WO2013077260A1 - Dispersion aqueuse de résine de polyuréthane et son utilisation - Google Patents

Dispersion aqueuse de résine de polyuréthane et son utilisation Download PDF

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Publication number
WO2013077260A1
WO2013077260A1 PCT/JP2012/079752 JP2012079752W WO2013077260A1 WO 2013077260 A1 WO2013077260 A1 WO 2013077260A1 JP 2012079752 W JP2012079752 W JP 2012079752W WO 2013077260 A1 WO2013077260 A1 WO 2013077260A1
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Prior art keywords
polyurethane resin
polyol
aqueous
meth
resin dispersion
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PCT/JP2012/079752
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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 JP2013545899A priority Critical patent/JP5983627B2/ja
Publication of WO2013077260A1 publication Critical patent/WO2013077260A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/08—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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • 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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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

Definitions

  • the present invention relates to a water-based urethane resin dispersion that can be cured by irradiation with active energy rays such as ultraviolet rays and the use thereof.
  • Polycarbonate polyol is a useful compound that can be used as a raw material for polyurethane resins, and can react with isocyanate compounds to produce polyurethane resins used in rigid foams, flexible foams, paints, adhesives, synthetic leather, ink binders, and the like. Moreover, it is known that the coating film obtained by apply
  • 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 of improved adhesion to a substrate and blocking resistance.
  • 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 of improved adhesion to a substrate and blocking resistance.
  • the active energy ray-curable resin composition having a radical polymerizable compound is an active ingredient for various coatings and adhesives such as metal paints, various plastic film overcoat agents, woodwork paints, and printing inks. It is used as For example, an energy ray curable aqueous resin composition in which a (meth) acrylate compound is dispersed in an aqueous polyurethane resin dispersion has been reported (see Patent Document 3). This method is characterized in that a coating film having high hardness is obtained after UV curing.
  • the energy ray curable aqueous resin composition has a drawback that it is inferior in the tack-free property of the coating film before being cured by active energy ray irradiation. If it is inferior in tack-free property, when used as a coating agent, contamination of the coating film such as adhesion of dust tends to occur. Moreover, when using it as components, such as a film comprised from a multilayer, the problem that lamination
  • the present invention relates to an active energy ray (for example, ultraviolet ray) curable aqueous polyurethane resin dispersion, the coating film before curing by irradiation with active energy rays exhibits excellent tack-free properties, and is due to irradiation with active energy rays. It is an object to obtain a water-based polyurethane resin dispersion in which a cured coating film is excellent in adhesion to various plastics.
  • active energy ray for example, ultraviolet ray
  • the present inventors have found that the polyurethane resin (A) having a polymerizable unsaturated bond and no specific polymerizable unsaturated bond are present. It has been found that the problem can be solved by using an aqueous polyurethane resin dispersion in which the polyurethane resin (B) is dispersed in an aqueous medium. According to the present invention, a coating film excellent in tack-free property can be obtained before curing by irradiation with active energy rays, and a coating film having high adhesion to various plastics can be obtained after curing by irradiation with active energy rays.
  • the present invention 1 is an aqueous polyurethane resin dispersion in which at least a polyurethane resin (A) having a polymerizable unsaturated bond and a polyurethane resin (B) having no polymerizable unsaturated bond are dispersed in an aqueous medium.
  • the polyurethane resin (B) is obtained by reacting at least a polyol (Ba), an acidic group-containing polyol (Bb), a polyisocyanate (Bc), and a chain extender (Bd), and
  • the present invention relates to an aqueous polyurethane resin dispersion characterized in that the polyurethane resin (B) has an alicyclic structure content of 16 to 70% by weight.
  • the present invention 2 relates to the aqueous polyurethane resin dispersion of the present invention 1, wherein the polyol (Ba) is a polycarbonate polyol.
  • the present invention 3 relates to the aqueous polyurethane resin dispersion of the present invention 2, wherein the polyol (Ba) is a polycarbonate polyol having an alicyclic structure content of 20 to 65% by weight.
  • Invention 4 comprises mixing an aqueous polyurethane resin dispersion in which the polyurethane resin (A) is dispersed in an aqueous medium and an aqueous polyurethane resin dispersion in which the polyurethane resin (B) is dispersed in an aqueous medium.
  • the present invention 5 has a weight ratio of the aqueous polyurethane resin dispersion in which the polyurethane resin (A) is dispersed in an aqueous medium and the aqueous polyurethane resin dispersion in which the polyurethane resin (B) is dispersed in an aqueous medium,
  • the water-based polyurethane resin dispersion of the present invention 4 is 80:20 to 30:70.
