of the carbonate ester are added to a reactor, and the temperature 160 to 200 ° C., pressure The reaction may be carried out at about 50 mmHg for 5 to 6 hours, and then at 200 to 220 ° C. for several hours at a pressure of several mmHg or less. It is preferable to make it react, extracting the byproduct alcohol out of the system in the said reaction. At that time, when the carbonate ester is azeotropically formed with the by-produced alcohol and thus comes out of the system, an excess amount of the carbonate ester may be added. In the reaction, a catalyst such as titanium tetrabutoxide may be used.
　ポリカーボネートポリオール（ａ）における脂環構造含有率は、２０～６５重量％であることが好ましい。脂環構造含有率がこの範囲であれば、脂環構造の存在により、硬度に優れた塗膜が得られ易く、塗膜の各種プラスチックへの密着性も充分である。その一方で、脂環構造の含有率が大きくなりすぎて、水性ポリウレタン樹脂分散体製造時のプレポリマーの粘度が高くなり取り扱いが困難となるといった事態を回避しやすく、良好な貯蔵安定性を容易に得られる。脂環構造含有率は、３０～５５重量％であることがより好ましい。 The alicyclic structure content in the polycarbonate polyol (a) is preferably 20 to 65% by weight. If the alicyclic structure content is in this range, a coating film excellent in hardness is easily obtained due to the presence of the alicyclic structure, and the adhesion of the coating film to various plastics is also sufficient. On the other hand, it is easy to avoid a situation where the content of the alicyclic structure becomes too high and the viscosity of the prepolymer becomes high at the time of production of the aqueous polyurethane resin dispersion and handling becomes difficult, and good storage stability is easy Obtained. The alicyclic structure content is more preferably 30 to 55% by weight.
　ここで、脂環構造含有率は、ポリカーボネートポリオール（ａ）に占める、脂環式基の重量割合をいうこととする。例えば、シクロヘキサン残基等のシクロアルカン残基（１，４－ヘキサンジメタノールの場合は、シクロヘキサンから２個の水素原子を除いた部分）や、テトラヒドロフラン残基等の不飽和へテロ環残基（テトラヒドロフランジメタノールの場合は、テトラヒドロフランから２個の水素原子を除いた部分）に基づき、算出した値をいう。 Here, the alicyclic structure content refers to the weight ratio of the alicyclic group in the polycarbonate polyol (a). For example, a cycloalkane residue such as a cyclohexane residue (in the case of 1,4-hexanedimethanol, a portion obtained by removing two hydrogen atoms from cyclohexane), or an unsaturated heterocyclic residue such as a tetrahydrofuran residue In the case of tetrahydrofuran dimethanol, the value calculated based on the part which remove | eliminated two hydrogen atoms from tetrahydrofuran is said.
　水系媒体の分散性の観点から、ポリカーボネートポリオール（ａ）は、他のポリオールを併用した共重合ポリカーボネートポリオールが好ましい。他のポリオールとしては、脂肪族ポリオール、芳香族ポリオール、ポリエステルポリオール、ポリエーテルポリオールを使用することができ、前記の具体例が適用される。中でも、主鎖に脂環構造を有するポリオールと脂肪族ポリオールの組み合わせが好ましく、特に、１，４－シクロへキサンジメタノールと１，６－ヘキサンジオールを併用して得られる共重合ポリカーボネートポリオールが好ましい。 From the viewpoint of the dispersibility of the aqueous medium, the polycarbonate polyol (a) is preferably a copolycarbonate polyol in which another polyol is used in combination. As other polyols, aliphatic polyols, aromatic polyols, polyester polyols, polyether polyols can be used, and the above-mentioned specific examples apply. Among them, a combination of a polyol having an alicyclic structure in the main chain and an aliphatic polyol is preferable, and in particular, a copolymerized polycarbonate polyol obtained by using 1,4-cyclohexanedimethanol and 1,6-hexanediol in combination is preferable. .
　ポリカーボネートポリオール（ａ）は、単独で用いてもよいし、複数種を併用してもよい。 The polycarbonate polyol (a) may be used alone or in combination of two or more.
II．酸性基含有ポリオール（ｂ）
　本発明で使用する酸性基含有ポリオール（ｂ）は、１分子中に２個以上の水酸基と、１個以上の酸性基を含有するものであれば、特に制限はない。酸性基としては、カルボキシ基、スルホン酸基、リン酸基、フェノール性水酸基等が挙げられる。特に酸性基含有ポリオール（ｂ）として、１分子中に２個の水酸基と１個のカルボキシ基を有する化合物を含有するものが好ましい。酸性基含有ポリオール（ｂ）は、単独で用いてもよいし、複数種を併用してもよい。 II. Acid group containing polyol (b)
The acidic group-containing polyol (b) used in the present invention is not particularly limited as long as it contains two or more hydroxyl groups and one or more acidic groups in one molecule. As an acidic group, a carboxy group, a sulfonic acid group, a phosphoric acid group, phenolic hydroxyl group etc. are mentioned. In particular, as the acidic group-containing polyol (b), one containing a compound having two hydroxyl groups and one carboxy group in one molecule is preferable. The acidic group-containing polyol (b) may be used alone or in combination of two or more.
　酸性基含有ポリオール（ｂ）としては、具体的には、２，２－ジメチロールプロピオン酸、２，２－ジメチロールブタン酸等のジメチロールアルカン酸をはじめとするジアルカノールアルカン酸；Ｎ，Ｎ－ビスヒドロキシエチルグリシン、Ｎ，Ｎ－ビスヒドロキシエチルアラニン、３，４－ジヒドロキシブタンスルホン酸、３，６－ジヒドロキシ－２－トルエンスルホン酸、酸性基含有ポリエーテルポリオール、酸性基含有ポリエステルポリオール等が挙げられる。中でも入手の容易さの観点から、２個のアルカノール基を含むジアルカノールアルカン酸が好ましく、２個のメチロール基を含む炭素数４～１２のアルカン酸（ジメチロールアルカン酸）がより好ましく、ジメチロールアルカン酸の中でも、２，２－ジメチロールプロピオン酸が特に好ましい。 Specific examples of the acidic group-containing polyol (b) include dialkanolalkanoic acids such as dimethylolalkanoic acid such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid; N, N -Bishydroxyethyl glycine, N, N-bishydroxyethyl alanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acid group-containing polyether polyol, acid group-containing polyester polyol, etc. It can be mentioned. Among them, a dialkanolalkanoic acid containing two alkanol groups is preferable, an alkanoic acid having 4 to 12 carbon atoms containing two methylol groups (dimethylolalkanoic acid) containing two alkanol groups is more preferable, and dimethylolol is more preferable. Among the alkanoic acids, 2,2-dimethylol propionic acid is particularly preferred.
III．その他のポリオール（ｃ）
　ポリカーボネートポリオール（ａ）及び酸性基含有ポリオール（ｂ）以外に、その他のポリオール（ｃ）（以下、「その他のポリオール（ｃ）」ということがある。）を用いることができる。その他のポリオール（ｃ）としては、ポリマーポリオール等の高分子ポリオールや低分子ポリオールが挙げられる。高分子ポリオールとしては、数平均分子量が４００～６０００のものが挙げられる。ポリオールは、ジオールであっても、３価以上の多価アルコールであってもよい。その他のポリオールは、単独で用いてもよいし、複数種を併用してもよい。塗膜の硬度が高くなるという点から、低分子ポリオールが好ましく、中でも低分子ジオールが好ましい。 III. Other polyols (c)
Besides the polycarbonate polyol (a) and the acidic group-containing polyol (b), other polyols (c) (hereinafter sometimes referred to as "other polyols (c)") can be used. Other polyols (c) include high molecular weight polyols such as polymer polyols and low molecular weight polyols. Examples of the high molecular weight polyol include those having a number average molecular weight of 400 to 6,000. The polyol may be a diol or a trivalent or higher polyhydric alcohol. Other polyols may be used alone or in combination of two or more. Low molecular weight polyols are preferred, and low molecular weight diols are particularly preferred, from the viewpoint that the hardness of the coating film is increased.
　高分子ポリマーポリオールは、特に制限されず、ポリエステルポリオール、ポリエーテルポリオール、アクリルポリオール、ポリジエンポリオール、主鎖に脂環構造を有しないポリカーボネートポリオールを好適に用いることができる。 The polymer polymer polyol is not particularly limited, and polyester polyol, polyether polyol, acrylic polyol, polydiene polyol, and polycarbonate polyol having no alicyclic structure in the main chain can be suitably used.
　ポリエステルポリオールは、特に制限されず、例えば、ポリエチレンアジペートポリオール、ポリブチレンアジペートポリオール、ポリエチレンブチレンアジペートポリオール、ポリへキサメチレンイソフタレートアジペートポリオール、ポリエチレンサクシネートポリオール、ポリブチレンサクシネートポリオール、ポリエチレンセバケートポリオール、ポリブチレンセバケートポリオール、ポリ－ε－カプロラクトンポリオール、ポリ（３－メチル－１，５－ペンチレンアジペート）ポリオール、１，６－ヘキサンジオールとダイマー酸の重縮合物等を挙げることができる。 The polyester polyol is not particularly limited. For example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene sebacate polyol, Examples thereof include polybutylene sebacate polyol, poly-ε-caprolactone polyol, poly (3-methyl-1,5-pentylene adipate) polyol, and polycondensate of 1,6-hexanediol and dimer acid.
　ポリエーテルポリオールは、特に制限されず、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、エチレンオキシドとプロピレンオキシド、エチレンオキシドとブチレンオキシドとのランダム共重合体やブロック共重合体等を挙げることができる。さらに、エーテル結合とエステル結合とを有するポリエーテルポリエステルポリオール等を用いることもできる。 The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, random copolymer and block copolymer of ethylene oxide and butylene oxide, and the like. Furthermore, polyether polyester polyols having an ether bond and an ester bond can also be used.
　ポリジエンポリオールは、特に制限されず、ブタジエン、イソプレン、１，３－ペンタジエン、クロロプレン、シクロペンタジエン等から誘導される単位を含むポリジエンポリオール等を挙げることができる。ポリジエンポリオールの具体的例としては、例えば、水酸基末端液状ポリブタジエン（出光興産社製「Ｐｏｌｙ　ｂｄ」）や二官能性水酸基末端液状ポリブタジエン（出光興産社製「ＫＲＡＳＯＬ」）、水酸基末端液状ポリイソプレン（出光興産社製「Ｐｏｌｙ　ｉｐ」）、水酸基末端液状ポリオレフィン（出光興産社製「エポール」）等が挙げられる。 The polydiene polyol is not particularly limited, and examples thereof include polydiene polyols containing units derived from butadiene, isoprene, 1,3-pentadiene, chloroprene, cyclopentadiene and the like. Specific examples of the polydiene polyol include, for example, hydroxyl terminated liquid polybutadiene ("Poly bd" manufactured by Idemitsu Kosan Co., Ltd.), difunctional hydroxyl terminated liquid polybutadiene ("KRASOL" manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl terminated liquid polyisoprene ( Idemitsu Kosan Co., Ltd. "Poly ip"), a hydroxyl group terminal liquid polyolefin (Idemitsu Kosan Co., Ltd. "EPOL"), etc. are mentioned.
　ポリアクリルポリオールは、特に制限されず、例えば、アクリル酸－２－ヒドロキシエチル、アクリル酸－２－ヒドロキシプロピル、アクリル酸－２－ヒドロキシブチル等の活性水素を持つアクリル酸エステル、又はグリセリンのアクリル酸モノエステルあるいはメタクリル酸モノエステル、トリメチロールプロパンのアクリル酸モノエステルあるいはメタクリル酸モノエステルの群から選ばれた単独又は混合物とアクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸－ｎ－ブチル、アクリル酸－２－エチルヘキシル等のアクリル酸エステル、メタクリル酸－２－ヒドロキシエチル、メタクリル酸－２－ヒドロキシプロピル、メタクリル酸－２－ヒドロキシブチル、メタクリル酸－３－ヒドロキシプロピル、メタクリル酸－４－ヒドロキシブチル等の活性水素を持つメタクリル酸エステル、又はメタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸－ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸－ｎ－ヘキシル、メタクリル酸ラウリル等のメタクリル酸エステルの群から選ばれた単独又は混合物を用い、アクリル酸、メタクリル酸、マレイン酸、イタコン酸等の不飽和カルボン酸、アクリルアミド、Ｎ－メチロールアクリルアミド、ジアセトンアクリルアミド等の不飽和アミド、及びメタクリル酸グリシジル、スチレン、ビニルトルエン、酢酸ビニル、アクリロニトリル、フマル酸ジブチル等のその他の重合性モノマーの群から選ばれた単独又は混合物の存在下、或いは非存在下において重合させて得られるポリアクリルポリオールが挙げられる。その重合方法としては、乳化重合、懸濁重合、分散重合、溶液重合等が挙げられる。乳化重合では段階的に重合することもできる。 The polyacrylic polyol is not particularly limited. For example, acrylic acid ester having active hydrogen such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, or acrylic acid of glycerin Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, alone or in a mixture selected from the group consisting of monoesters or methacrylic acid monoesters, acrylic monoesters of trimethylolpropane or methacrylic monoesters; Acrylic acid esters such as 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, methacrylate Methacrylate with an active hydrogen such as 4-hydroxybutyl lactate, or methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, methacrylic acid Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like, unsaturated carboxylic acids such as acrylamide, N-methylol acrylamide, diacetone acrylamide and the like using a single or a mixture selected from the group of methacrylic acid esters such as lauryl Obtained by polymerization in the presence or absence of an amide and a mixture selected from the group of other polymerizable monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate and the like Poly Acrylic polyols. Examples of the polymerization method include emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization and the like. In emulsion polymerization, polymerization can be carried out stepwise.
　主鎖に脂環構造を有しないポリカーボネートポリオールは、特に制限されず、例えば、ポリテトラメチレンカーボネートジオール、ポリペンタメチレンカーボネートジオール、ポリへキサメチレンカーボネートジオール等の脂肪族ポリカーボネートジオール；ポリ１，４－キシリレンカーボネートジオール等の芳香族ポリカーボネートジオール；複数種類の脂肪族ジオールと炭酸エステルとの反応生成物である共重合ポリカーボネートジオール；脂肪族ジオールと芳香族ジオールと炭酸エステルとの反応生成物である共重合ポリカーボネートジオール等の共重合ポリカーボネートジオール等を用いることができる。 The polycarbonate polyol having no alicyclic structure in the main chain is not particularly limited, and examples thereof include aliphatic polycarbonate diols such as polytetramethylene carbonate diol, polypentamethylene carbonate diol, and polyhexamethylene carbonate diol; Aromatic polycarbonate diol such as xylylene carbonate diol; Copolycarbonate diol which is a reaction product of a plurality of aliphatic diols and a carbonate ester; co-reaction product of an aliphatic diol, an aromatic diol and a carbonate ester Copolymerized polycarbonate diols such as polymerized polycarbonate diols can be used.
　共重合ポリカーボネートジオールとしては、例えば、１，３－プロパンジオールと１，４－ブタンジオールと炭酸エステルとの反応生成物である共重合ポリカーボネートジオール、１，４－ブタンジオールと１，５－ペンタンジオールと炭酸エステルとの反応生成物である共重合ポリカーボネートジオール、１，５－ペンタンジオールと１，６－ヘキサンジオールと炭酸エステルとの反応生成物である共重合ポリカーボネートジオール、１，４－ブタンジオールと１，６－ヘキサンジオールと炭酸エステルとの反応生成物である共重合ポリカーボネートジオール、１，３－プロパンジオールと１，６－ヘキサンジオールと炭酸エステルとの反応生成物である共重合ポリカーボネートジオール等が挙げられる。 As copolymerized polycarbonate diol, for example, copolymerized polycarbonate diol which is a reaction product of 1,3-propanediol, 1,4-butanediol and carbonate ester, 1,4-butanediol and 1,5-pentanediol Copolycarbonate diol which is a reaction product of esterification with carbonic acid ester, copolycarbonate diol which is a reaction product of 1,5-pentanediol, 1,6-hexanediol and carbonate ester, 1,4-butanediol, Copolymerized polycarbonate diol which is a reaction product of 1,6-hexanediol and carbonate ester, copolymerized polycarbonate diol which is a reaction product of 1,3-propanediol, 1,6-hexanediol and carbonate ester, etc. It can be mentioned.
　低分子ポリオールは、特に制限されず、数平均分子量が６０以上４００未満であるものが挙げられる。例えば、エチレングリコール、１，３－プロパンジオール、２－メチル－１，３－プロパンジオール、２，２－ジメチル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、１，９－ノナンジオール、２－メチル－１，８－オクタンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等の炭素数２～９の脂肪族ジオール；１，４－シクロヘキサンジメタノール、１，３－シクロヘキサンジメタノール、１，４－シクロヘキサンジオール、１，４－ビス（ヒドロキシエチル）シクロヘキサン、２，７－ノルボルナンジオール、テトラヒドロフランジメタノール、２，５－ビス（ヒドロキシメチル）－１，４－ジオキサン等の炭素数６～１２の脂環構造を有するジオール；１，４－ベンゼンジメタノール、１，３－ベンゼンジメタノール、１，４－ジヒドロキシベンゼン等の芳香族ジオール等を挙げることができる。また、低分子量ポリオールとして、トリメチロールプロパン、ペンタエリスリトール、ソルビトール等の三官能以上の低分子量多価アルコールを用いてもよい。 The low molecular weight polyol is not particularly limited, and includes those having a number average molecular weight of 60 or more and less than 400. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol , 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol Aliphatic diols having 2 to 9 carbon atoms such as diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (Hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydrofuran Diol having a C 6-12 alicyclic structure such as methanol, 2,5-bis (hydroxymethyl) -1,4-dioxane; 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,1 Aromatic diols such as 4-dihydroxybenzene and the like can be mentioned. Further, as the low molecular weight polyol, a trifunctional or higher functional low molecular weight polyhydric alcohol such as trimethylolpropane, pentaerythritol, or sorbitol may be used.
　ポリカーボネートポリオール（ａ）に対するその他のポリオール（ｃ）の割合は、４０重量％以下であることが好ましい。この範囲であれば、得られる塗膜の密着性が低下したり、水性ポリウレタン樹脂分散体の製造が困難になったりすることを回避し易い。その他のポリオール（ｃ）の割合は、より好ましくは、２０重量％以下である。 The proportion of the other polyol (c) to the polycarbonate polyol (a) is preferably 40% by weight or less. If it is this range, it will be easy to avoid that the adhesiveness of the obtained coating film falls or it becomes difficult to manufacture aqueous polyurethane resin dispersion. The proportion of the other polyol (c) is more preferably 20% by weight or less.
IV．ポリイソシアネート（ｄ）
　本発明で使用できるポリイソシアネート（ｄ）は、特に制限されず、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネート等が挙げられる。 IV. Polyisocyanate (d)
The polyisocyanate (d) which can be used in the present invention is not particularly limited, and aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be mentioned.
