WO2012026475A1 - Dispersion aqueuse de résine polyuréthanne, son procédé de préparation et utilisation - Google Patents

Dispersion aqueuse de résine polyuréthanne, son procédé de préparation et utilisation 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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Prior art keywords
polyurethane resin
compound
group
polymerizable unsaturated
resin dispersion
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PCT/JP2011/068997
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English (en)
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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Priority to JP2012530683A priority Critical patent/JP5821854B2/ja
Priority to CN201180041102.2A priority patent/CN103080164B/zh
Priority to KR1020137007268A priority patent/KR20130099070A/ko
Publication of WO2012026475A1 publication Critical patent/WO2012026475A1/fr

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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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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Cette invention concerne : une dispersion aqueuse de résine polyuréthanne qui manifeste une bonne stabilité au stockage, et une fois durcie par des rayons actiniques (tels que des rayons UV) et convertie en revêtement, adhère bien à diverses matières plastiques (résines ABS, résines acryliques, résines polycarbonates); et une dispersion aqueuse de résine polyuréthanne qui donne un revêtement de dureté élevée. Cette invention concerne une dispersion aqueuse de résine polyuréthanne qui comprend au moins les composés suivants, dispersés dans un milieu aqueux : une résine polyuréthanne (A) ayant des liaisons insaturées polymérisables; et un composé (B) ayant des liaisons insaturées polymérisables. Ladite résine polyuréthanne (A) ayant des liaisons insaturées polymérisables comprend : un polycarbonate diol (a) ayant une structure alicyclique dans sa chaîne principale; un polyol contenant un groupe acide (b); un polyisocyanate (d); et un composé (e), dont chaque molécule contient au moins un groupe qui peut réagir avec un groupe isocyanate et au moins une liaison insaturée polymérisable. Cette invention concerne également une composition de peinture et une composition de revêtement qui contiennent la dispersion aqueuse de résine polyuréthanne précitée et un procédé pour les préparer.
PCT/JP2011/068997 2010-08-25 2011-08-24 Dispersion aqueuse de résine polyuréthanne, son procédé de préparation et utilisation WO2012026475A1 (fr)

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JP2012530683A JP5821854B2 (ja) 2010-08-25 2011-08-24 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
CN201180041102.2A CN103080164B (zh) 2010-08-25 2011-08-24 水性聚氨酯树脂分散体及其制造方法、以及其使用
KR1020137007268A KR20130099070A (ko) 2010-08-25 2011-08-24 수성 폴리우레탄 수지 분산체 및 그의 제조 방법, 및 그의 용도

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JP2018150552A (ja) * 2014-09-29 2018-09-27 富士フイルム株式会社 ゲル粒子
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WO2020083755A1 (fr) * 2018-10-26 2020-04-30 Basf Se Formulation de liant aqueuse
EP3795599A4 (fr) * 2018-05-16 2022-01-26 Ube Industries, Ltd. Composition de résine photodurcissable et adhésif l'utilisant
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JP5821854B2 (ja) 2015-11-24
CN103080164B (zh) 2016-05-18
KR20130099070A (ko) 2013-09-05
CN103080164A (zh) 2013-05-01
JP2016074904A (ja) 2016-05-12
JPWO2012026475A1 (ja) 2013-10-28

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