  • the present invention 6 relates to the aqueous polyurethane resin dispersion according to any one of the present inventions 1 to 5, wherein the polyurethane resin (B) has an alicyclic structure content of 29 to 60% by weight.
  • the polyurethane resin (A) comprises at least a polyol (Aa), an acidic group-containing polyol (Ab), a polyisocyanate (Ac), one or more polymerizable unsaturated bonds, and one or more
  • the present invention relates to the aqueous polyurethane resin dispersion according to any one of the present inventions 1 to 6, which is a polyurethane resin obtained by reacting a compound having a hydroxyl group (Ad).
  • Invention 8 provides the polyurethane resin (A) as an aqueous polyurethane in which the polyurethane resin (A) and one or more compounds having a polymerizable unsaturated bond (Ae) are dispersed in an aqueous medium. No.
  • invention 9 is a compound in which the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has three or more polymerizable unsaturated bonds and one or more hydroxyl groups, The present invention relates to the aqueous polyurethane resin dispersion of 7 or 8.
  • invention 10 is a compound in which the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has 5 or more polymerizable unsaturated bonds and one or more hydroxyl groups, The aqueous polyurethane resin dispersion according to the ninth aspect of the present invention.
  • Invention 11 provides the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups as a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.
  • the weight ratio of the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups in the polyurethane resin (A) is 55 to 75% by weight.
  • the present invention 13 relates to the aqueous polyurethane resin dispersion according to any one of the present inventions 7 to 12, wherein the polyol (Aa) is a polycarbonate polyol.
  • the present invention 14 relates to a photocurable composition containing the aqueous polyurethane resin dispersion of any one of the present inventions 1 to 13 and a photopolymerization initiator.
  • the present invention 15 relates to a coating composition containing the aqueous polyurethane resin dispersion of any one of the present inventions 1 to 13.
  • the present invention 16 relates to a coating agent composition containing the aqueous polyurethane resin dispersion according to any one of the present inventions 1 to 13.
  • an aqueous polyurethane resin dispersion in which the coating film before curing by irradiation with active energy rays is excellent in tack-free properties. Moreover, according to this invention, the aqueous polyurethane resin dispersion with which the coating film after hardening by active energy ray irradiation has high hardness is provided.
  • the aqueous polyurethane resin dispersion of the present invention can be a raw material for paints, coating agents, and paint compositions.
  • the present invention includes at least a polyurethane resin (A) having a polymerizable unsaturated bond (hereinafter also referred to as (A)) and a polyurethane resin (B) having no polymerizable unsaturated bond (hereinafter also referred to as (B)).
  • a polyurethane resin (B) having no polymerizable unsaturated bond contains at least a polyol (Ba), an acidic group-containing polyol (Bb), a polyisocyanate (Bc), and a chain extender (Bd).
  • the present invention relates to an aqueous polyurethane resin dispersion characterized in that the polyurethane resin (B) obtained by reacting and having no polymerizable unsaturated bond has an alicyclic structure content of 16 to 70% by weight.
  • the polyurethane resin (A) having a polymerizable unsaturated bond that can be used in the present invention is not particularly limited, and includes at least a polyol (Aa), an acidic group-containing polyol (Ab), a polyisocyanate (Ac), and one piece.
  • a polyurethane resin obtained by reacting the above polymerizable unsaturated bond with a compound (Ad) having one or more hydroxyl groups is preferred, and may be in the form of an aqueous polyurethane dispersion dispersed in an aqueous medium.
  • polyol (Aa) examples include high molecular weight polyols (eg, polycarbonate polyols, polyester polyols, polyether polyols) and low molecular weight polyols.
  • high molecular weight polyols eg, polycarbonate polyols, polyester polyols, polyether polyols
  • low molecular weight polyols In view of ease of production of the polyurethane resin (A), it is preferable to use a high molecular weight diol or a low molecular weight diol.
  • a polyol containing two or more hydroxyl groups and one or more acidic groups in one molecule is included in the acidic group-containing polyol (Ab).
  • the high molecular weight diol is not particularly limited, but preferably has a number average molecular weight of 400 to 8000. If 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 aqueous polyurethane resin dispersion containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks, and further, polyisocyanate (Ac And the polyurethane resin (A) can be produced efficiently.
  • the number average molecular weight of the polyol (Aa) is more preferably 400 to 4000.