　芳香族ポリイソシアネートとしては、具体的には、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、２，４－トリレンジイソシアネート（ＴＤＩ）、２，６－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、２，４－ジフェニルメタンジイソシアネート、４，４’－ジイソシアナトビフェニル、３，３’－ジメチル－４，４’－ジイソシアナトビフェニル、３，３’－ジメチル－４，４’－ジイソシアナトジフェニルメタン、１，５－ナフチレンジイソシアネート、４，４’，４’’－トリフェニルメタントリイソシアネート、ｍ－イソシアナトフェニルスルホニルイソシアネート、ｐ－イソシアナトフェニルスルホニルイソシアネート等が挙げられる。 Specific examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'- Diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 Examples thereof include '-diisocyanatodiphenylmethane, 1,5-naphthyl diisocyanate, 4,4 ′, 4 ′ ′-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate and the like.
　脂肪族ポリイソシアネートとしては、具体的には、エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、ドデカメチレンジイソシアネート、１，６，１１－ウンデカントリイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２，６－ジイソシアナトメチルカプロエート、ビス（２－イソシアナトエチル）フマレート、ビス（２－イソシアナトエチル）カーボネート、２－イソシアナトエチル－２，６－ジイソシアナトヘキサノエート等が挙げられる。 Specific examples of aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecanetriisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexano And the like.
　脂環式ポリイソシアネートとしては、具体的には、イソホロンジイソシアネート（ＩＰＤＩ）、４，４’－ジシクロヘキシルメタンジイソシアネート（水素添加ＭＤＩ）、シクロヘキシレンジイソシアネート、メチルシクロヘキシレンジイソシアネート（水素添加ＴＤＩ）、ビス（２－イソシアナトエチル）－４－シクロヘキセン－１，２－ジカルボキシレート、２，５－ノルボルナンジイソシアネート、２，６－ノルボルナンジイソシアネート等が挙げられる。 Specific examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 And -isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.
　これらのポリイソシアネートは、単独で用いてもよいし、複数種を併用してもよい。 These polyisocyanates may be used alone or in combination of two or more.
　ポリイソシアネートの１分子当たりのイソシアナト基は通常２個であるが、本発明におけるポリウレタン樹脂がゲル化をしない範囲で、トリフェニルメタントリイソシアネートのようなイソシアナト基を３個以上有するポリイソシアネートも使用することができる。 The number of isocyanato groups per one molecule of polyisocyanate is generally two, but polyisocyanates having three or more isocyanato groups such as triphenylmethane triisocyanate are also used to the extent that the polyurethane resin in the present invention does not gel. be able to.
　ポリイソシアネートの中でも、反応性の制御、高い硬度、強度付与等の観点から、４，４’－ジフェニレンメタンジイソシアネート（ＭＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、４，４’－ジシクロヘキシルメタンジイソシアネート（水素添加ＭＤＩ）が好ましい。 Among polyisocyanates, from the viewpoint of control of reactivity, high hardness, imparting of strength, etc., 4,4'-diphenylenemethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenation MDI) is preferred.
Ｖ．１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）
　１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）（以下、「不飽和化合物（ｅ）」ということがある）における、重合性不飽和結合は、例えば、光重合開始剤により発生したラジカル等により重合し得る不飽和基に含まれる結合が挙げられる。このような不飽和基としては、公知のものでよく、エチレン性不飽和結合を含む基が挙げられ、入手容易な点及び反応性が高さから、（メタ）アクリロイル基が好ましい。本明細書において、（メタ）アクリロイル基とはアクリロイル基又は／及びメタクリロイル基であることを意味し、（メタ）アクリレートとはアクリレート又は／及びメタクリレートであることを意味し、（メタ）アクリル酸とは、アクリル酸又は／及びメタクリル酸であることを意味する。不飽和化合物（ｅ）は、重合性不飽和結合を、分子中に１個以上有する。 V. Compounds having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule (e)
Polymerization in a compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule (hereinafter sometimes referred to as "unsaturated compound (e)") The unsaturated bond includes, for example, a bond contained in an unsaturated group that can be polymerized by a radical or the like generated by a photopolymerization initiator. Such unsaturated groups may be known ones, and include groups containing an ethylenically unsaturated bond, and from the viewpoint of easy availability and high reactivity, (meth) acryloyl group is preferable. In the present specification, (meth) acryloyl group means acryloyl group and / or methacryloyl group, (meth) acrylate means acrylate or / and methacrylate, and (meth) acrylic acid and Means that it is acrylic acid or / and methacrylic acid. The unsaturated compound (e) has one or more polymerizable unsaturated bonds in the molecule.
　不飽和化合物（ｅ）におけるイソシアナト基と反応し得る基としては、例えば、水酸基、アミノ基、イソシアナト基、チオール基などが挙げられる。中でも、不飽和化合物（ｅ）の取り扱い易さの点から、水酸基が好ましい。不飽和化合物（ｅ）は、イソシアナト基と反応し得る基を、分子中に１個以上有する。 Examples of the group capable of reacting with the isocyanato group in the unsaturated compound (e) include a hydroxyl group, an amino group, an isocyanato group, a thiol group and the like. Among them, a hydroxyl group is preferable from the viewpoint of the handling ease of the unsaturated compound (e). The unsaturated compound (e) has one or more groups capable of reacting with the isocyanato group in the molecule.
　不飽和化合物（ｅ）としては、取り扱い易さの点から、１個以上の水酸基と１個以上の重合性不飽和結合を有する化合物（ｅ’）が好ましい。不飽和化合物（ｅ’）としては、例えば、１分子中に１個の水酸基と１個の重合性不飽和結合を有する不飽和化合物（ｅ’－１）、１分子中に１個の水酸基と２個以上の重合性不飽和基を有する不飽和化合物（ｅ’－２）、１分子中に２個以上の水酸基と１個の重合性不飽和基を有する不飽和化合物（ｅ’－３）、１分子中に２個以上の水酸基と２個以上の重合性不飽和基を有する不飽和化合物（ｅ’－４）等が挙げられる。 The unsaturated compound (e) is preferably a compound (e ′) having at least one hydroxyl group and at least one polymerizable unsaturated bond from the viewpoint of easy handling. As the unsaturated compound (e ′), for example, an unsaturated compound (e′-1) having one hydroxyl group and one polymerizable unsaturated bond in one molecule, and one hydroxyl group in one molecule Unsaturated compound (e'-2) having two or more polymerizable unsaturated groups, unsaturated compound (e'-3) having two or more hydroxyl groups and one polymerizable unsaturated group in one molecule And unsaturated compounds (e′-4) having two or more hydroxyl groups and two or more polymerizable unsaturated groups in one molecule.
　１分子中に１個の水酸基と１個の重合性不飽和結合を有する不飽和化合物（ｅ’－１）としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等が挙げられる。 As an unsaturated compound (e'-1) having one hydroxyl group and one polymerizable unsaturated bond in one molecule, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate And 4-hydroxybutyl (meth) acrylate.
　１分子中に１個の水酸基と２個以上の重合性不飽和結合を有する不飽和化合物（ｅ’－２）としては、例えば、グリセリンジ（メタ）アクリレート、ジグリセリントリ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ソルビトールペンタ（メタ）アクリレート、グリシジル（メタ）アクリレートの（メタ）アクリル酸付加物等が挙げられる。 As the unsaturated compound (e′-2) having one hydroxyl group and two or more polymerizable unsaturated bonds in one molecule, for example, glycerin di (meth) acrylate, diglycerin tri (meth) acrylate, tri Examples include methylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, and (meth) acrylic acid adduct of glycidyl (meth) acrylate.
　１分子中に２個以上の水酸基と１個の重合性不飽和結合を有する不飽和化合物（ｅ’－３）としては、例えば、グリセリンモノ（メタ）アクリレート、ジグリセリンモノ（メタ）アクリレート、ペンタエリスリトールモノ（メタ）アクリレート、ジペンタエリスリトールモノ（メタ）アクリレート、ソルビトールモノ（メタ）アクリレート等が挙げられる。 Examples of the unsaturated compound (e′-3) having two or more hydroxyl groups and one polymerizable unsaturated bond in one molecule include, for example, glycerin mono (meth) acrylate, diglycerin mono (meth) acrylate, penta Examples include erythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, and sorbitol mono (meth) acrylate.
　１分子中に２個以上の水酸基と２個以上の重合性不飽和結合を有する不飽和化合物（ｅ’－４）としては、例えば、ジグリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ソルビトールジ（メタ）アクリレート、ソルビトールトリ（メタ）アクリレート、ソルビトールテトラ（メタ）アクリレート、２分子の（メタ）アクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（例えばナガセケムテック社製「ＤＡ－２１２」）、２分子のエポキシ（メタ）アクリル酸と１分子のネオペンチルグリコールジグリシジルとの反応生成物、２分子の（メタ）アクリル酸と１分子のビスフェノールＡジグリシジルとの反応生成物（例えばナガセケムテック社製「ＤＡ－２５０」）、２分子の（メタ）アクリル酸とビスフェノールＡのプロピレンオキサイド付加物のジグリシジル体との反応生成物、２分子の（メタ）アクリル酸と１分子のフタル酸ジグリシジルとの反応生成物（例えばナガセケムテック社製「ＤＡ－７２１」）、２分子の（メタ）アクリル酸と１分子のポリエチレングリコールジグリシジルとの反応生成物（例えばナガセケムテック社製「ＤＭ－８１１」、「ＤＭ－８３２」、「ＤＭ－８５１」）、２分子の（メタ）アクリル酸と１分子のポリプロピレングリコールジグリシジルとの反応生成物などの（メタ）アクリル酸とポリオールジグリシジルとの反応生成物等が挙げられる。 Examples of the unsaturated compound (e′-4) having two or more hydroxyl groups and two or more polymerizable unsaturated bonds in one molecule include diglycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, and di Pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, 2 molecules Reaction product of (meth) acrylic acid with one molecule of 1,6-hexanediol diglycidyl (eg, "DA-212" manufactured by Nagase Chemtech Inc.), two molecules of epoxy (meth) acrylic acid and one molecule of neodymium Reaction with pentyl glycol diglycidyl , Reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of bisphenol A diglycidyl (eg Nagase ChemteX “DA-250”), 2 molecules of (meth) acrylic acid and propylene oxide of bisphenol A Reaction product of adduct with diglycidyl form, reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of diglycidyl phthalate (for example, “DA-721” manufactured by Nagase Chemtech Inc.) ) Reaction product of acrylic acid and one molecule of polyethylene glycol diglycidyl (eg Nagase ChemteX “DM-811”, “DM-832”, “DM-851”), 2 molecules of (meth) acrylic acid Reaction of (Meth) acrylic Acid with Polyol Diglycidyl, such as the Reaction Product of Polypropylene with 1 Molecule Polypropylene Glycol Diglycidyl Thing, and the like.
　不飽和化合物（ｅ）としては、イソシアナト基を有する化合物も使用することができ、例えば、イソシアナト基を有する（メタ）アクリル化合物として、２－イソシアナトエチルアクリレート（昭和電工製カレンズAOI）２－イソシアナトエチルメタクリレート（カレンズMOI）、１，１－ビス（アクリロイルオキシメチル）エチルイソシアネート（カレンズBEI）が挙げられる。不飽和化合物（ｅ）として、Ｎ－イソプロピル（メタ）アクリルアミド等を使用することもできる。 As the unsaturated compound (e), a compound having an isocyanato group can also be used. For example, as a (meth) acrylic compound having an isocyanato group, 2-isocyanatoethyl acrylate (Kalens AOI manufactured by Showa Denko K. K.) 2-isocyanate Natoethyl methacrylate (Karenz MOI) and 1,1-bis (acryloyloxymethyl) ethyl isocyanate (Karenz BEI) may be mentioned. As the unsaturated compound (e), N-isopropyl (meth) acrylamide and the like can also be used.
　また、不飽和化合物（ｅ’）をはじめとする不飽和化合物（ｅ）は、市販のものをそのまま用いてもよい。不飽和化合物（ｅ）は、単独で用いてもよいし、複数種を併用してもよい。例えば、不飽和化合物（ｅ’－１）～（ｅ’－４）のうち１種のみを用いてもよいし、２種以上を併用することもできる。 Moreover, you may use a commercially available thing as an unsaturated compound (e) including an unsaturated compound (e '). The unsaturated compounds (e) may be used alone or in combination of two or more. For example, only one type of unsaturated compounds (e′-1) to (e′-4) may be used, or two or more types may be used in combination.
　不飽和化合物（ｅ）の添加量は、得られる塗膜の硬度と、塗膜と基材との密着性の点から、水性ポリウレタン樹脂分散体の固形分（重合性不飽和結合を有する化合物（Ｂ）を含む）の全量を１００重量部とした場合、好ましくは２～５０重量部であり、より好ましくは５～４０重量である。不飽和化合物（ｅ）の添加量を２重量部以上とすることによって、得られる塗膜の表面硬度が低下するのを抑制することができる。不飽和化合物（ｅ）の添加量を５０重量部以下とすることによって、得られる塗膜と基材との密着性が低下するのを抑制することができる。 The amount of the unsaturated compound (e) added is the solid content of the aqueous polyurethane resin dispersion (a compound having a polymerizable unsaturated bond (a compound (a polymerizable unsaturated bond ( When the total amount of B) is 100 parts by weight, it is preferably 2 to 50 parts by weight, more preferably 5 to 40 parts by weight. By setting the addition amount of the unsaturated compound (e) to 2 parts by weight or more, it is possible to suppress the decrease in the surface hardness of the obtained coating film. By setting the addition amount of the unsaturated compound (e) to 50 parts by weight or less, it is possible to suppress the decrease in the adhesion between the obtained coating film and the substrate.
　不飽和化合物（ｅ）は、ポリウレタン水分散体の貯蔵安定性が向上する点から、不飽和化合物（ｅ’）の中でも１個の水酸基を有する化合物が好ましく、具体的には、１分子中に１個の水酸基と１個の重合性不飽和結合を有する不飽和化合物（ｅ’－１）、及び／又は１分子中に１個の水酸基と２個以上の重合性不飽和結合を有する不飽和化合物（ｅ’－２）を含むことが好ましい。中でも、得られる塗膜の硬度が向上する点から、１分子中に１個の水酸基と２個以上の重合性不飽和基を有する不飽和化合物（ｅ’－２）を含むことがより好ましく、不飽和化合物（ｅ’－２）の中でも、１分子内に１個の水酸基と３個の（メタ）アクリロイル基を有する化合物がより好ましい。 The unsaturated compound (e) is preferably a compound having one hydroxyl group among the unsaturated compounds (e ′) from the viewpoint of improving the storage stability of the polyurethane water dispersion, and specifically, in a molecule, it is specifically An unsaturated compound (e'-1) having one hydroxyl group and one polymerizable unsaturated bond, and / or an unsaturated compound having one hydroxyl group and two or more polymerizable unsaturated bonds in one molecule It is preferred to contain the compound (e'-2). Among them, it is more preferable to contain an unsaturated compound (e'-2) having one hydroxyl group and two or more polymerizable unsaturated groups in one molecule, from the viewpoint of improving the hardness of the obtained coating film, Among the unsaturated compounds (e′-2), compounds having one hydroxyl group and three (meth) acryloyl groups in one molecule are more preferable.
　不飽和化合物（ｅ’－１）及び／又は不飽和化合物（ｅ’－２）の使用量は、水性ポリウレタン樹脂分散体の固形分（重合性不飽和結合を有する化合物（Ｂ）を含む）全量を１００重量部とした場合、好ましくは２～５０重量部であり、より好ましくは、５～４０重量である。 The amount of the unsaturated compound (e'-1) and / or the unsaturated compound (e'-2) used is the total solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond) Is preferably 2 to 50 parts by weight, and more preferably 5 to 40 parts by weight.
　不飽和化合物（ｅ）は、得られる塗膜の硬度の点から、不飽和化合物（ｅ’）の中でも２個以上の水酸基を有する化合物が好ましく、具体的には、１分子中に２個以上の水酸基と１個の重合性不飽和結合を有する不飽和化合物（ｅ’－３）、及び／又は１分子中に２個以上の水酸基と２個以上の重合性不飽和結合を有する不飽和化合物（ｅ’－４）を含むことが好ましい。中でも、入手の容易さから、１分子中に２個以上の水酸基と２個以上の重合性不飽和基を有する不飽和化合物（ｅ’－４）を含むことがより好ましく、不飽和化合物（ｅ’－４）の中でも、１分子中に２個の水酸基と２個の（メタ）アクリロイル基を有する化合物がより好ましい。 The unsaturated compound (e) is preferably a compound having two or more hydroxyl groups among the unsaturated compounds (e ′) from the viewpoint of the hardness of the obtained coating film, and specifically, two or more in one molecule. Unsaturated compound (e'-3) having one hydroxyl group and one polymerizable unsaturated bond, and / or an unsaturated compound having two or more hydroxyl groups and two or more polymerizable unsaturated bonds in one molecule It is preferred to contain (e'-4). Among them, from the viewpoint of easy availability, it is more preferable to include an unsaturated compound (e'-4) having two or more hydroxyl groups and two or more polymerizable unsaturated groups in one molecule, and an unsaturated compound (e Among '-4), compounds having two hydroxyl groups and two (meth) acryloyl groups in one molecule are more preferable.
　不飽和化合物（ｅ’－３）及び／又は不飽和化合物（ｅ’－４）の使用量は、水性ポリウレタン樹脂分散体の固形分（重合性不飽和結合を有する化合物（Ｂ）を含む）全量を１００重量部とした場合、好ましくは２～３０重量部であり、より好ましくは５～２０重量である。 The amount of the unsaturated compound (e'-3) and / or the unsaturated compound (e'-4) used is the total solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond) Is preferably 2 to 30 parts by weight, and more preferably 5 to 20 parts by weight.
VI．ポリオール含有成分の水酸基当量
　本発明においては、ポリオール含有成分の水酸基当量数は１００～５００であることが好ましい。水酸基当量数が、この範囲であれば、水性ポリウレタン樹脂分散体の製造が容易であり、良好な水性ポリウレタン樹脂分散体の貯蔵安定性及び硬度に優れた塗膜が得られ易い。塗膜の硬度の観点から、好ましくは１２０～３００、より好ましくは１５０～２５０である。ここで、ポリオール含有成分は、ポリカーボネートポリオール（ａ）、酸性基含有ポリオール（ｂ）、及び任意のその他のポリオール（ｃ）に加えて、不飽和化合物（ｅ）が不飽和化合物（ｅ’－３）及び／又は（ｅ’－４）の場合、これらの不飽和化合物（ｅ’－３）及び／又は（ｅ’－４）を包含する。 VI. In the present invention, the hydroxyl equivalent number of the polyol-containing component is preferably 100 to 500. If the number of hydroxyl group equivalents is in this range, the production of the aqueous polyurethane resin dispersion is easy, and a coating film excellent in storage stability and hardness of a good aqueous polyurethane resin dispersion is easily obtained. From the viewpoint of the hardness of the coating, it is preferably 120 to 300, more preferably 150 to 250. Here, the polyol-containing component is, in addition to the polycarbonate polyol (a), the acidic group-containing polyol (b), and any other polyol (c), the unsaturated compound (e) is an unsaturated compound (e′-3) In the case of and / or (e'-4), these unsaturated compounds (e'-3) and / or (e'-4) are included.