  • the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1557. Specifically, the hydroxyl value is measured, and calculated by (56.1 ⁇ 1000 ⁇ valence) / hydroxyl value [mgKOH / g] by a terminal group quantification method.
  • the valence is the number of hydroxyl groups in one molecule.
  • Examples of the high molecular weight diol include polycarbonate diol, polyester diol, and polyether diol.
  • Polycarbonate diol is preferable from the viewpoint of light resistance (weather) resistance, heat resistance, hydrolysis resistance, and oil resistance of the aqueous polyurethane resin dispersion containing the obtained polyurethane resin and a coating film obtained using the same.
  • the diol component is preferably an aliphatic diol and / or an alicyclic diol, and the diol component is more preferably an aliphatic diol. That is, a polycarbonate diol having no alicyclic structure is more preferable.
  • Polycarbonate polyol is obtained by reacting one or more polyol monomers with carbonate ester or phosgene.
  • a polycarbonate polyol obtained by reacting one or more polyol monomers with a carbonate ester is preferred because it is easy to produce and has no by-product formation of terminal chlorinated products.
  • the polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, and a polyether polyol monomer.
  • the aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Linear aliphatic diols such as 1,8-octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Branched aliphatic diols such as pentanediol and 2-methyl-1,9-nonanediol; polyfunctional alcohols having three or more functional groups such as 1,1,1-trimethylolpropane and pentaerythritol.
  • the polyol monomer having an alicyclic structure is not particularly limited.
  • 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1, Alicyclic ring in the main chain such as 4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane
  • Examples include diols having a structure.
  • the aromatic polyol monomer is not particularly limited.
  • the polyester polyol monomer is not particularly limited.
  • a polyester polyol of hydroxycarboxylic acid and diol such as a polyester polyol of 6-hydroxycaproic acid and hexanediol, or a dicarboxylic acid such as polyester polyol of adipic acid and hexanediol.
  • polyester polyol of diol such as polyester polyol of adipic acid and hexanediol.
  • the polyether polyol monomer is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the carbonate ester is not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate.
  • aliphatic carbonates such as dimethyl carbonate and diethyl carbonate
  • aromatic carbonate esters such as diphenyl carbonate
  • cyclic carbonate esters such as ethylene carbonate.
  • phosgene or the like capable of producing a polycarbonate polyol can be used.
  • aliphatic carbonates are preferable and dimethyl carbonate is particularly preferable because of easy production of the polycarbonate polyol.
  • a method for producing a polycarbonate polyol from a polyol monomer and a carbonate ester for example, a carbonate ester and a polyol having an excess number of moles relative to the number of moles of the carbonate ester are added to a reactor, and the temperature is 160 to 200 ° C.
  • An example is a method of reacting at a pressure of about 50 mmHg for 5 to 6 hours and further reacting at 200 to 220 ° C. for several hours at a pressure of several mmHg or less.
  • a catalyst such as titanium tetrabutoxide may be used.
  • Polyester diol is not particularly limited, but for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol Polybutylene sebacate diol, poly- ⁇ -caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid, and the like.
  • the polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, and a random copolymer or block copolymer of ethylene oxide and butylene oxide. Further, a polyether polyester polyol having an ether bond and an ester bond may be used.
  • the low molecular weight diol is not particularly limited, and examples include 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-cyclohexaned
  • Polyol (Aa) may be used alone or in combination of two or more.
  • the acidic group-containing polyol (Ab) that can be 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.
  • the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • the acidic group-containing polyol (Ab) preferably contains a compound having two hydroxyl groups and one carboxy group in one molecule.
  • An acidic group containing polyol (Ab) may be used independently and may use multiple types together.
  • the acidic group-containing polyol (Ab) include dialkanol alkanoic acids including dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid; N, N -Bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acidic group-containing polyether polyol, acidic group-containing polyester polyol, etc. Can be mentioned.
  • dialkanol alkanoic acids including dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid
  • N N -Bishydroxyethylglycine
  • N N-bishydroxyethylalanine
  • 3,4-dihydroxybutanesulfonic acid 3,6-dihydroxy-2-toluenesul
  • dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable, and among dimethylol alkanoic acids, 2,2-dimethylolpropionic acid is more preferable.
  • the total number of hydroxyl equivalents of the polyol (Aa) and the acidic group-containing polyol (Ab) is preferably 120 to 600. If the number of hydroxyl equivalents is within this range, it is easy to produce an aqueous polyurethane resin dispersion containing the polyurethane resin (A), and a coating film excellent in hardness can be easily obtained. From the viewpoint of the storage stability of the resulting aqueous polyurethane resin dispersion and the hardness of the coating film obtained by coating, it is preferably 130 to 600, more preferably 150 to 500, and particularly preferably 170 to 400.
  • the hydroxyl equivalent can be calculated by the following formulas (1) and (2).
  • Number of hydroxyl equivalents of polyol molecular weight of each polyol / number of hydroxyl groups of polyol (1)
  • Total number of hydroxyl equivalents of polyol M / total number of moles of polyol (2)
  • M is [[number of hydroxyl equivalents of polyol (Aa) ⁇ number of moles of polyol (Aa)] + [number of hydroxyl equivalents of acidic group-containing polyol (Ab) ⁇ Mole number of acidic group-containing polyol (Ab)]].
  • 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 include '-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 ''-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate.
  • aliphatic polyisocyanate examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexano Eate.
  • alicyclic polyisocyanate examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-dichlorohexene-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 -Isocyanatoethyl) -4-dichlorohexene-1,2-dicarboxylate 2,5-norbornane diisocyan
  • the number of isocyanato groups per molecule of the polyisocyanate is usually two, but a polyisocyanate having three or more isocyanato groups such as triphenylmethane triisocyanate is also used as long as the polyurethane resin in the present invention does not gel. be able to.
  • polyisocyanates alicyclic polyisocyanates having an alicyclic structure are preferable from the viewpoint of increasing the hardness after UV curing, and isophorone diisocyanate (IPDI), 4,4 ′ is preferable from the viewpoint of easy control of the reaction.
  • IPDI isophorone diisocyanate
  • 4,4 ′ is preferable from the viewpoint of easy control of the reaction.
  • -Dicyclohexylmethane diisocyanate hydrogenated MDI
  • Polyisocyanate may be used alone or in combination of two or more.
  • the polymerizable unsaturated bond in the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups (hereinafter also referred to as unsaturated compound (Ad)) is generated by, for example, a photopolymerization initiator. And a bond contained in an unsaturated group that can be polymerized by a radical or the like.
  • an unsaturated group may be a known one, and includes a group containing an ethylenically unsaturated bond, and a (meth) acryloyl group is preferred from the viewpoint of easy availability and high reactivity.
  • (meth) acryloyl group means acryloyl group or / and methacryloyl group
  • (meth) acrylate means acrylate or / and methacrylate
  • the unsaturated compound (Ad) has at least one polymerizable unsaturated bond in the molecule.
  • the unsaturated compound (Ad) is preferably a compound having three or more polymerizable unsaturated bonds and one or more hydroxyl groups, and a compound having five or more polymerizable unsaturated bonds and one or more hydroxyl groups. It is more preferable that
  • the unsaturated compound (Ad) is preferably a compound having one or more hydroxyl groups and one or more (meth) acryloyl groups from the viewpoint of ease of handling.
  • Examples of the unsaturated compound (Ad) include a hydroxyl group-containing (meth) acrylate, specifically, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Glycerin di (meth) acrylate, diglycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) acrylate, glycidyl (meth) acrylate and (meth) acrylic acid Adducts, glycerin mono (meth) acrylate, diglycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, sorbitol mono (meth) acrylate, diglycerin di (meth) acrylate , Pentaerythritol di (
  • hydroxyl group-containing (meth) acrylates those having 3 or more (meth) acryloyl groups in one molecule are preferable from the viewpoint of increasing the hardness after curing by irradiation with active energy rays (for example, ultraviolet rays). .
  • (meth) acrylate diglycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate
  • Examples include dipentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, and sorbitol tetra (meth) acrylate.
  • the number of (meth) acryloyl groups in one molecule has a primary hydroxyl group in that the production time of the urethane (meth) acrylate resin (A) is shortened among three or more hydroxyl group-containing (meth) acrylates.
  • a (meth) acrylate compound is more preferable.
  • examples of such (meth) acrylates include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. From the viewpoint of the hardness of the coating film and the production time, dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate is a mixture of commercially available dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, It can be supplied as a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
  • Pentaerythritol triacrylate can be supplied as a mixture of commercially available pentaerythritol triacrylate and pentaerythritol tetraacrylate or the like.
  • the hydroxyl value of the mixture is preferably 80 to 130 mgKOH / g.
  • the hydroxyl value is more preferably 85 to 120 mgKOH / g.
  • dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, or mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate Is measured by the method described in JIS K 0070.
  • the unsaturated compound (Ad) a commercially available product may be used as it is.
  • examples of the mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate having a hydroxyl value of 80 mgKOH / g or more include Aronix M403 manufactured by Toagosei Co., Ltd.
  • the unsaturated compound (Ad) may be used alone or in combination of two or more.
  • the amount of the unsaturated compound (Ad) used is preferably 50 to 80% by weight in the polyurethane resin (A) having a polymerizable unsaturated bond. Within this range, the reaction time of the isocyanate group of the unsaturated compound (Ad) and the polyisocyanate (Ac) is set to an appropriate range, and the obtained aqueous polyurethane resin dispersion has good storage stability and is active.
  • the hardness of the coating film after curing by irradiation with energy rays (for example, ultraviolet rays) can be in a favorable range.
  • the amount used is more preferably 55 to 75% by weight, still more preferably 60 to 70% by weight.
  • the polyurethane resin (A) in the present invention is a polyurethane resin obtained by reacting at least a polyol (Aa), an acidic group-containing polyol (Ab), a polyisocyanate (Ac), and an unsaturated compound (Ad). Is preferred.
  • the ratio is preferably 0.3 to 0.95. Within this range, the problem of a long reaction time due to too few moles of hydroxyl groups can be easily avoided, and unreacted polyol (Aa), acidic group-containing polyol (Ab), and unsaturated compound It is easy to avoid the problem that a large amount of (Ad) remains and storage stability is lowered.
  • the ratio of the number of moles of isocyanate groups of the polyisocyanate (Ac) to the number of moles of all hydroxyl groups of the polyol component is preferably 0.4 to 0.9, particularly preferably 0.5 to 0.85.
  • the reaction of the polyol (Aa), the acidic group-containing polyol (Ab), the polyisocyanate (Ac) and the unsaturated compound (Ad) is carried out by (Aa), (Ab), (Ad ) May be reacted with (Ac) in any order, or a plurality of species may be mixed and reacted with (Ac).
  • a catalyst When reacting the polyol (Aa), the acidic group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad), a catalyst may be used.
  • the catalyst is not particularly limited, and examples thereof include salts of metals and organic and inorganic acids such as tin (tin) -based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead-based catalysts (lead octylate, etc.), and organic metals.
  • tin tin
  • amine catalysts triethylamine, N-ethylmorpholine, triethylenediamine, etc.
  • diazabicycloundecene catalysts dibutyltin dilaurate and dioctyltin dilaurate are preferable from the viewpoint of reactivity.
  • the reaction temperature for reacting the polyol (Aa), the acidic group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad) is not particularly limited, but is preferably 40 to 120 ° C. Within this range, the raw materials are sufficiently dissolved, the viscosity of the obtained aqueous dispersion is appropriate, easy to stir, and the polymerizable unsaturated bond in the unsaturated compound (Ad) is a polymerization reaction. It is easy to avoid problems such as gelation and side reactions of isocyanato groups in polyisocyanate (Ac).
  • the reaction temperature is more preferably 60 to 100 ° C.
  • the unsaturated compound (Ad) and the polyisocyanate (Ac) are reacted, it is preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond of the unsaturated compound (Ad). .
  • a polymerization inhibitor in the step of obtaining the polyurethane resin (A), can be added to the reaction system in order to avoid unnecessary consumption of the polymerizable unsaturated bond of the unsaturated compound (Ad). .
  • Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butylhydroquinone, p-tert-butylcatechol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2, Quinone polymerization inhibitors such as 5-bis (1,1-dimethylbutyl) hydroquinone; 2,6-bis (1,1-dimethylethyl) -4-methylphenol, 2,6-di-tert-butylphenol, 2 , 4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, etc.
  • Alkylphenol polymerization inhibitors such as phenothiazine; alkylated di Phenylamine, N, N′-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1 , 4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine, di-p-fluorophenylamine, 2,2 Amine polymerization inhibitors such as 2,6,6-tetramethylpiperidine-1-oxyl (TEMPO); 2,2-diphenylpicrylhydrazyl (DPPH), tri-p-nitrophenylmethyl, N- (3-N -Oxyanilino-1,3-dimethylbutylidene) -aniline oxide, benzyltrimethylammoni
  • TEMPO 2,6,6
  • Ammonium chloride diethylhydroxylamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, bis- (1,2,2,6,6 pentamethyl-4-pipedinyl) sebacate, lactic acid, oxalic acid, citric acid, tartaric acid, benzoic acid
  • Organic acids such as acids; organic phosphines, phosphites and the like. These may be used individually by 1 type and may use multiple types together. In particular, by using a quinone-based polymerization inhibitor and an alkylphenol-based polymerization inhibitor in combination, the consumption due to polymerization of the polymerizable unsaturated bond can be reduced.