　水酸基当量数は、以下の式（１）及び（２）で算出することができる。
　各ポリオールの水酸基当量数＝各ポリオールの分子量／各ポリオールの水酸基の数
・・・（１）
　ポリオールの合計の水酸基当量数＝Ｍ／ポリオールの合計モル数・・・（２）
　式（２）において、Ｍは、［〔ポリカーボネートポリオール（ａ）の水酸基当量数×ポリカーボネートポリオール（ａ）のモル数〕＋〔酸性基含有ポリオール（ｂ）の水酸基当量数×酸性基含有ポリオール（ｂ）のモル数〕＋〔その他のポリオール（ｃ）の水酸基当量数×その他のポリオール（ｃ）のモル数〕＋〔（ｅ’－３）の水酸基当量数×（ｅ’－３）のモル数〕］＋〔（ｅ’－４）の水酸基当量数×（ｅ’－４）のモル数〕］を示す。 The number of hydroxyl group equivalents can be calculated by the following formulas (1) and (2).
Number of hydroxyl group equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (1)
Total number of hydroxyl group equivalents of total polyol = M / total number of moles of polyol ... (2)
In the formula (2), M represents [[number of hydroxyl group equivalents of polycarbonate polyol (a) × number of moles of polycarbonate polyol (a)] + [number of hydroxyl group equivalents of acidic group-containing polyol (b) × acid group-containing polyol (b Number of hydroxyl groups of other polyol (c) × number of moles of other polyol (c)} + number of hydroxyl groups equivalent of (e′-3) × number of (e′-3) moles ]] + [Number of hydroxyl group equivalents of (e'-4) x number of moles of (e'-4)]] is shown.
VII．ポリウレタン樹脂（Ａ）又はポリウレタンプレポリマー（Ａ１）
　本発明におけるポリウレタン樹脂（Ａ）は、少なくとも、ポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、不飽和化合物（ｅ）を反応させて得られるポリウレタン樹脂であるか、あるいはポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、不飽和化合物（ｅ）とを反応させてポリウレタンプレポリマー（Ａ１）を得て、これをさらに鎖延長剤（Ｃ）と反応させて得られたポリウレタン樹脂である。 VII. Polyurethane resin (A) or polyurethane prepolymer (A1)
The polyurethane resin (A) in the present invention is a polyurethane resin obtained by reacting at least a polycarbonate polyol (a), an acidic group-containing polyol (b), a polyisocyanate (d) and an unsaturated compound (e). Or a polycarbonate polyol (a), an acid group-containing polyol (b), a polyisocyanate (d), and an unsaturated compound (e) to obtain a polyurethane prepolymer (A1). Further, it is a polyurethane resin obtained by reacting with a chain extender (C).
　ポリウレタン樹脂（Ａ）を得る場合において、ポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、場合により存在するその他のポリオール（ｃ）及び不飽和化合物（ｅ’）の全水酸基のモル数に対する、ポリイソシアネート（ｄ）のイソシアナト基のモル数の比は、０．８５～１．１が好ましい。この範囲より大きかったり、小さかったりする場合、ポリウレタン樹脂（Ａ）の分子量が、小さくなり、タックフリー性に劣る場合がある。前記成分の全水酸基のモル数に対する、ポリイソシアネート（ｄ）のイソシアナト基のモル数の比は、好ましくは０．９０～１．０５、特に好ましくは０．９５～１．０１である。 In the case of obtaining the polyurethane resin (A), the number of moles of all hydroxyl groups of the polycarbonate polyol (a), the acidic group-containing polyol (b), and the other polyols (c) and unsaturated compounds (e ') optionally present The ratio of the number of moles of isocyanato groups of polyisocyanate (d) to is preferably 0.85 to 1.1. When it is larger or smaller than this range, the molecular weight of the polyurethane resin (A) may be small and the tack-free property may be inferior. The ratio of the number of moles of isocyanato groups of polyisocyanate (d) to the number of moles of total hydroxyl groups of the component is preferably 0.90 to 1.05, and particularly preferably 0.95 to 1.01.
　ポリウレタン樹脂（Ａ）及びポリウレタンプレポリマー（Ａ１）は、ポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、その他のポリオール（ｃ）と、ポリイソシアネート（ｄ）と、不飽和化合物（ｅ）とを反応させて得られる反応生成物であるか、ポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、その他のポリオール（ｃ）と、ポリイソシアネート（ｄ）と、不飽和化合物（ｅ）とを反応させてポリウレタンプレポリマー（Ａ１）を得て、これをさらに鎖延長剤（Ｃ）と反応させて得られたポリウレタン樹脂であってもよい。
　ポリウレタンプレポリマー（Ａ１）と鎖延長剤（Ｃ）とを反応させてポリウレタン樹脂を得る場合には、ポリウレタンプレポリマー（Ａ１）と鎖延長剤（Ｃ）との反応の温度は、例えば０～８０℃、好ましくは０～６０℃である。 The polyurethane resin (A) and the polyurethane prepolymer (A1) are polycarbonate polyol (a), acid group-containing polyol (b), other polyols (c), polyisocyanate (d), unsaturated compound (e) Or an acid group-containing polyol (b), another polyol (c), a polyisocyanate (d), and an unsaturated compound (a). It may be a polyurethane resin obtained by reacting e) with the polyurethane prepolymer (A1) and further reacting it with a chain extender (C).
When the polyurethane prepolymer (A1) and the chain extender (C) are reacted to obtain a polyurethane resin, the temperature of the reaction between the polyurethane prepolymer (A1) and the chain extender (C) is, for example, 0 to 80. ° C., preferably 0 to 60 ° C.
　ポリウレタンプレポリマー（Ａ１）を得る場合において、ポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、場合により存在するその他のポリオール（ｃ）及び不飽和化合物（ｅ’）の全水酸基のモル数に対する、ポリイソシアネート（ｄ）のイソシアナト基のモル数の比は、１．０１～２．５が好ましい。この範囲であれば、前記水酸基含有成分の水酸基のモル数が多すぎることによって、分子末端にイソシアナト基を有しないポリウレタンプレポリマー（Ａ１）が多くなり、鎖延長剤（Ｃ）と反応しない分子が多くなって、水性ポリウレタン樹脂分散体を塗布して得られる塗膜の強度が低下するという問題を回避し易く、また、前記水酸基含有成分の水酸基のモル数が少なすぎることによって、未反応のポリイソシアネート（ｄ）が多量に反応系内に残り、鎖延長剤と反応したり、水と反応して分子伸長を起こして、水性ポリウレタン樹脂分散体を塗布して得られる塗膜に凹凸が生じるという問題も回避し易い。前記成分の全水酸基のモル数に対する、ポリイソシアネート（ｄ）のイソシアナト基のモル数の比は、好ましくは１．２～２．２、特に好ましくは１．３～２．０である。 In the case of obtaining the polyurethane prepolymer (A1), the moles of all hydroxyl groups of the polycarbonate polyol (a), the acid group-containing polyol (b), and the other polyols (c) and unsaturated compounds (e ') optionally present The ratio of the number of moles of isocyanato groups of polyisocyanate (d) to the number is preferably 1.01 to 2.5. Within this range, when the number of moles of hydroxyl groups in the hydroxyl group-containing component is too large, the number of polyurethane prepolymers (A1) having no isocyanato group at the molecular end increases and the molecules which do not react with the chain extender (C) It is easy to avoid the problem that the strength of the coating film obtained by applying the aqueous polyurethane resin dispersion is increased by a large amount, and the number of moles of the hydroxyl group of the hydroxyl group-containing component is too small. A large amount of isocyanate (d) remains in the reaction system, reacts with the chain extender, or reacts with water to cause molecular elongation, resulting in the occurrence of irregularities in the coating film obtained by applying the aqueous polyurethane resin dispersion. It is easy to avoid the problem. The ratio of the number of moles of isocyanato groups of polyisocyanate (d) to the number of moles of total hydroxyl groups of the component is preferably 1.2 to 2.2, and particularly preferably 1.3 to 2.0.
　ポリウレタン樹脂（Ａ）又ポリウレタンプレポリマー（Ａ１）を得る場合において、ポリカーボネートポリオール（ａ）、酸性基含有ポリオール（ｂ）、場合によりその他のポリオール（ｃ）、及び不飽和化合物（ｅ）とからなる成分と、ポリイソシアネート（ｄ）との反応は、（ａ）、（ｂ）、場合により（ｃ）、（ｅ）を順不同で（ｄ）と反応させてもよく、複数種を混合して（ｄ）と反応させてもよい。前記成分とポリイソシアネート（ｄ）とを反応させる際には、触媒を用いることもできる。 When a polyurethane resin (A) or polyurethane prepolymer (A1) is obtained, it comprises polycarbonate polyol (a), acid group-containing polyol (b), optionally other polyol (c), and unsaturated compound (e) The reaction of the component with the polyisocyanate (d) may be carried out by reacting (a), (b), optionally (c), (e) with (d) in a random order, and a plurality of types are mixed ((c) It may be reacted with d). When making the said component and polyisocyanate (d) react, a catalyst can also be used.
　触媒は、特に制限されず、例えば、スズ（錫）系触媒（トリメチル錫ラウレート、ジブチル錫ジラウレート等）や鉛系触媒（オクチル酸鉛等）等の金属と有機及び無機酸の塩、並びに有機金属誘導体、アミン系触媒（トリエチルアミン、Ｎ－エチルモルホリン、トリエチレンジアミン等）、ジアザビシクロウンデセン系触媒等が挙げられる。中でも、反応性の観点から、ジブチル錫ジラウレートが好ましい。 The catalyst is not particularly limited. For example, salts of metals such as tin (tin) -based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead-based catalysts (lead acid octylate, etc.) and salts of organic and inorganic acids, and organometallics Derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine etc.), diazabicycloundecene catalysts, etc. may be mentioned. Among them, dibutyltin dilaurate is preferable from the viewpoint of reactivity.
　前記成分とポリイソシアネート（ｄ）とを反応させる際の反応温度は、特に制限されないが、４０～１２０℃が好ましい。この範囲であれば、原料の溶解が充分であり、得られたポリウレタン（Ａ）又はウレタンプレポリマー（Ａ１）の粘度が適切であり、撹拌しやすく、また、不飽和化合物（ｅ）中の重合性不飽和結合が、重合反応を起こし、ゲル化したり、ポリイソシアネート（ｄ）中のイソシアナト基の副反応が起こしたりする等の不具合を回避し易い。反応温度は、より好ましくは６０～１００℃である。 The reaction temperature in the reaction of the component with the polyisocyanate (d) is not particularly limited but is preferably 40 to 120.degree. Within this range, dissolution of the raw materials is sufficient, the viscosity of the resulting polyurethane (A) or urethane prepolymer (A1) is appropriate, stirring is easy, and polymerization in the unsaturated compound (e) It is easy to avoid problems such as the occurrence of polymerization reaction, gelation, and side reaction of the isocyanate group in the polyisocyanate (d). The reaction temperature is more preferably 60 to 100 ° C.
　不飽和化合物（ｅ）と、ポリイソシアネート（ｄ）とを反応させる際には、不飽和化合物（ｅ）中の重合性不飽和結合の不必要な消費を避けるため、酸素存在下で行うのが好ましい。 When the unsaturated compound (e) and the polyisocyanate (d) are reacted, it is carried out in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond in the unsaturated compound (e). preferable.
　本発明において、ポリウレタン樹脂（Ａ）又はポリウレタンプレポリマー（Ａ１）を得る工程おいて、不飽和化合物（ｅ）の重合性不飽和結合の不必要な消費を避けるため、反応系中に重合禁止剤を添加しておくこともできる。 In the present invention, in the step of obtaining the polyurethane resin (A) or the polyurethane prepolymer (A1), a polymerization inhibitor is added to the reaction system to avoid unnecessary consumption of the polymerizable unsaturated bond of the unsaturated compound (e). Can also be added.
　重合禁止剤としては、ヒドロキノン、ヒドロキノンモノメチルエーテル、ベンゾキノン、２－ｔｅｒｔ－ブチルヒドロキノン、ｐ－ｔｅｒｔ－ブチルカテコール、２，５－ビス（１，１，３，３－テトラメチルブチル）ヒドロキノン、２，５－ビス（１，１－ジメチルブチル）ヒドロキノンなどのキノン系重合禁止剤；２，６－ビス（１，１－ジメチルエチル）－４－メチルフェノール、２，６－ジ－ｔｅｒｔ－ブチルフェノール、２，４－ジ－ｔｅｒｔ－ブチルフェノール、２－ｔｅｒｔ－ブチル－４，６－ジメチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，４，６－トリ－ｔｅｒｔ－ブチルフェノールなどのアルキルフェノール系重合禁止剤；フェノチアジンなどの芳香族アミン系重合禁止剤；アルキル化ジフェニルアミン、Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミン、フェノチアジン、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン、４－ベンゾイルオキシ－２，２，６，６－テトラメチルピペリジン、１，４－ジヒドロキシ－２，２，６，６－テトラメチルピペリジン、１－ヒドロキシ－４－ベンゾイリオキシ－２，２，６，６－テトラメチルピペリジン、ジ－ｐ－フルオロフェニルアミン、２，２，６，６－テトラメチルピペリジン－１－オキシル（ＴＥＭＰＯ）等のアミン系重合禁止剤；ほか２，２－ジフェニルピクリルヒドラジル（ＤＰＰＨ）、トリ－ｐ－ニトロフェニルメチル、Ｎ－（３Ｎ－オキシアニリノ－１，３－ジメチルブチリデン）－アニリンオキシド、ベンジルトリメチルアンモニウムクロライドなどの第４級アンモニウムクロライド；ジエチルヒドロキシルアミン、環状アミド、ニトリル化合物、置換尿素、ベンゾチアゾール、ビス－（１，２，２，６，６－ペンタメチル－４－ピペジニル）セパケート、乳酸、シュウ酸、クエン酸、酒石酸、安息香酸などの有機酸；有機ホスフィン、亜リン酸塩などが挙げられる。これらは一種を単独で用いてもよいし、複数種を併用してもよい。特にキノン系重合禁止剤とアルキルフェノール系重合禁止剤とを併用することにより、重合性不飽和結合の重合による消費がより少なくできる。 As a polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butyl hydroquinone, p-tert-butyl catechol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2, Quinone type polymerization inhibitors such as 5-bis (1,1-dimethylbutyl) hydroquinone; 2,6-bis (1,1-dimethylethyl) -4-methylphenol, 2,6-di-tert-butylphenol, 2 Such as 4, 4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol Alkylphenol polymerization inhibitors; aromatic amine polymerization inhibitors such as phenothiazine; Diphenylamine, N, N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine, di-p-fluorophenylamine, 2, Amine polymerization inhibitors such as 2,6,6-tetramethylpiperidine-1-oxyl (TEMPO); others 2,2-diphenylpicrylhydrazyl (DPPH), tri-p-nitrophenylmethyl, N- (3N) -Oxyanilino-1,3-dimethylbutylidene) -aniline oxide, benzyltrimethylammonium chloride Which quaternary ammonium chloride; diethylhydroxylamine, cyclic amides, nitrile compounds, substituted ureas, benzothiazole, bis- (1,2,2,6,6-pentamethyl-4-pipedinyl) separate, lactic acid, oxalic acid, citric acid Acids, organic acids such as tartaric acid and benzoic acid; organic phosphines and phosphites. One of these may be used alone, or two or more of these may be used in combination. In particular, by using a quinone type polymerization inhibitor and an alkylphenol type polymerization inhibitor in combination, the consumption by polymerization of the polymerizable unsaturated bond can be further reduced.
　重合禁止剤の添加量は、ポリウレタン樹脂（Ａ）１００重量部に対し０．００１～１重量部とすることができ、好ましくは０．０１～０．５重量部である。 The amount of the polymerization inhibitor added can be 0.001 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of the polyurethane resin (A).
　ポリカーボネートポリオール（ａ）、酸性基含有ポリオール（ｂ）、場合によりその他のポリオール（ｃ）、及び不飽和化合物（ｅ）と、ポリイソシアネート（ｄ）との反応は、無溶媒でも、有機溶媒を加えて行なってもよい。有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン、ジオキサン、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、酢酸エチル等が挙げられる。中でも、アセトン、メチルエチルケトン、酢酸エチルは、ポリウレタンプレポリマーの水への分散及び鎖伸長反応後に加熱減圧により除去できるので好ましい。また、Ｎ－メチルピロリドン、Ｎ－エチルピロリドンは、得られた水性ポリウレタン樹脂分散体から塗膜を作製する際に造膜助剤として働くため好ましい。有機溶媒の添加量は、ポリカーボネートポリオール（ａ）、酸性基含有ポリオール（ｂ）、場合によりその他のポリオール（ｃ）、及び不飽和化合物（ｅ）の全量に対して重量基準で、好ましくは０～２．０倍であり、より好ましくは０．１～０．７倍である。この範囲であれば、ポリウレタンプレポリマー（Ａ１）を得る際の粘度を適切な範囲とし、良好な分散を得ることができる。その一方で、有機溶媒の除去に要する時間がかかりすぎることがなく、水性ポリウレタン樹脂分散体を用いて得られる塗膜中に有機溶媒が残存することで塗膜物性が低下したりするといった事態を容易に回避することができる。 The reaction of polycarbonate polyol (a), acidic group-containing polyol (b), optionally other polyol (c), and unsaturated compound (e) with polyisocyanate (d) can be carried out either without solvent or with an organic solvent You may do it. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, N-ethyl pyrrolidone, ethyl acetate and the like. Among them, acetone, methyl ethyl ketone and ethyl acetate are preferable because they can be removed by heating and reducing pressure after dispersion of polyurethane prepolymer in water and chain elongation reaction. In addition, N-methyl pyrrolidone and N-ethyl pyrrolidone are preferable because they function as a film forming aid when producing a coating film from the obtained aqueous polyurethane resin dispersion. The addition amount of the organic solvent is preferably 0 to 5 by weight based on the total amount of polycarbonate polyol (a), acid group-containing polyol (b), optionally other polyol (c), and unsaturated compound (e). It is 2.0 times, more preferably 0.1 to 0.7 times. If it is this range, the viscosity at the time of obtaining a polyurethane prepolymer (A1) can be made into a suitable range, and a favorable dispersion | distribution can be obtained. On the other hand, the time taken to remove the organic solvent does not take too long, and the physical properties of the coating film may be deteriorated due to the organic solvent remaining in the coating film obtained using the aqueous polyurethane resin dispersion. It can be easily avoided.
　本発明において、ポリウレタン樹脂（Ａ）又ポリウレタンプレポリマー（Ａ１）の酸価は、２０～５０ｍｇＫＯＨ／ｇが好ましい。この範囲であれば、良好な水系媒体への分散性及び塗膜の耐水性を確保し易い。前記酸価は、より好ましくは２５～４５ｍｇＫＯＨ／ｇであり、さらに好ましくは３０～４０ｍｇＫＯＨ／ｇである。 In the present invention, the acid value of the polyurethane resin (A) or polyurethane prepolymer (A1) is preferably 20 to 50 mg KOH / g. Within this range, it is easy to ensure good dispersibility in an aqueous medium and water resistance of the coating film. The acid value is more preferably 25 to 45 mg KOH / g, still more preferably 30 to 40 mg KOH / g.