  • the addition amount of the polymerization inhibitor can be 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polyurethane resin (A).
  • the reaction of the polyol (Aa), the acidic group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad) may be carried out without a solvent or by adding an organic solvent.
  • the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl acetate.
  • acetone, methyl ethyl ketone, and ethyl acetate are preferable because they can be removed by heating and decompression after the polyurethane prepolymer is dispersed in water.
  • N-methylpyrrolidone and N-ethylpyrrolidone are preferable because they function as a film-forming aid when a coating film is produced from the obtained aqueous polyurethane resin dispersion.
  • the amount of organic solvent added is preferably 0 to 2.0 times based on the weight of the total amount of polyol (Aa), acidic group-containing polyol (Ab), unsaturated compound (Ad), and polyisocyanate (Ac). More preferably, it is 0.05 to 0.7 times.
  • the viscosity at the time of obtaining the aqueous dispersion of a polyurethane resin (A) can be made into an appropriate range, and favorable dispersion
  • the acid value of the polyurethane resin (A) is preferably 10 to 80 mgKOH / g. If it is this range, it will be easy to ensure the dispersibility to an aqueous medium and the water resistance of a coating film.
  • the acid value is more preferably 12 to 70 mgKOH / g, and still more preferably 14 to 60 mgKOH / g.
  • the acid value of the polyurethane resin (A) is an average content of acidic groups in a so-called solid content, and can be derived from the following formula (3).
  • a solvent is used in producing the polyurethane resin (A)
  • a neutralizing agent is used to disperse the polyurethane resin (A) in an aqueous medium, these are excluded in the calculation of the solid content. I will do it.
  • [Acid Value of Polyurethane Resin (A)] [Mole Number of Acid Group of Acid Group-Containing Polyol (Ab)] ⁇ 56.11 / [Polyol (Aa), Acid Group-Containing Polyol (Ab), Unsaturated Compound (Ad And the total weight of polyisocyanate (Ac)] (3)
  • the aqueous dispersion contains a compound (Ae) having a polymerizable unsaturated bond (sometimes referred to as an unsaturated compound (Ae)).
  • the unsaturated compound (Ae) is preferably a radically polymerizable compound.
  • the radical polymerizable compound is not particularly limited as long as it is polymerized in the presence of a photo radical generator or in the presence of a thermal radical generator, but a (meth) acrylate compound is preferable.
  • the unsaturated compound (Ae) does not include the polyurethane resin (A) having a polymerizable unsaturated bond.
  • the unsaturated compound (Ad) is substantially consumed in the synthesis of the polyurethane resin (A).
  • the compound exemplified as the unsaturated compound (Ad) is used. Since it may be added, the unsaturated compound (Ae) may be a compound exemplified as the unsaturated compound (Ad).
  • the unsaturated compound (Ad) When the unsaturated compound (Ad) is supplied to the unsaturated compound (Ae) as a mixture with a compound having a hydroxyl group-free polymerizable unsaturated bond, unreacted in the synthesis of the polyurethane resin (A).
  • a compound having a hydroxyl group-free polymerizable unsaturated bond can constitute an unsaturated compound (Ae).
  • radical polymerizable compound examples include monomers (meth) acrylate compounds, polyurethane (meth) acrylate compounds, polyester (meth) acrylate compounds, polyalkylene (meth) acrylate compounds, and the like.
  • Monomer (meth) acrylate compounds include mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate and the like ( (Meth) acrylates can be used.
  • Examples of the mono (meth) acrylate include acryloylmorpholine, 2-ethylhexyl (meth) acrylate, styrene, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, N-vinyl-2-pyrrolidone, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( (Meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) L) mono (meth) acrylate, poly (prop
  • di (meth) acrylate examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate.
  • tri (meth) acrylate examples include trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and ethylene oxide.
  • tetra (meth) acrylate examples include pentaerythritol tetra (meth) acrylate, ethylene oxide (4 mol) modified pentaerythritol tetra (meth) acrylate (Daicel Cytec, Ebecryl 40), and the like. And (meth) acrylate.
  • penta (meth) acrylate examples include dipentaerythritol penta (meth) acrylate.
  • hexa (meth) acrylate examples include dipentaerythritol hexa (meth) acrylate.
  • known polymers can be used as the (meth) acrylate compound.
  • the (meth) acrylate compounds of the polymers include poly (meth) acrylates such as di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate in addition to mono (meth) acrylate.
  • poly (meth) acrylates such as tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate are preferable from the viewpoint of the hardness of the resulting coating film. .
  • the unsaturated compound (Ae) may be used alone or in combination of two or more.
  • the polyol (Aa) is preferably 2 to 50 when the total amount of the solid content (including the unsaturated compound (Ae)) of the aqueous dispersion is 100 parts by weight.
  • the acidic group-containing polyol (Ab) is preferably 1 to 15 parts by weight. If a polyol (Aa) is the said range, the dispersibility to the water of a polyurethane resin (A) will be favorable, and the outstanding film forming property will be easily obtained about the aqueous polyurethane resin dispersion containing this.
  • the polyol (Aa) is preferably 2 to 50 parts by weight, more preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight.
  • the acidic group-containing polyol (Ab) is preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, and particularly preferably 3 to 7 parts by weight.
  • the total amount of the unsaturated compound (Ad) and the unsaturated compound (Ae) in the polyurethane resin (A) having a polymerizable unsaturated bond is the total amount of the polyurethane resin (A) (including the unsaturated compound (Ae)). 50 to 85% by weight is preferable. If it is this range, the hardness of the coating film obtained is suitable, adhesiveness with PMMA resin is also favorable, and it can avoid that reaction time of an isocyanate group and an unsaturated compound (Ad) becomes long. And the storage stability of the obtained aqueous polyurethane resin dispersion can be made appropriate. More preferably, it is 60 to 80% by weight, and still more preferably 65 to 75% by weight.
  • the polyurethane resin (A) may be used in a form dispersed in an aqueous medium.
  • the aqueous medium include water and a mixed medium of water and a hydrophilic organic solvent.
  • Examples of water include clean water, ion exchange water, distilled water, and ultrapure water.
  • ion-exchanged water is preferable in consideration of easy availability and the fact that particles become unstable due to the influence of salt.
  • hydrophilic organic solvents examples include lower monohydric alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol and glycerin; aprotic groups such as N-methylmorpholine, dimethyl sulfoxide, 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.
  • aqueous dispersion is A step (A ⁇ ) of obtaining a polyurethane resin (A) by reacting at least the polyol (Aa), the acidic group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad); A step of neutralizing acidic groups of the polyurethane resin (A) (A ⁇ ); A step of dispersing the polyurethane resin (A) in an aqueous medium (A ⁇ ); It can obtain by the manufacturing method containing.
  • the polyurethane resin (A) and the unsaturated compound (Ae) are contained, and these are dispersed in the aqueous medium.
  • An aqueous dispersion can be obtained.
  • the step (A ⁇ ) for obtaining the polyurethane resin (A) is 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 necessary.
  • the temperature of the step (A ⁇ ) can be 0 to 120 ° C., preferably 0 to 100 ° C., in order to avoid unnecessary polymerization of polymerizable unsaturated bonds.
  • Examples of the acidic group neutralizing agent that can be used in the step (A ⁇ ) of neutralizing the acidic group of the polyurethane resin (A) include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, and N-phenyl.
  • Organic amines such as diethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine and pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; ammonia and the like.
  • the acidic group of the polyurethane resin (A) refers to a carboxylic acid group, a sulfonic acid group, or the like.
  • the amount of the acidic group neutralizing agent used is preferably such that the molar number is 0.8 to 1.5 with respect to the acidic group of the polyurethane resin (A). Within this range, the dispersibility of the polyurethane resin (A) in water does not decrease, the storage stability of the resulting polyurethane resin aqueous dispersion does not decrease, and the odor of the aqueous polyurethane resin dispersion is strong. This situation can be easily avoided.
  • the polyurethane resin (A) and the arbitrary unsaturated compound (Ae) are dispersed in the aqueous medium.
  • the method and operation order thereof are not particularly limited.
  • the unsaturated compound (Ae) is mixed with the polyurethane resin (A) and dispersed in an aqueous medium, or the unsaturated compound ( Ae) is mixed with a polyurethane resin (A) and dispersed in an aqueous medium, or a polyurethane resin (A) is dispersed in an aqueous medium and then an unsaturated compound (Ae) is mixed and dispersed.