　ここで、ポリウレタン樹脂（Ａ）又はポリウレタンプレポリマー（Ａ１）の酸価とは、ポリウレタン樹脂（Ａ）又はポリウレタンプレポリマー（Ａ１）を製造するにあたって用いられる溶媒及びポリウレンプレポリマー（Ａ１）を水系媒体中に分散させるための中和剤を除いたいわゆる固形分中の酸基の平均含有量であり、ポリカーボネートポリオール（ａ）、酸性基含有ポリオール（ｂ）、場合によりその他のポリオール（ｃ）、不飽和化合物（ｅ）及びポリイソシアネート（ｄ）の重量、並びに酸性基含有ポリオール（ｂ）に含まれる酸性基から求められ、下記式（３）によって導き出すことができる。
〔ポリウレタン樹脂（Ａ）又はポリウレタンプレポリマー（Ａ１）の酸価〕＝
〔酸性基含有ポリオール（ｂ）の酸性基のモル数〕×５６．１１／〔ポリカーボネートポリオール（ａ）、酸性基含有ポリオール（ｂ）、場合によりその他のポリオール（ｃ）、不飽和化合物（ｅ）及びポリイソシアネート（ｄ）の合計の重量〕・・・（３）
　ポリウレタンプレポリマー（Ａ１）を得た後、水系溶媒への分散と鎖延長剤（Ｃ）による鎖延長とを行って本発明の水性ポリウレタン樹脂分散体を得る場合には、前記酸価は、ポリウレタンプレポリマー（Ａ１）の酸価と同義である。 Here, the acid value of the polyurethane resin (A) or polyurethane prepolymer (A1) refers to the solvent used for producing the polyurethane resin (A) or polyurethane prepolymer (A1) and the polyurethane prepolymer (A1). Average content of acid groups in the so-called solid content excluding the neutralizing agent for dispersing in the medium, polycarbonate polyol (a), acidic group-containing polyol (b), optionally other polyol (c), It can be derived from the weight of the unsaturated compound (e) and the polyisocyanate (d), and the acid group contained in the acid group-containing polyol (b), and can be derived by the following formula (3).
[Acid Value of Polyurethane Resin (A) or Polyurethane Prepolymer (A1)] =
[Mole number of acidic group of acidic group-containing polyol (b)] × 56.11 / [polycarbonate polyol (a), acidic group-containing polyol (b), optionally other polyol (c), unsaturated compound (e) And total weight of polyisocyanate (d)] (3)
After the polyurethane prepolymer (A1) is obtained, dispersion in an aqueous solvent and chain extension with a chain extender (C) are carried out to obtain the aqueous polyurethane resin dispersion of the present invention, the acid value is polyurethane It is synonymous with the acid value of prepolymer (A1).
　ポリウレタン樹脂（Ａ）又ポリウレタンプレポリマー（Ａ１）を得る場合において、水性ポリウレタン樹脂分散体の固形分（重合性不飽和結合を有する化合物（Ｂ）を含む）全量を１００重量部とした場合に、ポリカーボネートポリオール（ａ）は、好ましくは２～５０量部、酸性基含有ポリオール（ｂ）は、好ましくは２～１５重量部、その他のポリオール（ｃ）は、好ましくは０～３０重量部、不飽和化合物（ｅ）は、好ましくは、５～５０重量部である。ポリカーボネートポリオール（ａ）が前記の範囲であれば、水性ポリウレタン樹脂分散体から得られる塗膜の密着性が高く、また、ポリウレタン樹脂（Ａ）の水系媒体への分散性が良好で、優れた製膜性が容易に得られる。ポリカーボネートポリオール（ａ）は、より好ましくは３～４０重量部、特に好ましくは５～３０重量部である。酸性基含有ポリオール（ｂ）が前記の範囲であれば、水性ポリウレタン樹脂分散体から得られる塗膜の耐水性が良好で、ポリウレタン樹脂（Ａ）の水系媒体への分散性が良好である。酸性基含有ポリオール（ｂ）は、より好ましくは３～１０重量部、特に好ましくは４～７重量部である。不飽和化合物（ｅ）が前記の範囲であれば、水性ポリウレタン樹脂分散体から得られる塗膜の硬度及び密着性が良好で、水性ポリウレタン樹脂分散体の貯蔵安定性にも優れたものが得られる。不飽和化合物（ｅ）は、より好ましくは、１０～４０重量である。 When the polyurethane resin (A) or the polyurethane prepolymer (A1) is obtained, the total amount of solids (including the compound (B) having a polymerizable unsaturated bond) of the aqueous polyurethane resin dispersion is 100 parts by weight, The polycarbonate polyol (a) is preferably 2 to 50 parts by weight, the acid group-containing polyol (b) is preferably 2 to 15 parts by weight, and the other polyol (c) is preferably 0 to 30 parts by weight, unsaturated. The compound (e) is preferably 5 to 50 parts by weight. When the polycarbonate polyol (a) is in the above range, the adhesion of the coating film obtained from the aqueous polyurethane resin dispersion is high, and the dispersibility of the polyurethane resin (A) in the aqueous medium is good and excellent. Membrane properties are easily obtained. The polycarbonate polyol (a) is more preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight. If the acidic group-containing polyol (b) is in the above range, the water resistance of the coating film obtained from the aqueous polyurethane resin dispersion is good, and the dispersibility of the polyurethane resin (A) in the aqueous medium is good. The acidic group-containing polyol (b) is more preferably 3 to 10 parts by weight, particularly preferably 4 to 7 parts by weight. When the unsaturated compound (e) is in the above range, a film obtained from the aqueous polyurethane resin dispersion has excellent hardness and adhesion, and the storage stability of the aqueous polyurethane resin dispersion is also excellent. . The unsaturated compound (e) is more preferably 10 to 40 weight.
VIII．鎖延長剤（Ｃ）
　本発明における重合性不飽和結合を有するポリウレタン樹脂（Ａ）は、鎖延長剤（Ｃ）を用いることによって活性エネルギー線（例えば、紫外線）照射前の乾燥塗膜にベタツキが少なく、タックフリーとなるため、鎖延長剤（Ｃ）を使用して調製したものであることが好ましい。鎖延長剤（Ｃ）としては、例えば、エチレンジアミン、１，４－テトラメチレンジアミン、２－メチル－１，５－ペンタンジアミン、１，４－ブタンジアミン、１，６－ヘキサメチレンジアミン、１，４－ヘキサメチレンジアミン、３－アミノメチル－３，５，５－トリメチルシクロヘキシルアミン、１，３－ビス（アミノメチル）シクロヘキサン、キシリレンジアミン、ピペラジン、２，５－ジメチルピペラジン、ヒドラジン、アジポイルジヒドラジド、ジエチレントリアミン、トリエチレンテトラミン等のアミン化合物、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール等のジオール化合物、ポリエチレングリコールに代表されるポリアルキレングリコール類、水等が挙げられ、中でも得られる塗膜の活性エネルギー線（例えば、紫外線）硬化後の塗膜の硬度の点から、鎖延長剤（Ｃ）は有機化合物であることが好ましく、ポリアミン化合物であることがより好ましく、１級ポリアミン化合物であることが特に好ましい。これらは、単独で用いてもよいし、複数種を併用してもよい。 VIII. Chain extender (C)
The polyurethane resin (A) having a polymerizable unsaturated bond in the present invention becomes less tacky to the dried coating before irradiation with active energy rays (for example, ultraviolet rays) by using the chain extender (C), and becomes tack free Therefore, it is preferable to use one prepared using a chain extender (C). As the chain extender (C), for example, ethylene diamine, 1,4-tetramethylene diamine, 2-methyl-1,5-pentane diamine, 1,4-butane diamine, 1,6-hexamethylene diamine, 1,4 -Hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, hydrazine, adipoyl dihydrazide Amine compounds such as diethylenetriamine and triethylenetetramine, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol, polyalkylene glycols represented by polyethylene glycol, water and the like And above all The chain extender (C) is preferably an organic compound, more preferably a polyamine compound, and more preferably a primary polyamine, from the viewpoint of the hardness of the coating after curing of active energy rays (for example, ultraviolet rays) Particular preference is given to compounds. These may be used alone or in combination of two or more.
　鎖延長剤（Ｃ）の添加量は、ポリウレタンプレポリマー（Ａ１）中の鎖延長起点となるイソシアナト基の当量以下であることが好ましく、より好ましくはイソシアナト基の０．７～０．９９当量である。この範囲であれば、鎖延長されたポリウレタン樹脂（Ａ）の分子量を適切な範囲とし、ひいては、これを含む水性ポリウレタン樹脂分散体を塗布して得た塗膜の強度を良好にすることができる。鎖延長剤（Ｃ）は、ポリウレタンプレポリマー（Ａ１）の水への分散後に添加してもよく、分散中に添加してもよい。鎖延長は水によっても行うことができる。この場合は分散媒としての水が鎖延長剤を兼ねることになる。 The addition amount of the chain extender (C) is preferably not more than the equivalent of the isocyanato group as the chain extension origin in the polyurethane prepolymer (A1), and more preferably 0.7 to 0.99 equivalent of the isocyanato group. is there. Within this range, the molecular weight of the chain-extended polyurethane resin (A) can be made an appropriate range, and in turn, the strength of the coating film obtained by applying the aqueous polyurethane resin dispersion containing this can be improved. . The chain extender (C) may be added after dispersing the polyurethane prepolymer (A1) in water, or may be added during the dispersion. Chain extension can also be performed with water. In this case, water as a dispersion medium also serves as a chain extender.
<重合性不飽和結合を有する化合物（Ｂ）>
　本発明における重合性不飽和結合を有する化合物（Ｂ）は、光ラジカル発生剤の共存下や、熱ラジカル発生剤の共存下で重合するものが好ましいが、２５℃においてイソシアナト基とは反応しない化合物を用いるのが好ましい。 <Compound (B) Having a Polymerizable Unsaturated Bond>
The compound (B) having a polymerizable unsaturated bond in the present invention is preferably a compound which is polymerized in the coexistence of a photo radical generator or in the coexistence of a heat radical generator, but a compound which does not react with the isocyanato group at 25 ° C. It is preferred to use
　重合性不飽和結合を有する化合物（Ｂ）としては、ビニル基又はアリル基等のエチレン性不飽和結合を有する化合物が挙げられ、（メタ）アクリロイル基を有する化合物が挙げられる。重合性不飽和結合を有する化合物（Ｂ）は、（メタ）アクリロイル基等の重合性不飽和結合を有する基を１個有する、１官能性の化合物であっても、複数個有する多官能性の化合物であってもよく、３個以上の（メタ）アクリロイル基を有する化合物や５個以上の（メタ）アクリロイル基を有する化合物も好適に使用可能である。 As a compound (B) which has a polymerizable unsaturated bond, the compound which has ethylenic unsaturated bonds, such as a vinyl group or an allyl group, is mentioned, and the compound which has a (meth) acryloyl group is mentioned. The compound (B) having a polymerizable unsaturated bond is a polyfunctional compound having a plurality of even a monofunctional compound having one group having a polymerizable unsaturated bond such as a (meth) acryloyl group. It may be a compound, and a compound having three or more (meth) acryloyl groups or a compound having five or more (meth) acryloyl groups can also be suitably used.
　重合性不飽和結合を有する化合物（Ｂ）としては、（メタ）アクリレート化合物が好ましい。（メタ）アクリレート化合物としては、モノマー類の（メタ）アクリレート化合物や、ポリウレタン（メタ）アクリレート化合物、ポリエステル（メタ）アクリレート系化合物、ポリアルキレン（メタ）アクリレート系化合物等が挙げられる。 As a compound (B) which has a polymerizable unsaturated bond, a (meth) acrylate compound is preferable. Examples of (meth) acrylate compounds include (meth) acrylate compounds of monomers, polyurethane (meth) acrylate compounds, polyester (meth) acrylate compounds, and polyalkylene (meth) acrylate compounds.
　モノマー類の（メタ）アクリレート化合物としては、モノ（メタ）アクリレートやジ（メタ）アクリレート、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート、ヘキサ（メタ）アクリレート等のモノ（メタ）アクリレートやポリ（メタ）アクリレートが使用可能である。 Monomer (meth) acrylate compounds such as mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate and the like (mono) Meta) acrylates and poly (meth) acrylates can be used.
　前記モノ（メタ）アクリレートとしては、例えば、２－エチルヘキシル（メタ）アクリレート、メチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ドデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート等が挙げられる。 Examples of the mono (meth) acrylate include 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) 2.) Acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate and the like.
　ジ（メタ）アクリレートとしては、例えば、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート等のアルキレングリコールジ（メタ）アクリレート；ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等のポリエーテルジ（メタ）アクリレート；ビスフェノールＡエチレンオキサイド変性ジ（メタ）アクリレート、ビスフェノールＡプロピレンオキサイド変性ジ（メタ）アクリレート、ネオペンチルグリコールエチレンオキサイド変性ジ（メタ）アクリレート、ネオペンチルグリコールプロピレンオキサイド変性ジ（メタ）アクリレート等のアルキレンオキサイド変性ジ（メタ）アクリレート；１，６－ヘキサンジオールエポキシジ（メタ）アクリレート、ネオペンチルグリコールエポキシジ（メタ）アクリレート、ビスフェノールＡエポキシジ（メタ）アクリレート、ビスフェノールＡプロピレンオキサイド変性エポキシジ（メタ）アクリレート、フタル酸エポキシジ（メタ）アクリレート、ポリエチレングリコールエポキシジ（メタ）アクリレート、ポリプロピレングリコールエポキシジ（メタ）アクリレートなどのエポキシジ（メタ）アクリレート等が挙げられる。 Examples of di (meth) acrylates include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Alkylene glycol di (meth) acrylates such as hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A di (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Polyether di (meth) acrylates such as acrylates; Bisphenol A ethylene oxide modified di (meth) acrylate, Bisphenol A propylene oxide modified di (meth) acrylate, Alkylene oxide modified di (meth) acrylates such as pentyl glycol ethylene oxide modified di (meth) acrylate, neopentyl glycol propylene oxide modified di (meth) acrylate; 1,6-hexanediol epoxy di (meth) acrylate, neopentyl glycol epoxy Di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, bisphenol A propylene oxide modified epoxy di (meth) acrylate, phthalic acid epoxy di (meth) acrylate, polyethylene glycol epoxy di (meth) acrylate, polypropylene glycol epoxy di (meth) acrylate And epoxy di (meth) acrylates and the like.
　トリ（メタ）アクリレートとしては、例えば、トリメチロールプロパントリアクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等が挙げられる。 Examples of tri (meth) acrylates include trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. Be
　テトラ（メタ）アクリレートとしては、例えば、ジペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、エチレンオキサイド（４モル）変性ペンタエリスリトールテトラ（メタ）アクリレート（ダイセル・サイテック社、Ｅｂｅｃｒｙｌ ４０）等のアルキレンオキサイド変性ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラアクリレート等が挙げられる。
　ペンタ（メタ）アクリレートとしては、例えば、ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられる。
　ヘキサ（メタ）アクリレートとしては、例えば、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 Examples of tetra (meth) acrylates include dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide (4 moles) modified pentaerythritol tetra (meth) acrylate (Dasel Cytech Co., Ltd. Ebecryl 40) And alkylene oxide-modified pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate and the like.
Examples of penta (meth) acrylates include dipentaerythritol penta (meth) acrylate and the like.
Examples of hexa (meth) acrylates include dipentaerythritol hexa (meth) acrylate and the like.
　これらのモノマー類の（メタ）アクリレート化合物の中でも、硬度の点から、ジ（メタ）アクリレート、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート、ヘキサ（メタ）アクリレートといったポリ（メタ）アクリレートが好ましい。これは、分子内に複数の（メタ）アクリロイル基を有することによって、モノ（メタ）アクリレート同士の場合よりも、より高分子量化し易いためである。中でも、硬度の点から、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート、ヘキサ（メタ）アクリレートが好ましい。より好ましくは、ペンタ（メタ）アクリレート、ヘキサ（メタ）アクリレートである。 Among the (meth) acrylate compounds of these monomers, from the viewpoint of hardness, poly (di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate) Meta) acrylate is preferred. This is because, by having a plurality of (meth) acryloyl groups in the molecule, the molecular weight can be increased more easily than in the case of mono (meth) acrylates. Among them, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate are preferable in terms of hardness. More preferably, penta (meth) acrylate and hexa (meth) acrylate are used.
　ポリマー類の（メタ）アクリレートとしては、ポリアルキレングリコール構造を有する（メタ）アクリレート以外にも、ポリウレタン（メタ）アクリレート化合物、ポリエステル（メタ）アクリレート系化合物、ポリアルキレン（メタ）アクリレート系化合物等を使用することができ、例えば、分子内に重合性不飽和結合を有するアクリル系ポリマー等を使用することができ、例えば、分子片末端に重合性二重結合を有するポリブチルアクリレート（綜研化学社製「アクトフローＢＧＶ－１００Ｔ」）や、分子両末端に重合性二重結合を有するポリブチルアクリレート（綜研化学社製「アクトフロー」などが挙げられる。 As (meth) acrylates of polymers, in addition to (meth) acrylates having a polyalkylene glycol structure, polyurethane (meth) acrylate compounds, polyester (meth) acrylate compounds, polyalkylene (meth) acrylate compounds, etc. are used For example, an acrylic polymer or the like having a polymerizable unsaturated bond in the molecule can be used, for example, polybutyl acrylate having a polymerizable double bond at the end of one molecule (manufactured by Soken Chemical Co., Ltd.) Actflow BGV-100T "), and polybutyl acrylate having polymerizable double bonds at both molecular ends (" Aktoflow "manufactured by Soken Chemical Co., Ltd.).
　重合性不飽和結合を有する化合物（Ｂ）としては、アクリロイルモルホリン、スチレン、Ｎ－ビニル－２－ピロリドン等の（メタ）アクリレート化合物以外のビニル基やアリル基を含有する化合物も使用することができる。 As the compound (B) having a polymerizable unsaturated bond, compounds having a vinyl group or an allyl group other than (meth) acrylate compounds such as acryloyl morpholine, styrene, N-vinyl-2-pyrrolidone and the like can also be used. .
　重合性不飽和結合を有する化合物（Ｂ）としては、市販のものをそのまま用いてもよい。重合性不飽和結合を有する化合物（Ｂ）は、単独で用いてもよいし、複数種を併用してもよい。 As the compound (B) having a polymerizable unsaturated bond, a commercially available one may be used as it is. The compound (B) having a polymerizable unsaturated bond may be used alone or in combination of two or more.
　水性ポリウレタン樹脂分散体の固形分（重合性不飽和結合を有する化合物（Ｂ）を含む）の全量を１００重量部とした場合、好ましくは２～５０重量部であり、より好ましくは５～４０重量である。 The total amount of solids (including the compound (B) having a polymerizable unsaturated bond) in the aqueous polyurethane resin dispersion is 100 parts by weight, preferably 2 to 50 parts by weight, and more preferably 5 to 40 parts by weight It is.
　重合性不飽和結合を有する化合物（Ｂ）は、水性ポリウレタン樹脂分散体の固形分（ポリウレタン樹脂（Ａ）を含む）の全量１００重量部とした場合、好ましくは１０～６０重量部である。この範囲であれば、水性ポリウレタン樹脂分散体から得られる塗膜の密着性及び硬度を良好にすることが容易にでき、かつ水性ポリウレタン樹脂分散体について、良好な貯蔵安定性を得ることができる。重合性不飽和結合を有する化合物（Ｂ）は、より好ましくは２０～５０重量部であり、特に好ましくは３０～４５重量部である。 The compound (B) having a polymerizable unsaturated bond is preferably 10 to 60 parts by weight, based on 100 parts by weight of the total solid content of the aqueous polyurethane resin dispersion (including the polyurethane resin (A)). Within this range, the adhesion and hardness of the coating film obtained from the aqueous polyurethane resin dispersion can be easily improved, and good storage stability can be obtained for the aqueous polyurethane resin dispersion. The compound (B) having a polymerizable unsaturated bond is more preferably 20 to 50 parts by weight, and particularly preferably 30 to 45 parts by weight.
<水性ポリウレタン樹脂分散体>
Ｘ．水系媒体
　本発明においては、ポリウレタン樹脂（Ａ）は水系媒体中に分散されている。水系媒体としては、水や、水と親水性有機溶媒との混合媒体等が挙げられる。 <Aqueous polyurethane resin dispersion>
X. Aqueous Medium In the present invention, the polyurethane resin (A) is dispersed in an aqueous medium. Examples of the aqueous medium include water, a mixed medium of water and a hydrophilic organic solvent, and the like.
　水としては、例えば、上水、イオン交換水、蒸留水、超純水等が挙げられる。中でも、入手の容易さや塩の影響で粒子が不安定になること等を考慮して、イオン交換水が好ましい。 Examples of water include, for example, fresh water, ion-exchanged water, distilled water, ultrapure water and the like. Among them, ion-exchanged water is preferable in consideration of easiness of obtaining and instability of particles due to the influence of salt and the like.
　親水性有機溶媒としては、メタノール、エタノール、プロパノール等の低級１価アルコール；エチレングリコール、グリセリン等の多価アルコール；Ｎ－メチルモルホリン、ジメチルスルホキサイド、ジメチルホルムアミド、Ｎ－メチルピロリドン等の非プロトン性の親水性有機溶媒等が挙げられる。水系媒体中の親水性有機溶媒の量としては、０～２０重量％が好ましい。 Examples of hydrophilic organic solvents include lower monohydric alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol and glycerol; aprotics such as N-methylmorpholine, dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone Hydrophilic organic solvents and the like. The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by weight.
XI．水性ポリウレタン樹脂分散体の製造方法
　次に、水性ポリウレタン樹脂分散体の製造方法について説明する。
　本発明の水性ポリウレタン樹脂は、少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）とを反応させてポリウレタン樹脂（Ａ）を得て、
　ポリウレタン樹脂（Ａ）及び重合性不飽和結合を有する化合物（Ｂ）を水系媒体に分散させることによる得られる。 XI. Method of Producing Aqueous Polyurethane Resin Dispersion Next, a method of producing an aqueous polyurethane resin dispersion will be described.
The aqueous polyurethane resin of the present invention comprises at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one or more isocyanates in one molecule. A polyurethane resin (A) is obtained by reacting a group (e) having a group capable of reacting with the group and a compound (e) having one or more polymerizable unsaturated bonds,
It is obtained by dispersing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium.
　また、本発明の水性ポリウレタン樹脂分散体の製造方法は、ポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）とを反応させてポリウレタンプレポリマー（Ａ１）を得る工程（α１）と、
　ポリウレタンプレポリマー（Ａ１）の酸性基を中和する工程（β）と、
　ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）と、
　ポリウレタンプレポリマー（Ａ１）と、ポリウレタンプレポリマー（Ａ１）のイソシアナト基と反応性を有する鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂を得る工程（δ）とを含むことができる。 Moreover, the method for producing an aqueous polyurethane resin dispersion of the present invention comprises polycarbonate polyol (a), acidic group-containing polyol (b), polyisocyanate (d), and a group capable of reacting with one or more isocyanate groups. A step (α1) of reacting with a compound (e) having one or more polymerizable unsaturated bonds to obtain a polyurethane prepolymer (A1);
Neutralizing the acid group of the polyurethane prepolymer (A1) (β);
Dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium (γ);
A step (δ) of reacting the polyurethane prepolymer (A1) with a chain extender (C) having reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin can be included.
　また、ポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、その他のポリオール（ｃ）と、ポリイソシアネート（ｄ）と、１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）とを反応させてポリウレタンプレポリマー（Ａ１）を得る工程（α２）と、
　ポリウレタンプレポリマー（Ａ１））の酸性基を中和する工程（β）と、
　ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）と、
　ポリウレタンプレポリマー（Ａ１）と、ポリウレタンプレポリマー（Ａ１）のイソシアナト基と反応性を有する鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂を得る工程（δ）とを含むことができる。 In addition, polycarbonate polyol (a), acidic group-containing polyol (b), other polyols (c), polyisocyanate (d), one or more groups capable of reacting with one or more isocyanato groups, and one or more polymerizations Reacting with a compound (e) having a heterocyclic unsaturated bond to obtain a polyurethane prepolymer (A1) (α2);
Neutralizing the acid groups of the polyurethane prepolymer (A1)) (β),
Dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium (γ);
A step (δ) of reacting the polyurethane prepolymer (A1) with a chain extender (C) having reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin can be included.
　ポリウレタンプレポリマー（Ａ１）を得る工程（α１）及び（α２）は、重合性不飽和結合の不必要な消費を避けるため、酸素存在下で行うのが好ましい。また、必要に応じて反応系内に重合禁止剤を添加することが望ましい。ポリウレタンプレポリマー（Ａ１）を得る工程（α１）及び（α２）の温度は、重合性不飽和結合の不必要な重合を回避するため、０～１２０℃で行うことができる。好ましくは０～１００℃で行うのが好ましい。 The steps (α1) and (α2) for obtaining the polyurethane prepolymer (A1) are preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Moreover, it is desirable to add a polymerization inhibitor into the reaction system as needed. The temperature of the steps (α1) and (α2) for obtaining the polyurethane prepolymer (A1) can be performed at 0 to 120 ° C. in order to avoid unnecessary polymerization of the polymerizable unsaturated bond. It is preferable to carry out at 0 to 100 ° C.
　ポリウレタンプレポリマー（Ａ１）の酸性基を中和する工程（β）において使用できる酸性基中和剤としては、トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン、トリエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－フェニルジエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、Ｎ－メチルモルホリン、ピリジン等の有機アミン類；水酸化ナトリウム、水酸化カリウム等の無機アルカリ類、アンモニア等が挙げられる。中でも、好ましくは有機アミン類であり、より好ましくは３級アミンであり、最も好ましくはトリエチルアミンである。ここで、ポリウレタンプレポリマー（Ａ１）の酸性基とは、カルボン酸基、スルホン酸基等をいう。 As an acidic group neutralizer that can be used in the step (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N- Organic amines such as phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, and pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and ammonia. Among them, preferred is an organic amine, more preferred is a tertiary amine, and most preferred is triethylamine. Here, the acidic group of a polyurethane prepolymer (A1) means a carboxylic acid group, a sulfonic acid group, etc.
　酸性基中和剤の使用量は、ポリウレタンプレポリマー（Ａ１）の酸性基に対し、モル数で０．８～１．５になるような量が好ましい。この範囲であれば、ポリウレタンプレポリマー（Ａ１）の水への分散性が十分であり、得られる水性ポリウレタン樹脂分散体の貯蔵安定性が低下することもなく、かつ水性ポリウレタン樹脂分散体の臭気が強くなるといった事態も容易に回避できる。 The amount of the acidic group neutralizer used is preferably such that the number of moles is from 0.8 to 1.5 with respect to the acidic group of the polyurethane prepolymer (A1). Within this range, the dispersibility of the polyurethane prepolymer (A1) in water is sufficient, and the storage stability of the resulting aqueous polyurethane resin dispersion does not decrease, and the odor of the aqueous polyurethane resin dispersion is reduced. It can easily be avoided that the situation becomes stronger.
　ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）においては、（Ａ１）と（Ｂ）とが水系媒体中に分散できるのであれば、その方法及び操作順序等は、特に制限されないが、例えば、（Ａ１）に（Ｂ）を混合して水系媒体中に分散させる方法や、（Ｂ）に（Ａ１）を混合して水系媒体中に分散させる方法や、（Ａ１）を水系媒体中に分散させた後に（Ｂ）を混合分散させる方法や、（Ｂ）を水系媒体中に分散させた後に（Ａ１）を混合分散させる方法や、（Ａ１）と（Ｂ）とをそれぞれ水系媒体中に分散させた後に混合する方法等が挙げられる。 In the step (γ) of dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium, it is possible to disperse (A1) and (B) in an aqueous medium For example, the method and operation sequence thereof are not particularly limited, but, for example, a method of mixing (A1) with (B) and dispersing in an aqueous medium, or (B) mixing (A1) with an aqueous medium (A1) is dispersed in an aqueous medium, (B) is mixed and dispersed, (B) is dispersed in an aqueous medium, and (A1) is mixed and dispersed, , (A1) and (B) are each dispersed in an aqueous medium and then mixed.
　前記の混合や撹拌、分散には、ホモミキサーやホモジナイザー等の公知の撹拌装置を用いることができる。また、ポリウレタンプレポリマー（Ａ１）や重合性不飽和結合を有する化合物（Ｂ）には、粘度調整や作業性向上、分散性向上のために、混合前に予め親水性有機溶媒や水等を加えておくこともできる。 A well-known stirring apparatus such as a homomixer or a homogenizer can be used for the above-mentioned mixing, stirring and dispersion. Further, to the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond, a hydrophilic organic solvent, water, etc. are added in advance before mixing in order to adjust the viscosity, to improve the workability, and to improve the dispersibility. You can also
　また、ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）を混合する工程（γ）は、重合性不飽和結合の不必要な消費を避けるため、酸素存在下で行うのが好ましい。また、必要に応じて重合禁止剤を添加してもよい。ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）を混合する際の温度は、重合性不飽和結合の不必要な消費を回避するため、０～１００℃で行うことができ、０～８０℃で行うのがより好ましく、０～７０℃で行うのがさらに好ましく、５０～７０℃で行うのが特に好ましい。 Also, the step (γ) of mixing the polyurethane prepolymer (A1) with the compound (B) having a polymerizable unsaturated bond is carried out in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. preferable. Moreover, you may add a polymerization inhibitor as needed. The temperature at which the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond are mixed can be performed at 0 to 100 ° C. in order to avoid unnecessary consumption of the polymerizable unsaturated bond. C., more preferably 0.degree. To 70.degree. C., and most preferably 50.degree. To 70.degree.
　本発明の製造方法において、ポリウレタンプレポリマー（Ａ１）の酸性基を中和する工程（β）と、ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）とは、どちらを先に行ってもよいし、同時に行うこともできる。この場合、（Ａ１）と（Ｂ）と水系媒体と酸性基中和剤とを一度に混合してもよいし、酸性基中和剤を予め水系媒体や（Ｂ）に混合しておき、これらと（Ａ１）とを混合してもよい。 In the production method of the present invention, the step (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium The dispersing step (γ) may be carried out earlier or simultaneously. In this case, (A1), (B), the aqueous medium and the acidic group neutralizing agent may be mixed at one time, or the acidic group neutralizing agent is previously mixed in the aqueous medium or (B), And (A1) may be mixed.
　ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）と、ポリウレタンプレポリマー（Ａ１）と鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂を得る工程（δ）とは同時に行うこともできる。この場合、（Ａ１）と（Ｃ）と（Ｂ）と水系媒体とを一度に混合してもよいし、（Ｃ）を予め水系媒体に混合しておき、これらと（Ａ１）や（Ｂ）とを混合してもよい。 A step (γ) of dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium, and reacting the polyurethane prepolymer (A1) and the chain extender (C) It can also be performed simultaneously with the process ((delta)) which obtains aqueous polyurethane resin. In this case, (A1), (C), (B) and the aqueous medium may be mixed at one time, or (C) may be mixed in advance with the aqueous medium, and these may be mixed with (A1) or (B) And may be mixed.
　ポリウレタンプレポリマー（Ａ１）の酸性基を中和する工程（β）と、ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）と、ポリウレタンプレポリマー（Ａ）と鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂を得る工程（δ）とを同時に行うこともできる。この場合、（Ａ１）と（Ｃ）と（Ｂ）と酸性基中和剤と水系媒体とを一度に混合してもよいし、（Ｃ）や酸性基中和剤を、予め水系媒体や（Ｂ）に混合しておき、これらと（Ａ１）や（Ｂ）とを混合してもよい。 A step (β) of neutralizing the acid group of the polyurethane prepolymer (A1), and a step (γ) of dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium The step (δ) of reacting the polyurethane prepolymer (A) with the chain extender (C) to obtain an aqueous polyurethane resin can also be carried out simultaneously. In this case, (A1), (C), (B), the acidic group neutralizing agent and the aqueous medium may be mixed at one time, or (C) or the acidic group neutralizing agent may It may be mixed in B), and these may be mixed with (A1) or (B).
　ポリウレタンプレポリマー（Ａ１）と鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂を得る工程（δ）において、反応は冷却下でゆっくりと行ってもよく、また場合によっては６０℃以下の加熱条件下で反応を促進して行ってもよい。冷却下における反応時間は、０．５～２４時間程度とすることができ、６０℃以下の加熱条件下における反応時間は、０．１～６時間程度とすることができる。 In the step (δ) of reacting the polyurethane prepolymer (A1) with the chain extender (C) to obtain an aqueous polyurethane resin, the reaction may be carried out slowly with cooling, and in some cases, heating up to 60 ° C. or less The reaction may be promoted under conditions. The reaction time under cooling can be about 0.5 to 24 hours, and the reaction time under heating conditions of 60 ° C. or less can be about 0.1 to 6 hours.
　水性ポリウレタン樹脂分散体の固形分（重合性不飽和結合を有する化合物（Ｂ）を含む）の全量を１００重量部とした場合、ポリウレタン樹脂（Ａ）は、５～６０重量部が好ましく、より好ましくは１５～５０重量部であり、さらに好ましくは２５～４０重量部である。ポリウレタン樹脂（Ａ）の数平均分子量は、１,０００～１,０００,０００であることが好ましい。光硬化前の乾燥塗膜のタックフリー性の観点から、より好ましくは、１０，０００～１,０００,０００である。 When the total amount of solid content (including the compound (B) having a polymerizable unsaturated bond) of the aqueous polyurethane resin dispersion is 100 parts by weight, the polyurethane resin (A) is preferably 5 to 60 parts by weight, and more preferably Is 15 to 50 parts by weight, more preferably 25 to 40 parts by weight. The number average molecular weight of the polyurethane resin (A) is preferably 1,000 to 1,000,000. From the viewpoint of tack-free property of the dried coating before light curing, it is more preferably 10,000 to 1,000,000.
XII．光重合開始剤
　本発明の水性ポリウレタン樹脂分散体には、光重合開始剤を添加することもできる。光重合開始剤は、特に制限されず、公知のものを使用することができる。具体的には、活性エネルギー線（例えば、紫外線）照射によって、容易に開裂して２個のラジカルができる光開裂型又は水素引き抜き型の光重合開始剤を使用することができる。これらを併用することもできる。 XII. Photopolymerization initiator A photopolymerization initiator can also be added to the aqueous polyurethane resin dispersion of the present invention. The photopolymerization initiator is not particularly limited, and known ones can be used. Specifically, a photocleavage type or hydrogen abstraction type photopolymerization initiator capable of being easily cleaved to form two radicals by irradiation with active energy rays (for example, ultraviolet light) can be used. These can also be used together.
　このような光重合開始剤としては、例えば、アセトフェノン、２，２－ジエトキシアセトフェノン、ｐ－ジメチルアミノアセトフェノン、ベンゾフェノン、２－クロロベンゾフェノン、ｐ，ｐ’－ビスジエチルアミノベンゾフェノン、ベンゾインエチルエーテル、ベンゾインｎ－プロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾインｎ－ブチルエーテル、ベンゾインジメチルケタール、チオキサントン、ｐ－イソプロピル－α－ヒドロキシイソブチルフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロシクロヘキシルフェニルケトン、２－メチル－１［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２，４，６，－トリメチルベンゾフェノン、４－メチルベンゾフェノン、２，２－ジメトキシ－１、２－ジフェニルエタノン等が挙げられる。中でも、ヒドロキシシクロヘキシルフェニルケトンが好ましい。 Examples of such a photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, benzoin ethyl ether, benzoin n. -Propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl Ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl- - phenylpropan-1-one, 2,4,6, - trimethyl benzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenyl-ethanone, and the like. Among them, hydroxycyclohexyl phenyl ketone is preferred.
　光重合開始剤を添加する場合は、ポリウレタンプレポリマー（Ａ１）と鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂（Ａ）を得る工程（δ）の後に添加することが好ましい。光重合開始剤の添加量としては、水性ポリウレタン樹脂分散体の全固形分（重合性不飽和結合を有する化合物（Ｂ）を含む）に対して０．５～５重量部が好ましい。 When adding a photoinitiator, it is preferable to add after the process ((delta)) which makes a polyurethane prepolymer (A1) and a chain extender (C) react, and obtains aqueous polyurethane resin (A). The addition amount of the photopolymerization initiator is preferably 0.5 to 5 parts by weight with respect to the total solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond).
XIII．添加剤
　また、本発明の水性ポリウレタン樹脂分散体には、必要に応じて、増粘剤、光増感剤、硬化触媒、紫外線吸収剤、光安定剤、消泡剤、可塑剤、表面調整剤、沈降防止剤等の添加剤を添加することもできる。添加剤は、単独で用いてもよく、複数種を併用してもよい。本発明の水性ポリウレタン樹脂分散体は、得られる塗膜の硬度、耐薬品性の点から、実質的に、保護コロイド、乳化剤、界面活性剤を含まないことが好ましい。 XIII. Additives In the aqueous polyurethane resin dispersion of the present invention, if necessary, a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoamer, a plasticizer, and a surface conditioner Additives such as anti-settling agents can also be added. The additives may be used alone or in combination of two or more. The aqueous polyurethane resin dispersion of the present invention is preferably substantially free of a protective colloid, an emulsifier and a surfactant from the viewpoint of the hardness and chemical resistance of the resulting coating film.
<塗料組成物及びコーティング剤組成物>
　本発明は、前記水性ポリウレタン樹脂分散体を含有する塗料組成物及びコーティング剤組成物にも関する。 <Coating composition and coating composition>
The present invention also relates to a coating composition and a coating composition comprising the aqueous polyurethane resin dispersion.
　本発明の塗料組成物及びコーティング剤組成物には、前記水性ポリウレタン樹脂分散体以外にも、その他の樹脂を添加することもできる。その他の樹脂としては、ポリエステル樹脂、アクリル樹脂、ポリエーテル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、エポキシ樹脂、アルキド樹脂、ポリオレフィン樹脂等が挙げられる。これらは単独で用いてもよいし、複数種を併用してもよい。 Other resins can also be added to the coating composition and the coating agent composition of the present invention in addition to the aqueous polyurethane resin dispersion. Other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins and the like. These may be used alone or in combination of two or more.
　その他の樹脂は、１個以上の親水性基を有することが好ましい。親水性基としては、水酸基、カルボキシ基、スルホン酸基、ポリエチレングリコール基等が挙げられる。 Other resins preferably have one or more hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, a polyethylene glycol group and the like.
　その他の樹脂は、ポリエステル樹脂、アクリル樹脂、ポリオレフィン樹脂からなる群より選ばれる少なくとも１種であることが好ましい。 The other resin is preferably at least one selected from the group consisting of polyester resin, acrylic resin, and polyolefin resin.
　ポリエステル樹脂は、通常、酸成分とアルコ－ル成分とのエステル化反応又はエステル交換反応によって製造することができる。酸成分としては、ポリエステル樹脂の製造に際して酸成分として通常使用される化合物を使用することができる。酸成分としては、例えば、脂肪族多塩基酸、脂環族多塩基酸、芳香族多塩基酸等を使用することができる。
　ポリエステル樹脂の水酸基価は、１０～３００ｍｇＫＯＨ／ｇ程度が好ましく、５０～２５０ｍｇＫＯＨ／ｇ程度がより好ましく、８０～１８０ｍｇＫＯＨ／ｇ程度がさらに好ましい。ポリエステル樹脂の酸価は、１～２００ｍｇＫＯＨ／ｇ程度が好ましく、１５～１００ｍｇＫＯＨ／ｇ程度がより好ましく、２５～６０ｍｇＫＯＨ／ｇ程度がさらに好ましい。
　ポリエステル樹脂の重量平均分子量は、５００～５００，０００が好ましく、１，０００～３００，０００がより好ましく、１，５００～２００，０００がさらに好ましい。 The polyester resin can be usually produced by an esterification reaction or transesterification reaction of an acid component and an alcohol component. As the acid component, compounds which are usually used as an acid component in the production of polyester resins can be used. As an acid component, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid etc. can be used, for example.
The hydroxyl value of the polyester resin is preferably about 10 to 300 mg KOH / g, more preferably about 50 to 250 mg KOH / g, and still more preferably about 80 to 180 mg KOH / g. The acid value of the polyester resin is preferably about 1 to 200 mg KOH / g, more preferably about 15 to 100 mg KOH / g, and still more preferably about 25 to 60 mg KOH / g.
The weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, and still more preferably 1,500 to 200,000.
　アクリル樹脂としては、水酸基含有アクリル樹脂が好ましい。水酸基含有アクリル樹脂は、水酸基含有重合性不飽和モノマー及び該水酸基含有重合性不飽和モノマーと共重合可能な他の重合性不飽和モノマーとを、例えば、有機溶媒中での溶液重合法、水中でのエマルション重合法等の既知の方法によって共重合させることにより製造できる。
　水酸基含有重合性不飽和モノマーは、１分子中に水酸基及び重合性不飽和結合をそれぞれ１個以上有する化合物である。例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物；これらのモノエステル化物のε－カプロラクトン変性体；Ｎ－ヒドロキシメチル（メタ）アクリルアミド；アリルアルコール；分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等を挙げることができる。 As an acrylic resin, a hydroxyl group-containing acrylic resin is preferable. The hydroxyl group-containing acrylic resin comprises, for example, a solution polymerization method in an organic solvent, a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, in water It can manufacture by copolymerizing by well-known methods, such as the emulsion polymerization method of this.
The hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl group and one or more polymerizable unsaturated bond in one molecule. For example, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like, and having 2 to 8 carbon atoms Monoesters with dihydric alcohols; ε-caprolactone modified products of these monoesters; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is a hydroxyl group Etc. can be mentioned.
　水酸基含有アクリル樹脂は、アニオン性官能基を有することが好ましい。アニオン性官能基を有する水酸基含有アクリル樹脂については、例えば、重合性不飽和モノマーの１種として、カルボン酸基、スルホン酸基、リン酸基等のアニオン性官能基を有する重合性不飽和モノマーを用いることにより製造できる。
　水酸基含有アクリル樹脂の水酸基価は、水性ポリウレタン樹脂分散体の貯蔵安定性や得られる塗膜の耐水性等の観点から、１～２００ｍｇＫＯＨ／ｇ程度が好ましく、２～１００ｍｇＫＯＨ／ｇ程度がより好ましく、３～６０ｍｇＫＯＨ／ｇ程度がさらに好ましい。
　水酸基含有アクリル樹脂がカルボキシ基等の酸性基を有する場合、水酸基含有アクリル樹脂の酸価は、得られる塗膜の耐水性等の観点から、１～２００ｍｇＫＯＨ／ｇ程度が好ましく、２～１５０ｍｇＫＯＨ／ｇ程度がより好ましく、５～１００ｍｇＫＯＨ／ｇ程度がさらに好ましい。
　水酸基含有アクリル樹脂の重量平均分子量は、１，０００～２００，０００が好ましく、２，０００～１００，０００がより好ましく、さらに好ましくは３，０００～５０，０００の範囲内である。 The hydroxyl group-containing acrylic resin preferably has an anionic functional group. The hydroxyl group-containing acrylic resin having an anionic functional group may be, for example, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group or a phosphoric acid group as one of the polymerizable unsaturated monomers. It can be manufactured by using.
The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mg KOH / g, and more preferably about 2 to 100 mg KOH / g, from the viewpoint of storage stability of the aqueous polyurethane resin dispersion and water resistance of the obtained coating film. About 3 to 60 mg KOH / g is more preferable.
When the hydroxyl group-containing acrylic resin has an acidic group such as a carboxy group, the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mg KOH / g, and preferably 2 to 150 mg KOH / g from the viewpoint of water resistance and the like of the obtained coating. The degree is more preferable, and about 5 to 100 mg KOH / g is more preferable.
The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably 3,000 to 50,000.
　ポリエーテル樹脂としては、エーテル結合を有する重合体又は共重合体が挙げられ、例えばポリオキシエチレン系ポリエーテル、ポリオキシプロピレン系ポリエーテル、ポリオキシブチレン系ポリエーテル、ビスフェノールＡ又はビスフェノールＦ等の芳香族ポリヒドロキシ化合物から誘導されるポリエーテル等が挙げられる。
　ポリカーボネート樹脂としては、ビスフェノール化合物から製造された重合体が挙げられ、例えばビスフェノールＡ・ポリカーボネート等が挙げられる。
　ポリウレタン樹脂としては、アクリル、ポリエステル、ポリエーテル、ポリカーボネート等の各種ポリオール成分とポリイソシアネートとの反応によって得られるウレタン結合を有する樹脂が挙げられる。 Examples of the polyether resin include polymers or copolymers having an ether bond, and examples thereof include polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether, bisphenol A, bisphenol F and the like. And polyethers derived from group polyhydroxy compounds.
As polycarbonate resin, the polymer manufactured from the bisphenol compound is mentioned, For example, bisphenol A polycarbonate etc. are mentioned.
As a polyurethane resin, resin which has a urethane bond obtained by reaction of various polyol components, such as an acryl, polyester, a polyether, and a polycarbonate, and polyisocyanate is mentioned.
　エポキシ樹脂としては、ビスフェノール化合物とエピクロルヒドリンの反応によって得られる樹脂等が挙げられる。ビスフェノールとしては、例えば、ビスフェノールＡ、ビスフェノールＦが挙げられる。
　アルキド樹脂としては、フタル酸、テレフタル酸、コハク酸等の多塩基酸と多価アルコールに、さらに油脂・油脂脂肪酸（大豆油、アマニ油、ヤシ油、ステアリン酸等）、天然樹脂（ロジン、コハク等）等の変性剤を反応させて得られたアルキド樹脂が挙げられる。 As an epoxy resin, the resin etc. which are obtained by reaction of a bisphenol compound and epichlorohydrin are mentioned. Examples of bisphenols include bisphenol A and bisphenol F.
Examples of alkyd resins include polybasic acids such as phthalic acid, terephthalic acid and succinic acid and polyhydric alcohols, as well as fats and oils / fat fatty acids (soybean oil, linseed oil, coconut oil, stearic acid etc.), natural resins (rosin, succinic acid) Alkyd resins obtained by reacting modifiers such as e.g.
　ポリオレフィン樹脂としては、オレフィン系モノマーを適宜他のモノマーと通常の重合法に従って重合又は共重合することにより得られるポリオレフィン樹脂を、乳化剤を用いて水分散するか、あるいはオレフィン系モノマーを適宜他のモノマーと共に乳化重合することにより得られる樹脂が挙げられる。また、場合により、前記のポリオレフィン樹脂が塩素化されたいわゆる塩素化ポリオレフィン変性樹脂を用いてもよい。
　オレフィン系モノマーとしては、例えば、エチレン、プロピレン、１－ブテン、３－メチル－１－ブテン、４－メチル－１－ペンテン、３－メチル－１－ペンテン、１－ヘプテン、１－ヘキセン、１－デセン、１－ドデセン等のα－オレフィン；ブタジエン、エチリデンノルボルネン、ジシクロペンタジエン、１，５－ヘキサジエン、スチレン類、等の共役ジエン又は非共役ジエン等が挙げられ、これらのモノマーは、単独で用いてもよいし、複数種を併用してもよい。
　オレフィン系モノマーと共重合可能な他のモノマーとしては、例えば、酢酸ビニル、ビニルアルコール、マレイン酸、シトラコン酸、イタコン酸、無水マレイン酸、無水シトラコン酸、無水イタコン酸等が挙げられ、これらのモノマーは、単独で用いてもよいし、複数種を併用してもよい。 As a polyolefin resin, a polyolefin resin obtained by polymerizing or copolymerizing an olefin monomer with another monomer appropriately according to a general polymerization method is dispersed in water using an emulsifying agent, or an olefin monomer is suitably used with another monomer And resins obtained by emulsion polymerization. Moreover, you may use what is called chlorinated polyolefin modified resin in which the said polyolefin resin was chlorinated depending on the case.
Examples of olefin monomers include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1- Α-olefins such as decene and 1-dodecene; conjugated dienes and non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and styrenes, etc. may be mentioned, and these monomers may be used alone You may use together and may use multiple types.
Examples of other monomers copolymerizable with olefin monomers include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, etc., and these monomers These may be used alone or in combination of two or more.
　本発明の塗料組成物及びコーティング剤組成物には、硬化剤を含有させることにより、塗料組成物又はコーティング剤組成物を用いた塗膜又は複層塗膜、コーティング膜の耐水性等を向上させることができる。 The coating composition and the coating agent composition of the present invention improve the water resistance and the like of the coating film or multilayer coating film, coating film using the coating composition or the coating agent composition, by containing a curing agent. be able to.
　硬化剤としては、例えば、アミノ樹脂、ポリイソシアネート、ブロック化ポリイソシアネート、メラミン樹脂、カルボジイミド等を用いることできる。硬化剤は、１種のみを単独で用いてもよいし、複数種を併用してもよい。 As the curing agent, for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like can be used. The curing agent may be used alone or in combination of two or more.
　アミノ樹脂としては、例えば、アミノ成分とアルデヒド成分との反応によって得られる部分もしくは完全メチロール化アミノ樹脂が挙げられる。アミノ成分としては、例えば、メラミン、尿素、ベンゾグアナミン、アセトグアナミン、ステログアナミン、スピログアナミン、ジシアンジアミド等が挙げられる。アルデヒド成分としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンツアルデヒド等が挙げられる。 The amino resin includes, for example, partially or completely methylated amino resin obtained by the reaction of an amino component and an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiloganamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
　ポリイソシアネートとしては、例えば、１分子中に２個以上のイソシアナト基を有する化合物が挙げられ、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等が挙げられる。 Examples of the polyisocyanate include compounds having two or more isocyanato groups in one molecule, and examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
　ブロック化ポリイソシアネートとしては、前述のポリイソシアネートのポリイソシアナト基にブロック剤を付加することによって得られるものが挙げられ、ブロック化剤としては、フェノール、クレゾール等のフェノール系、メタノール、エタノール等の脂肪族アルコール系、マロン酸ジメチル、アセチルアセトン等の活性メチレン系、ブチルメルカプタン、ドデシルメルカプタン等のメルカプタン系、アセトアニリド、酢酸アミド等の酸アミド系、ε－カプロラクタム、δ－バレロラクタム等のラクタム系、コハク酸イミド、マレイン酸イミド等の酸イミド系、アセトアルドオキシム、アセトンオキシム、メチルエチルケトオキシム等のオキシム系、ジフェニルアニリン、アニリン、エチレンイミン等のアミン系等のブロック化剤が挙げられる。 Examples of blocked polyisocyanates include those obtained by adding a blocking agent to the polyisocyanate group of the aforementioned polyisocyanate, and examples of blocking agents include phenols such as phenol and cresol, etc., methanol, ethanol and the like. Aliphatic alcohols, active methylenes such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetic acid amide, lactams such as ε-caprolactam and δ-valerolactam, and amber Blocking agents such as acid imides such as acid imides and maleimides, oximes such as acetoaldoxime, acetone oxime and methyl ethyl ketoxime, and amines such as diphenyl aniline, aniline and ethylene imine; Be
　メラミン樹脂としては、例えば、ジメチロールメラミン、トリメチロールメラミン等のメチロールメラミン；これらのメチロールメラミンのアルキルエーテル化物又は縮合物；メチロールメラミンのアルキルエーテル化物の縮合物等をあげることができる。 Examples of melamine resins include methylolmelamines such as dimethylolmelamine and trimethylolmelamine; alkyl ethers or condensates of these methylolmelamines; and condensates of alkylolates of methylolmelamine.
　本発明の塗料組成物及びコーティング剤組成物には、着色顔料や体質顔料、光輝性顔料を添加することができる。
　着色顔料としては、例えば、酸化チタン、亜鉛華、カーボンブラック、モリブデンレッド、プルシアンブルー、コバルトブルー、アゾ顔料、フタロシアニン顔料、キナクリドン顔料、イソインドリン顔料、スレン系顔料、ペリレン顔料等が挙げられる。これらは、単独で用いてもよいし、複数種を併用してもよい。特に、着色顔料として、酸化チタン及び／又はカーボンブラックを使用することが好ましい。
　体質顔料としては、例えば、クレー、カオリン、硫酸バリウム、炭酸バリウム、炭酸カルシウム、タルク、シリカ、アルミナホワイト等が挙げられる。これらは、単独で用いてもよいし、複数種を併用してもよい。特に、体質顔料として、硫酸バリウム及び／又はタルクを使用することが好ましく、硫酸バリウムを使用することがより好ましい。
　光輝性顔料は、例えば、アルミニウム、銅、亜鉛、真ちゅう、ニッケル、酸化アルミニウム、雲母、酸化チタンや酸化鉄で被覆された酸化アルミニウム、酸化チタンや酸化鉄で被覆された雲母等を使用することができる。 A color pigment, an extender pigment and a bright pigment can be added to the coating composition and the coating agent composition of the present invention.
Examples of color pigments include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, graphene pigments, perylene pigments and the like. These may be used alone or in combination of two or more. In particular, it is preferable to use titanium oxide and / or carbon black as a color pigment.
Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white and the like. These may be used alone or in combination of two or more. In particular, it is preferable to use barium sulfate and / or talc as an extender pigment, and it is more preferable to use barium sulfate.
As the bright pigment, for example, aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, etc. may be used. it can.
　本発明の塗料組成物及びコーティング剤組成物には、必要に応じて、増粘剤、硬化触媒、紫外線吸収剤、光安定剤、消泡剤、可塑剤、表面調整剤、沈降防止剤等の通常の塗料用添加剤を含有することができる。これらは、単独で用いてもよいし、複数種を併用してもよい。
　本発明の塗料組成物及びコーティング剤組成物の製造方法は、特に制限されないが、公知の製造方法を用いることができる。一般的には、塗料組成物及びコーティング剤組成物は、前記水性ポリウレタン樹脂分散体と上述した各種添加剤を混合し、水系媒体を添加し、塗装方法に応じた粘度に調整することにより製造される。 The coating composition and the coating agent composition of the present invention may optionally contain a thickener, a curing catalyst, an ultraviolet light absorber, a light stabilizer, an antifoamer, a plasticizer, a surface conditioner, an antisettling agent, etc. Conventional paint additives can be included. These may be used alone or in combination of two or more.
The method for producing the coating composition and the coating agent composition of the present invention is not particularly limited, but any known production method can be used. Generally, a coating composition and a coating agent composition are produced by mixing the aqueous polyurethane resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the coating method. Ru.
　塗料組成物の被塗装材質又はコーティング剤組成物の被コーティング材質としては、金属、プラスチック、無機物、木材等が挙げられる。
　塗料組成物の塗装方法又はコーティング剤組成物のコーティング方法としては、ベル塗装、スプレー塗装、ロール塗装、シャワー塗装、浸漬塗装等が挙げられる。 As a to-be-coated material of a coating composition or to-be-coated material of a coating agent composition, a metal, a plastics, an inorganic substance, a wood etc. are mentioned.
Examples of the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, dip coating and the like.
　本発明の水性ポリウレタン樹脂分散体、水性ポリウレタン樹脂分散体組成物、塗料組成物、コーティング剤組成物は、所望の基材に塗布又は塗装又はコーティングした後、加熱下又は非加熱下で、水性媒体の少なくとも一部を蒸発させた後、活性エネルギー線を照射することにより硬化させることが好ましい。活性エネルギー線としては、電子線、紫外線又はγ線のような電離性放射線が挙げられ、中でも紫外線が好ましい。 The aqueous polyurethane resin dispersion, the aqueous polyurethane resin dispersion composition, the coating composition, and the coating composition of the present invention are applied to or coated or coated on a desired substrate, and then an aqueous medium with or without heating. After evaporating at least a part of the compound, it is preferable to cure by irradiating active energy rays. As the active energy ray, ionizing radiation such as electron beam, ultraviolet ray or γ ray may be mentioned, and among them, ultraviolet ray is preferable.
　紫外線の光源は、紫外線領域の光を発する光源であれば、特に制限はなく、例えば、キセノンランプ、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク灯、タングステンランプ等が使用できる。照射時間は、重合性不飽和結合を有する化合物の種類、光重合開始剤の種類、被膜厚、紫外線源等の条件により、適宜、変動ささせることができる。作業性の点から、１～６０秒照射することが好ましい。さらに硬化反応を完結させる目的で、紫外線照射後加熱処理することもできる。 The light source of ultraviolet light is not particularly limited as long as it emits light in the ultraviolet region, and for example, a xenon lamp, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc lamp, tungsten lamp and the like can be used. The irradiation time can be appropriately varied depending on conditions such as the type of the compound having a polymerizable unsaturated bond, the type of the photopolymerization initiator, the film thickness, the ultraviolet light source and the like. It is preferable to irradiate for 1 to 60 seconds from the viewpoint of workability. Furthermore, in order to complete the curing reaction, it can also be subjected to heat treatment after ultraviolet irradiation.
　本発明の水性ポリウレタン樹脂分散体、塗料組成物、コーティング剤組成物等を硬化させる際に使用する紫外線の照射量としては、速硬化性、作業性の観点から、３００～３，０００ｍＪ／ｃｍ2が好ましい。 The irradiation amount of the ultraviolet light used when curing the aqueous polyurethane resin dispersion, the coating composition, the coating composition and the like of the present invention is 300 to 3,000 mJ / cm 2 from the viewpoint of fast curing and workability. Is preferred.
　硬化のために、紫外線の他に電子線等を使用することもできる。電子線により硬化させる場合は、光重合開始剤は添加しなくても良く、１００～５００ｅＶのエネルギーを有する電子線加速装置を使用することが好ましい。 In addition to ultraviolet light, electron beams and the like can also be used for curing. In the case of curing by electron beam, a photopolymerization initiator may not be added, and it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.
　次に、実施例及び比較例を挙げて、本発明をさらに詳細に説明する。 Next, the present invention will be described in more detail by way of examples and comparative examples.
［実施例１］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、２５．９ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、１１．１ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、５７．５ｇ）とを、Ｎ－エチルピロリドン（４３．９ｇ）中、ジブチル錫ジラウリレート（０．１ｇ）存在下、窒素雰囲気下で、８０－９０℃で２．５時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。さらに、２分子のアクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（１，６-ＨＤＬ-ＥＰ-Ａ、１２．６ｇ）と、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、１９．７ｇ）を入れ、９０℃で、６時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、４．０１重量％であった。反応混合物を７０℃まで冷却し、これにジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ、７９．９ｇ）と、トリエチルアミン（８．９ｇ）とを添加・混合した。反応混合物（２２６ｇ）を、強攪拌下のもと水（３８６ｇ）の中に加えた。次いで、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、２０．１ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 Example 1
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a mixture of polyols and a carbonate ester, the content of alicyclic structure 39% by weight, 25.9 g), and 2,2-dimethylol Propionic acid (DMPA, 11.1 g) and isophorone diisocyanate (IPDI, 57.5 g) in N-ethylpyrrolidone (43.9 g) in the presence of dibutyltin dilaurate (0.1 g) under a nitrogen atmosphere, Heat at 80-90 ° C. for 2.5 hours. 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. Furthermore, the reaction product of 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl (1,6-HDL-EP-A, 12.6 g), and pentaerythritol triacrylate (PETA, 19. 7 g) was added and heated at 90 ° C. for 6 hours. The NCO group content at the end of the urethanization reaction was 4.01% by weight. The reaction mixture was cooled to 70 ° C., to which dipentaerythritol hexaacrylate (DPHA, 79.9 g) and triethylamine (8.9 g) were added and mixed. The reaction mixture (226 g) was added into water (386 g) under vigorous stirring. Then, 35% by weight of an aqueous 2-methyl-1,5-pentanediamine solution (MPMD, 20.1 g) was added to obtain an aqueous polyurethane resin dispersion.
［実施例２］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、４０．３ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、９．７ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、４６．３ｇ）とを、Ｎ－エチルピロリドン（４０．５ｇ）中、ジブチル錫ジラウリレート（０．１ｇ）存在下、窒素雰囲気下で、８０－９０℃で２．５時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。さらに、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、１６．１ｇ）を入れ、９０℃で、５時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、３．５１重量％であった。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、７２．５ｇ）と、トリエチルアミン（７．８ｇ）とを添加・混合した。反応混合物（２１０ｇ）を、強攪拌下のもと水（３５３ｇ）の中に加えた。次いで、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、１５．８ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 Example 2
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a polyol mixture with a molar ratio of 3: 1, an alicyclic structure content of 39% by weight, 40.3 g), and 2,2-dimethylol Propionic acid (DMPA, 9.7 g) and isophorone diisocyanate (IPDI, 46.3 g) in N-ethylpyrrolidone (40.5 g) in the presence of dibutyltin dilaurate (0.1 g) under a nitrogen atmosphere, Heat at 80-90 ° C. for 2.5 hours. 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. Further, pentaerythritol triacrylate (PETA, 16.1 g) was added and heated at 90 ° C. for 5 hours. The NCO group content at the end of the urethanization reaction was 3.51% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 72.5 g) and triethylamine (7.8 g) were added and mixed. The reaction mixture (210 g) was added into water (353 g) under vigorous stirring. Then, 35% by weight of an aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 15.8 g) was added to obtain an aqueous polyurethane resin dispersion.
［実施例３］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、５６．１ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、２３．５ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、１２４ｇ）とを、Ｎ－エチルピロリドン（９６．４ｇ）中、ジブチル錫ジラウリレート（０．２ｇ）存在下、窒素雰囲気下で、８０－９０℃で３時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．５ｇ）と、４－メトキシフェノール（０．５ｇ）とを加え、雰囲気を空気とした。さらに、２分子のアクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（１，６-ＨＤＬ-ＥＰ-Ａ、２７．７ｇ）と、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、４２．３ｇ）を入れ、９０℃で、５時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、４．０５重量％であった。反応混合物を７０℃まで冷却し、これにジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ、１７８ｇ）と、トリエチルアミン（１９．５ｇ）とを添加・混合した。反応混合物（２５１ｇ）を、強攪拌下のもと水（４２３ｇ）の中に加えた。次いで、３５重量％のジエチレントリアミン水溶液（ＤＥＴＡ、１３．３ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 [Example 3]
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a mixture of polyols and a carbonate, molar ratio 39% by weight of alicyclic structure, 56.1 g), and 2,2-dimethylol Propionic acid (DMPA, 23.5 g) and isophorone diisocyanate (IPDI, 124 g) in N-ethylpyrrolidone (96.4 g) in the presence of dibutyltin dilaurate (0.2 g) under nitrogen atmosphere. Heated at 90 ° C. for 3 hours. 2,6-Di-tert-butyl-4-methylphenol (0.5 g) and 4-methoxyphenol (0.5 g) were added and the atmosphere was air. Furthermore, the reaction product of 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl (1,6-HDL-EP-A, 27.7 g) and pentaerythritol triacrylate (PETA, 42. 3 g) was added and heated at 90 ° C. for 5 hours. The NCO group content at the end of the urethanization reaction was 4.05% by weight. The reaction mixture was cooled to 70 ° C., to which dipentaerythritol hexaacrylate (DPHA, 178 g) and triethylamine (19.5 g) were added and mixed. The reaction mixture (251 g) was added into water (423 g) under vigorous stirring. Then, 35 wt% aqueous diethylenetriamine solution (DETA, 13.3 g) was added to obtain an aqueous polyurethane resin dispersion.
［実施例４］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、５６．１ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、２３．５ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、１２４ｇ）とを、Ｎ－エチルピロリドン（９６．４ｇ）中、ジブチル錫ジラウリレート（０．２ｇ）存在下、窒素雰囲気下で、８０－９０℃で３時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．５ｇ）と、４－メトキシフェノール（０．５ｇ）とを加え、雰囲気を空気とした。さらに、２分子のアクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（１，６-ＨＤＬ-ＥＰ-Ａ、２７．７ｇ）と、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、４２．３ｇ）を入れ、９０℃で、５時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、４．０５重量％であった。反応混合物を７０℃まで冷却し、これにジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ、１７８ｇ）と、トリエチルアミン（１９．５ｇ）とを添加・混合した。反応混合物（２３２ｇ）を、強攪拌下のもと水（３９１ｇ）の中に加えた。次いで、３５重量％のジエチレントリアミン水溶液（ＤＥＴＡ、６．１ｇ）と、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、１０．４ｇ）とを加えて、水性ポリウレタン樹脂分散体を得た。 Example 4
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a mixture of polyols and a carbonate, molar ratio 39% by weight of alicyclic structure, 56.1 g), and 2,2-dimethylol Propionic acid (DMPA, 23.5 g) and isophorone diisocyanate (IPDI, 124 g) in N-ethylpyrrolidone (96.4 g) in the presence of dibutyltin dilaurate (0.2 g) under nitrogen atmosphere. Heated at 90 ° C. for 3 hours. 2,6-Di-tert-butyl-4-methylphenol (0.5 g) and 4-methoxyphenol (0.5 g) were added and the atmosphere was air. Furthermore, the reaction product of 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl (1,6-HDL-EP-A, 27.7 g) and pentaerythritol triacrylate (PETA, 42. 3 g) was added and heated at 90 ° C. for 5 hours. The NCO group content at the end of the urethanization reaction was 4.05% by weight. The reaction mixture was cooled to 70 ° C., to which dipentaerythritol hexaacrylate (DPHA, 178 g) and triethylamine (19.5 g) were added and mixed. The reaction mixture (232 g) was added into water (391 g) under vigorous stirring. Next, a 35 wt% aqueous solution of diethylenetriamine (DETA, 6.1 g) and a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 10.4 g) are added to obtain an aqueous polyurethane resin dispersion. Obtained.
［実施例５］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、２５．２ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、１０．６ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、５６．１ｇ）とを、Ｎ－エチルピロリドン（４２．９ｇ）中、ジブチル錫ジラウリレート（０．１ｇ）存在下、窒素雰囲気下で、８０－９０℃で２時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。さらに、２分子のアクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（１，６-ＨＤＬ-ＥＰ-Ａ、１２．２ｇ）と、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、１９．９ｇ）を入れ、９０℃で、６時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、３．９５重量％であった。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、７９．１ｇ）と、トリエチルアミン（８．６ｇ）とを添加・混合した。反応混合物（２３３ｇ）を、強攪拌下のもと水（４０１ｇ）の中に加えた。次いで、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、１９．７ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 [Example 5]
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a polyol mixture with a carbonic ester, the content of alicyclic structure 39% by weight, 25.2 g), and 2,2-dimethylol Propionic acid (DMPA, 10.6 g) and isophorone diisocyanate (IPDI, 56.1 g) in N-ethylpyrrolidone (42.9 g) in the presence of dibutyltin dilaurate (0.1 g) under a nitrogen atmosphere, Heat at 80-90 ° C. for 2 hours. 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. Furthermore, the reaction product of two molecules of acrylic acid and one molecule of 1,6-hexanediol diglycidyl (1,6-HDL-EP-A, 12.2 g) and pentaerythritol triacrylate (PETA, 19. 9 g) were placed and heated at 90 ° C. for 6 hours. The NCO group content at the end of the urethanization reaction was 3.95% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 79.1 g) and triethylamine (8.6 g) were added and mixed. The reaction mixture (233 g) was added into water (401 g) under vigorous stirring. Then, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 19.7 g) was added to obtain an aqueous polyurethane resin dispersion.
［実施例６］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、１２１ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、２９．４ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、１３９ｇ）とを、Ｎ－エチルピロリドン（１２１ｇ）中、ジブチル錫ジラウリレート（０．２ｇ）存在下、窒素雰囲気下で、８０－９０℃で２時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．８ｇ）と、４－メトキシフェノール（０．８ｇ）とを加え、雰囲気を空気とした。さらに、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、４６．１ｇ）を入れ、９０℃で、６時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、３．８３重量％であった。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、２２１ｇ）と、トリエチルアミン（２４．１ｇ）とを添加・混合した。反応混合物（２０１ｇ）を、強攪拌下のもと水（３３２ｇ）の中に加えた。次いで、アジピン酸ジヒドラジド（ＡＨ、８．５ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 [Example 6]
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a polyol mixture with a carbonic ester, an alicyclic structure content of 39% by weight, 121 g), and 2,2-dimethylol propionic acid (DMPA, 29.4 g) and isophorone diisocyanate (IPDI, 139 g) in N-ethylpyrrolidone (121 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere at 2 at 80-90 ° C. Heated for time. 2,6-Di-tert-butyl-4-methylphenol (0.8 g) and 4-methoxyphenol (0.8 g) were added, and the atmosphere was changed to air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was added and heated at 90 ° C. for 6 hours. The NCO group content at the end of the urethanization reaction was 3.83% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 221 g) and triethylamine (24.1 g) were added and mixed. The reaction mixture (201 g) was added into water (332 g) under vigorous stirring. Adipic acid dihydrazide (AH, 8.5 g) was then added to obtain an aqueous polyurethane resin dispersion.
［実施例７］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、１２１ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、２９．４ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、１３９ｇ）とを、Ｎ－エチルピロリドン（１２１ｇ）中、ジブチル錫ジラウリレート（０．２ｇ）存在下、窒素雰囲気下で、８０－９０℃で２時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．８ｇ）と、４－メトキシフェノール（０．８ｇ）とを加え、雰囲気を空気とした。さらに、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、４６．１ｇ）を入れ、９０℃で、６時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、３．８３重量％であった。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、２２１ｇ）と、トリエチルアミン（２４．１ｇ）とを添加・混合した。反応混合物（１９９ｇ）を、強攪拌下のもと水（３３７ｇ）の中に加えた。次いで、３５重量％のヒドラジン水溶液（４．８ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 [Example 7]
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a polyol mixture with a carbonic ester, an alicyclic structure content of 39% by weight, 121 g), and 2,2-dimethylol propionic acid (DMPA, 29.4 g) and isophorone diisocyanate (IPDI, 139 g) in N-ethylpyrrolidone (121 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere at 2 at 80-90 ° C. Heated for time. 2,6-Di-tert-butyl-4-methylphenol (0.8 g) and 4-methoxyphenol (0.8 g) were added, and the atmosphere was changed to air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was added and heated at 90 ° C. for 6 hours. The NCO group content at the end of the urethanization reaction was 3.83% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 221 g) and triethylamine (24.1 g) were added and mixed. The reaction mixture (199 g) was added into water (337 g) under vigorous stirring. Next, a 35 wt% aqueous hydrazine solution (4.8 g) was added to obtain an aqueous polyurethane resin dispersion.
［実施例８］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、１２１ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、２９．４ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、１３９ｇ）とを、Ｎ－エチルピロリドン（１２１ｇ）中、ジブチル錫ジラウリレート（０．２ｇ）存在下、窒素雰囲気下で、８０－９０℃で２時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．８ｇ）と、４－メトキシフェノール（０．８ｇ）とを加え、雰囲気を空気とした。さらに、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、４６．１ｇ）を入れ、９０℃で、６時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、３．８３重量％であった。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、２２１ｇ）と、トリエチルアミン（２４．１ｇ）とを添加・混合した。反応混合物（２５３ｇ）を、強攪拌下のもと水（４１０ｇ）の中に加えた。次いで、１３重量％のピペラジン水溶液（４．８ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 [Example 8]
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a polyol mixture with a carbonic ester, an alicyclic structure content of 39% by weight, 121 g), and 2,2-dimethylol propionic acid (DMPA, 29.4 g) and isophorone diisocyanate (IPDI, 139 g) in N-ethylpyrrolidone (121 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere at 2 at 80-90 ° C. Heated for time. 2,6-Di-tert-butyl-4-methylphenol (0.8 g) and 4-methoxyphenol (0.8 g) were added, and the atmosphere was changed to air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was added and heated at 90 ° C. for 6 hours. The NCO group content at the end of the urethanization reaction was 3.83% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 221 g) and triethylamine (24.1 g) were added and mixed. The reaction mixture (253 g) was added into water (410 g) under vigorous stirring. Then, 13 wt% piperazine aqueous solution (4.8 g) was added to obtain an aqueous polyurethane resin dispersion.
［実施例９］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、１００ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、３６．７ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、１４４ｇ）とを、Ｎ－エチルピロリドン（１１４ｇ）中、ジブチル錫ジラウリレート（０．２ｇ）存在下、窒素雰囲気下で、８０－９０℃で２．５時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。さらに、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、２２５ｇ）を入れ、９０℃で、ＮＣＯ基含量が、ほぼ０重量％になるまで加熱した。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、２１９ｇ）と、トリエチルアミン（２８．４ｇ）とを添加・混合した。反応混合物（１１３ｇ）を、強攪拌下のもと水（２０２ｇ）の中に加え、水性ポリウレタン樹脂分散体を得た。 [Example 9]
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a polyol mixture with a carbonic ester, an alicyclic structure content of 39% by weight, 100 g), and 2,2-dimethylol propionic acid (DMPA, 36.7 g) and isophorone diisocyanate (IPDI, 144 g) in N-ethylpyrrolidone (114 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere at 2 at 80-90 ° C. Heated for .5 hours. 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. Furthermore, pentaerythritol triacrylate (PETA, 225 g) was added and heated at 90 ° C. until the NCO group content was approximately 0% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 219 g) and triethylamine (28.4 g) were added and mixed. The reaction mixture (113 g) was added into water (202 g) under strong stirring to obtain an aqueous polyurethane resin dispersion.
［比較例１］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、４０．９ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、１１．８ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、５２．７ｇ）とを、Ｎ－エチルピロリドン（４４．３ｇ）中、ジブチル錫ジラウリレート（０．１ｇ）存在下、窒素雰囲気下で、８０－９０℃で４時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、０．４２重量％であった。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、１０１ｇ）と、トリエチルアミン（８．７ｇ）とを添加・混合した。反応混合物（２２２ｇ）を、強攪拌下のもと水（３６９ｇ）の中に加えた。次いで、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、２４．８ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 Comparative Example 1
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a mixture of polyols and a carbonate, molar ratio 39% by weight of alicyclic structure, 40.9 g), and 2,2-dimethylol Propionic acid (DMPA, 11.8 g) and isophorone diisocyanate (IPDI, 52.7 g) in N-ethylpyrrolidone (44.3 g) in the presence of dibutyltin dilaurate (0.1 g) under a nitrogen atmosphere, Heat at 80-90 ° C. for 4 hours. The NCO group content at the end of the urethanization reaction was 0.42% by weight. 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 101 g) and triethylamine (8.7 g) were added and mixed. The reaction mixture (222 g) was added into water (369 g) under vigorous stirring. Then, 35% by weight of an aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 24.8 g) was added to obtain an aqueous polyurethane resin dispersion.
［比較例２］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＨ１００（宇部興産製；数平均分子量１００４；水酸基価１１２ｍｇＫＯＨ／ｇ；１，６－ヘキサンジオールと炭酸エステルとを反応させて得られたポリカーボネートジオール、４０．８ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、７．４ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、５５．５ｇ）とを、Ｎ－エチルピロリドン（４９．０ｇ）中、ジブチル錫ジラウリレート（０．１ｇ）存在下、窒素雰囲気下で、８０－９０℃で２．５時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。さらに、２分子のアクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（１，６-ＨＤＬ-ＥＰ-Ａ、１５．１ｇ）を入れ、９０℃で、２時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、５．４７重量％であった。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、７８．７ｇ）と、トリエチルアミン（５．６ｇ）とを添加・混合した。反応混合物（２４１ｇ）を、強攪拌下のもと水（３９０ｇ）の中に加えた。次いで、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、２９．１ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 Comparative Example 2
ETERNACOLL (registered trademark) UH 100 (manufactured by Ube Industries, Ltd .; number average molecular weight 1004; hydroxyl value 112 mg KOH / g; obtained by reacting 1,6-hexanediol with carbonate ester in a reaction apparatus equipped with a stirrer and a heater Polycarbonate diol, 40.8 g), 2,2-dimethylol propionic acid (DMPA, 7.4 g) and isophorone diisocyanate (IPDI, 55.5 g) in N-ethylpyrrolidone (49.0 g), dibutyl The mixture was heated at 80-90 ° C. for 2.5 hours in a nitrogen atmosphere in the presence of tin dilaurate (0.1 g). 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. Furthermore, the reaction product of two molecules of acrylic acid and one molecule of 1,6-hexanediol diglycidyl (1,6-HDL-EP-A, 15.1 g) was added and heated at 90 ° C. for 2 hours . The NCO group content at the end of the urethanization reaction was 5.47% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 78.7 g) and triethylamine (5.6 g) were added and mixed. The reaction mixture (241 g) was added into water (390 g) under vigorous stirring. Then, 35% by weight of a 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 29.1 g) was added to obtain an aqueous polyurethane resin dispersion.
［比較例３］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＨ１００（宇部興産製；数平均分子量１００４；水酸基価１１２ｍｇＫＯＨ／ｇ；１，６－ヘキサンジオールと炭酸エステルとを反応させて得られたポリカーボネートジオール、３０．４ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、８．６ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、５０．９ｇ）とを、Ｎ－エチルピロリドン（４３．２ｇ）中、ジブチル錫ジラウリレート（０．１ｇ）存在下、窒素雰囲気下で、８０－９０℃で２時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。さらに、２分子のアクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（１，６-ＨＤＬ-ＥＰ-Ａ、１２．５ｇ）と、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、１６．７ｇ）を入れ、９０℃で、６時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、３．５９重量％であった。反応混合物を７０℃まで冷却し、これにトリメチロールプロパントリアクリレート（ＴＭＰＴＡ、７５．０ｇ）と、トリエチルアミン（６．８ｇ）とを添加・混合した。反応混合物（２２２ｇ）を、強攪拌下のもと水（３７５ｇ）の中に加えた。次いで、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、１６．５ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 Comparative Example 3
ETERNACOLL (registered trademark) UH 100 (manufactured by Ube Industries, Ltd .; number average molecular weight 1004; hydroxyl value 112 mg KOH / g; obtained by reacting 1,6-hexanediol with carbonate ester in a reaction apparatus equipped with a stirrer and a heater Polycarbonate diol, 30.4 g), 2,2-dimethylol propionic acid (DMPA, 8.6 g) and isophorone diisocyanate (IPDI, 50.9 g) in N-ethylpyrrolidone (43.2 g), dibutyl The mixture was heated at 80-90 ° C. for 2 hours in a nitrogen atmosphere in the presence of tin dilaurate (0.1 g). 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. Furthermore, the reaction product of two molecules of acrylic acid and one molecule of 1,6-hexanediol diglycidyl (1,6-HDL-EP-A, 12.5 g), and pentaerythritol triacrylate (PETA, 16). 7 g) was added and heated at 90 ° C. for 6 hours. The NCO group content at the end of the urethanization reaction was 3.59% by weight. The reaction mixture was cooled to 70 ° C., to which trimethylolpropane triacrylate (TMPTA, 75.0 g) and triethylamine (6.8 g) were added and mixed. The reaction mixture (222 g) was added into water (375 g) under vigorous stirring. Then, 35% by weight of an aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 16.5 g) was added to obtain an aqueous polyurethane resin dispersion.
［比較例４］
　攪拌機及び加熱器を備えた反応装置で、ＥＴＥＲＮＡＣＯＬＬ（登録商標）　ＵＭ９０（３／１）（宇部興産製；数平均分子量９１６；水酸基価１２２ｍｇＫＯＨ／ｇ；ポリオール成分が１，４－シクロヘキサンジメタノール：１，６－ヘキサンジオール＝３：１のモル比のポリオール混合物と炭酸エステルとを反応させて得られたポリカーボネートジオール、脂環構造含有率３９重量％、４１．１ｇ）と、２，２－ジメチロールプロピオン酸（ＤＭＰＡ、１７．６ｇ）と、イソホロンジイソシアネート（ＩＰＤＩ、９１．３ｇ）とを、Ｎ－エチルピロリドン（６９．８ｇ）中、ジブチル錫ジラウリレート（０．１ｇ）存在下、窒素雰囲気下で、８０－９０℃で２．５時間加熱した。２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（０．２ｇ）と、４－メトキシフェノール（０．２ｇ）とを加え、雰囲気を空気とした。さらに、２分子のアクリル酸と１分子の１，６－ヘキサンジオールジグリシジルとの反応生成物（１，６-ＨＤＬ-ＥＰ-Ａ、２１．６ｇ）と、ペンタエリスリトールトリアクリレート（ＰＥＴＡ、２９．３ｇ）を入れ、９０℃で、６時間加熱した。ウレタン化反応終了時のＮＣＯ基含量は、３．９６重量％であった。反応混合物を７０℃まで冷却し、トリエチルアミン（１４．３ｇ）を添加・混合した。反応混合物（２４１ｇ）を、強攪拌下のもと水（３３４ｇ）の中に加えた。次いで、３５重量％の２－メチル－１，５－ペンタンジアミン水溶液（ＭＰＭＤ、２９．５ｇ）を加えて、水性ポリウレタン樹脂分散体を得た。 Comparative Example 4
A reactor equipped with a stirrer and a heater, ETERACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mg KOH / g; polyol component: 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate mixture obtained by reacting a mixture of polyols and a carbonate, molar ratio 39% by weight of alicyclic structure, 41.1 g), and 2,2-dimethylol Propionic acid (DMPA, 17.6 g) and isophorone diisocyanate (IPDI, 91.3 g) in N-ethylpyrrolidone (69.8 g) in the presence of dibutyltin dilaurate (0.1 g) under a nitrogen atmosphere, Heat at 80-90 ° C. for 2.5 hours. 2,6-Di-tert-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (0.2 g) were added, and the atmosphere was changed to air. Furthermore, the reaction product of 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl (1,6-HDL-EP-A, 21.6 g) and pentaerythritol triacrylate (PETA, 29. 3 g) was added and heated at 90 ° C. for 6 hours. The NCO group content at the end of the urethanization reaction was 3.96% by weight. The reaction mixture was cooled to 70 ° C., and triethylamine (14.3 g) was added and mixed. The reaction mixture (241 g) was added into water (334 g) under vigorous stirring. Then, 35% by weight of an aqueous 2-methyl-1,5-pentanediamine solution (MPMD, 29.5 g) was added to obtain an aqueous polyurethane resin dispersion.
［鉛筆硬度と密着性の試料作成］
　実施例１～９、比較例１～４の各水性ポリウレタン樹脂分散体に、重合開始剤（ＩＲＧＡＣＵＲＥ５００、チバスペシャリティケミカル社製）を３重量％／固形分を添加し、よく撹拌してコーティング剤を得た。これをＡＢＳ樹脂、アクリル樹脂、ＰＣ樹脂上に乾燥後の膜厚が約２０μｍになるように均一にそれぞれ塗布した。次いで、６０℃にて３０分乾燥することで、塗膜（紫外線照射前）を得た。得られた塗膜を、高圧水銀ランプの下に通過させた（１回照射、紫外線照射量１０００ｍＪ／ｃｍ２）。得られたポリウレタン樹脂塗膜を、鉛筆硬度測定、及び、密着性の評価に供した。 [Sample preparation of pencil hardness and adhesion]
To each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4, 3% by weight / solid content of a polymerization initiator (IRGACURE 500, manufactured by Ciba Specialty Chemical Co., Ltd.) is added, and the coating agent is Obtained. This was uniformly applied on ABS resin, acrylic resin and PC resin so that the film thickness after drying was about 20 μm. Subsequently, the coating film (before ultraviolet irradiation) was obtained by drying at 60 degreeC for 30 minutes. The obtained coating film was passed under a high pressure mercury lamp (single irradiation, ultraviolet irradiation amount 1000 mJ / cm 2 ). The obtained polyurethane resin coating film was subjected to pencil hardness measurement and adhesion evaluation.
（硬さの評価）
　ポリウレタン樹脂塗膜の鉛筆硬度を測定することにより、評価した。
［鉛筆硬度の測定］
　前記で得られたアクリル樹脂上のポリウレタン樹脂塗膜において、樹脂塗膜の鉛筆硬度をＪＩＳ　Ｋ　５６００－５－４に準拠した方法で測定した。 (Evaluation of hardness)
It evaluated by measuring the pencil hardness of a polyurethane resin coating film.
[Measurement of pencil hardness]
In the polyurethane resin coating on the acrylic resin obtained above, the pencil hardness of the resin coating was measured by the method according to JIS K 5600-5-4.
（密着性の評価）
　前記で得られたＡＢＳ樹脂、アクリル樹脂、ＰＣ樹脂上のポリウレタン樹脂塗膜において、碁盤目剥離法により評価した。すなわち試験片にカッターで４ｍｍ２の桝目を２５個作製し、セロハンテープにより剥離性を調べた。 (Evaluation of adhesion)
The polyurethane resin coating film on the ABS resin, acrylic resin, and PC resin obtained above was evaluated by the cross-cut peeling method. That is, 25 square grids of 4 mm 2 were prepared on a test piece with a cutter, and peelability was examined using a cellophane tape.
（貯蔵安定性の評価）
　実施例１～９、比較例１～４の各水性ポリウレタン樹脂分散体の外観を、製造後１週間後に観察し、貯蔵安定性を確認した。評価基準は以下の通りである。
○：変化なし。
×：凝集物が見られる。 (Evaluation of storage stability)
The appearance of each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4 was observed one week after production to confirm storage stability. Evaluation criteria are as follows.
○: No change.
X: Aggregates are observed.
（タックフリー性の評価）
　実施例１～９、比較例１～４の各水性ポリウレタン樹脂分散体に、重合開始剤（ＩＲＧＡＣＵＲＥ５００、チバスペシャリティケミカル社製）を３重量％／固形分を添加し、よく撹拌してコーティング剤を得た。これをアクリル樹脂上に乾燥後の膜厚が約２０μｍになるように均一にそれぞれ塗布した。次いで、６０℃にて３０分乾燥することで、塗膜（紫外線照射前）を得た。塗膜を指でさわり、タックフリー性を評価した。評価基準は以下の通りである。
○：変化なし。
×：指や指紋の跡が残る。 (Evaluation of tack freeness)
To each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4, 3% by weight / solid content of a polymerization initiator (IRGACURE 500, manufactured by Ciba Specialty Chemical Co., Ltd.) is added, and the coating agent is Obtained. This was uniformly applied on an acrylic resin so that the film thickness after drying was about 20 μm. Subsequently, the coating film (before ultraviolet irradiation) was obtained by drying at 60 degreeC for 30 minutes. The coated film was touched with a finger to evaluate tack freeness. Evaluation criteria are as follows.
○: No change.
X: Traces of fingers and fingerprints remain.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表中の重量部は、樹脂中の全固形分（アクリル化合物を含む）を１００重量部としたときの各化合物の重量部を表す。
　表中の鉛筆硬度は、例えば、「Ｈ」とは、Ｈの鉛筆で全く傷がつかないことを示す。「「２Ｈ～３Ｈ」とは、３Ｈの鉛筆で、傷がついたり、つかなかったりし、２Ｈでは、全く傷がつかないことを示す。
　表中の密着性は、剥離試験の結果を示す。「２５/２５」とは、試験後、２５マス中、２５マス密着していることを示す。 The parts by weight in the table represent the parts by weight of each compound when the total solid content (including the acrylic compound) in the resin is 100 parts by weight.
The pencil hardness in the table, for example, “H” indicates that the pencil of H does not scratch at all. "" 2H-3H "indicates that a 3H pencil is scratched or not, and 2H is not scratched at all.
The adhesion in the table indicates the result of the peeling test. "25/25" indicates that 25 cells in 25 cells are in close contact with each other after the test.
　前記表に示されるように実施例の水性ポリウレタン樹脂分散体は、密着性に優れる塗膜を形成することができ、かつ貯蔵安定性に優れていた。
　ポリウレタン樹脂（Ａ）の調製に、不飽和化合物（ｅ）を使用していない比較例１では、貯蔵安定性に劣っていた。
　ポリウレタン樹脂（Ａ）の調製に、主鎖に脂環構造を有するポリカーボネートジオール（ａ）を使用していない比較例２及び３、水性ポリウレタン樹脂分散体に重合性不飽和結合を有する化合物（Ｂ）を配合していない比較例４は、いずれも密着性に劣っていた。
　比較例２と比較例３との結果を比較することにより、１分子中に水酸基を１個有する不飽和化合物（ｅ’）を用いることによって、水性ポリウレタン樹脂分散体の貯蔵安定性が向上することが分かった。
　また、実施例５と実施例６との結果を比較することにより、１分子中に水酸基を２個以上有する不飽和化合物（ｅ’）を用いることによって、水性ポリウレタン樹脂分散体から得られる塗膜の硬度が高くなることが分かった。
　さらに、実施例１と実施例９との結果を比較することにより、鎖延長剤を用いることによって、紫外線照射前の乾燥塗膜のタックフリー性が高いことが分かった。 As shown in the above table, the aqueous polyurethane resin dispersion of the example was able to form a coating film having excellent adhesion and was excellent in storage stability.
In Comparative Example 1 in which the unsaturated compound (e) was not used for preparation of the polyurethane resin (A), the storage stability was inferior.
Comparative Examples 2 and 3 in which the polycarbonate diol (a) having an alicyclic structure in the main chain is not used for preparation of the polyurethane resin (A), a compound (B) having a polymerizable unsaturated bond in the aqueous polyurethane resin dispersion All were inferior in adhesiveness in Comparative Example 4 which did not mix.
By comparing the results of Comparative Example 2 and Comparative Example 3, the storage stability of the aqueous polyurethane resin dispersion is improved by using the unsaturated compound (e ') having one hydroxyl group in one molecule. I understand.
Further, by comparing the results of Example 5 and Example 6, a coating film obtained from the aqueous polyurethane resin dispersion by using the unsaturated compound (e ′) having two or more hydroxyl groups in one molecule It was found that the hardness of the
Furthermore, by comparing the results of Example 1 and Example 9, it was found that the tack-free property of the dried coating film before UV irradiation was high by using a chain extender.
　本発明の水性ポリウレタン樹脂分散体は、塗料やコーティング剤の原料等として広く利用できる。 The aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for paints and coatings.

Claims (13)

  1. 　少なくとも、重合性不飽和結合を有するポリウレタン樹脂（Ａ）と重合性不飽和結合を有する化合物（Ｂ）を水系媒体中に分散してなる水性ポリウレタン樹脂分散体であって、
    　重合性不飽和結合を有するポリウレタン樹脂（Ａ）が、少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）とを反応させて得られるポリウレタン樹脂であることを特徴とする、水性ポリウレタン樹脂分散体。     An aqueous polyurethane resin dispersion comprising at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond dispersed in an aqueous medium,
    The polyurethane resin (A) having a polymerizable unsaturated bond has at least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and one molecule. An aqueous polyurethane resin dispersion characterized in that it is a polyurethane resin obtained by reacting a compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in body.
  2. 　重合性不飽和結合を有する化合物（Ｂ）が、少なくとも３個の（メタ）アクリロイル基を有する化合物を含む、請求項１に記載の水性ポリウレタン樹脂分散体。 The aqueous polyurethane resin dispersion according to claim 1, wherein the compound (B) having a polymerizable unsaturated bond comprises a compound having at least three (meth) acryloyl groups.
  3. 　重合性不飽和結合を有する化合物（Ｂ）が、少なくとも５個の（メタ）アクリロイル基を有する化合物を含む、請求項１又は２に記載の水性ポリウレタン樹脂分散体。 The aqueous polyurethane resin dispersion according to claim 1 or 2, wherein the compound (B) having a polymerizable unsaturated bond contains a compound having at least five (meth) acryloyl groups.
  4. 　１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）が、１個のイソシアナト基と反応性の基と１個以上の（メタ）アクリロイル基を有する化合物を含む、請求項１～３のいずれか１項に記載の水性ポリウレタン樹脂分散体。 The compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule, and one or more groups having reactivity with one isocyanato group The aqueous polyurethane resin dispersion according to any one of claims 1 to 3, which comprises a compound having a acryloyl group.
  5. 　１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）が、１個のイソシアナト基と反応し得る基と３個以上の（メタ）アクリロイル基を有する化合物を含む、請求項１～４のいずれか１項に記載の水性ポリウレタン樹脂分散体。 A compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule is a group capable of reacting with one isocyanato group and three or more groups ((e) The aqueous polyurethane resin dispersion according to any one of claims 1 to 4, which comprises a compound having a acryloyl group.
  6. 　１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）が、２個の水酸基と２個の（メタ）アクリロイル基を有する化合物を含む、請求項１～５のいずれか１項に記載の水性ポリウレタン樹脂分散体。 Compound (e) having one or more groups capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule, a compound having two hydroxyl groups and two (meth) acryloyl groups The aqueous polyurethane resin dispersion according to any one of claims 1 to 5, which comprises
  7. 　重合性不飽和結合を有するポリウレタン樹脂が、少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）と、鎖延長剤（Ｃ）とを反応させて得られる、請求項１～６のいずれか１に記載の水性ポリウレタン樹脂分散体。 The polyurethane resin having a polymerizable unsaturated bond has at least one polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), and one polyisocyanate (d) in one molecule. The compound according to any one of claims 1 to 6, which is obtained by reacting a compound (e) having the above group capable of reacting with an isocyanato group and one or more polymerizable unsaturated bonds with a chain extender (C). The aqueous polyurethane resin dispersion as described in 1.
  8. 　鎖延長剤（Ｃ）が、１級ポリアミン化合物である、請求項７に記載の水性ポリウレタン樹脂分散体。 The aqueous polyurethane resin dispersion according to claim 7, wherein the chain extender (C) is a primary polyamine compound.
  9. 　少なくとも、主鎖に脂環構造を有するポリカーボネートジオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１分子中に１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合とを有する化合物（ｅ）とを反応させてポリウレタン樹脂（Ａ）を得て、
    　ポリウレタン樹脂（Ａ）及び重合性不飽和結合を有する化合物（Ｂ）を水系媒体に分散させることを含む、請求項１～６のいずれか１項記載の水性ポリウレタン樹脂分散体の製造方法。     At least a polycarbonate diol (a) having an alicyclic structure in its main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and a group capable of reacting with one or more isocyanato groups in one molecule, and 1 A polyurethane resin (A) is obtained by reacting with a compound (e) having at least one polymerizable unsaturated bond,
    The method for producing an aqueous polyurethane resin dispersion according to any one of claims 1 to 6, comprising dispersing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium.
  10. 　少なくとも、主鎖に脂環構造を有するポリカーボネートポリオール（ａ）と、酸性基含有ポリオール（ｂ）と、ポリイソシアネート（ｄ）と、１個以上のイソシアナト基と反応し得る基と１個以上の重合性不飽和結合を有する化合物（ｅ）とを反応させてポリウレタンプレポリマー（Ａ１）を得る工程（α１）と、
    　ポリウレタンプレポリマー（Ａ１）の酸性基を中和する工程（β）と、
    　ポリウレタンプレポリマー（Ａ１）と重合性不飽和結合を有する化合物（Ｂ）とを水系媒体中に分散させる工程（γ）と、
    　ポリウレタンプレポリマー（Ａ１）と、ポリウレタンプレポリマー（Ａ１）のイソシアナト基と反応性を有する鎖延長剤（Ｃ）とを反応させて水性ポリウレタン樹脂を得る工程（δ）とを含む、請求項７又は８記載の水性ポリウレタン樹脂分散体の製造方法。     At least a polycarbonate polyol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and a group capable of reacting with one or more isocyanato groups and one or more polymers. Reacting with a compound (e) having a heterocyclic unsaturated bond to obtain a polyurethane prepolymer (A1) (α1),
    Neutralizing the acid group of the polyurethane prepolymer (A1) (β);
    Dispersing the polyurethane prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium (γ);
    The process according to claim 7 or 8, comprising the step (δ) of reacting the polyurethane prepolymer (A1) with a chain extender (C) having reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin. The manufacturing method of the aqueous polyurethane resin dispersion of 8 statement.
  11. 　さらに光重合開始剤を含有する、請求項１～８のいずれか１項に記載の水性ポリウレタン樹脂分散体。 The aqueous polyurethane resin dispersion according to any one of claims 1 to 8, further comprising a photopolymerization initiator.
  12. 　請求項１～８及び１１のいずれか１項に記載の水性ポリウレタン樹脂分散体を含有する塗料組成物。 A paint composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 8 and 11.
  13. 　請求項１～８及び１１のいずれか１項に記載の水性ポリウレタン樹脂分散体を含有するコーティング剤組成物。 A coating composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 8 and 11.
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