  • a method of mixing and the like after dispersing in When both the polyurethane resin (A) and the unsaturated compound (Ae) are present during dispersion in the aqueous dispersion, the polyurethane resin (A) and the unsaturated compound (Ae) are combined to form an unsaturated compound (Ae). Can be easily dispersed in an aqueous medium.
  • the aqueous dispersion containing the polyurethane resin (A) and the unsaturated compound (Ae) and dispersed in the aqueous medium is obtained by mixing the unsaturated compound (Ae) during the production of the polyurethane resin (A).
  • the unsaturated compound (Ae) can be mixed before, during or after (A ⁇ ).
  • the unsaturated compound (Ae) is preferably present in the step (A ⁇ ) and / or after the step (A ⁇ ) and before neutralization in the step (A ⁇ ).
  • a stirring device such as a homomixer or a homogenizer can be used.
  • a hydrophilic organic solvent, water, or the like can be added to the polyurethane resin (A) or the unsaturated compound (Ae) in advance before mixing in order to adjust viscosity, improve workability, and improve dispersibility.
  • the mixing, stirring, and dispersion are preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Moreover, you may add a polymerization inhibitor to each process as needed.
  • the temperature at which the polyurethane resin (A) and the arbitrary saturated compound (Ae) are mixed is preferably 0 to 100 ° C. in order to avoid unnecessary consumption of the polymerizable unsaturated bond. More preferably, it is carried out at 0 ° C, more preferably 0-80 ° C, and particularly preferably 50-70 ° C.
  • either the step of neutralizing the acidic group of the polyurethane resin (A) (A ⁇ ) or the step of dispersing the polyurethane resin (A) in the aqueous medium (A ⁇ ) can be performed first. It can be done at the same time.
  • the polyurethane resin (A), an optional unsaturated compound (Ae), an aqueous medium, and an acidic group neutralizing agent may be mixed at once, or the acidic group neutralizing agent may be mixed in advance with an aqueous medium or in some cases. These may be mixed with the saturated compound (Ae), and these and the polyurethane resin (A) may be mixed.
  • the proportion of the polyurethane resin (A) in the aqueous dispersion is preferably 5 to 60% by weight, more preferably 15 to 50% by weight, still more preferably. 25 to 40% by weight.
  • the number average molecular weight of the polyurethane resin (A) is preferably 1,000 to 1,000,000.
  • the polyurethane resin (B) having no polymerizable unsaturated bond in the present invention comprises at least a polyol (Ba), an acidic group-containing polyol (Bb), a polyisocyanate (Bc), and a chain extender (Bd).
  • the polyurethane resin (B) has a alicyclic structure content of 16 to 70% by weight.
  • polyol (Ba) (hereinafter also referred to as (Ba)) that can be used in the present invention
  • a high molecular weight polyol for example, polycarbonate polyol, polyester polyol, polyether polyol, etc.
  • a low molecular weight polyol can be used.
  • a polyol containing two or more hydroxyl groups and one or more acidic groups in one molecule is included in the acidic group-containing polyol (Bb).
  • the high molecular weight diol is not particularly limited, but preferably has a number average molecular weight of 400 to 8000. If 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 an aqueous polyurethane resin dispersion containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks, and polyisocyanate (Bc) And the polyurethane resin (B) can be produced efficiently.
  • the polyol (Ba) preferably has a number average molecular weight of 400 to 4000.
  • Examples of the high molecular weight diol include polycarbonate diol, polyester diol, and polyether diol.
  • the diol component is preferably an aliphatic diol and / or an alicyclic diol, and the diol component is more preferably an alicyclic diol.
  • Polycarbonate polyol is obtained by reacting one or more polyol monomers with carbonate ester or phosgene.
  • a polycarbonate polyol obtained by reacting one or more polyol monomers with a carbonate ester is preferred because it is easy to produce and has no by-product formation of terminal chlorinated products.
  • the polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, and a polyether polyol monomer.
  • the aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Linear aliphatic diols such as 1,8-octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Branched aliphatic diols such as pentanediol and 2-methyl-1,9-nonanediol; polyfunctional alcohols having three or more functional groups such as 1,1,1-trimethylolpropane and pentaerythritol.
  • the polyol monomer having an alicyclic structure is not particularly limited.
  • 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1, Alicyclic ring in the main chain such as 4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane
  • Examples include diols having a structure.
  • the aromatic polyol monomer is not particularly limited.
  • the polyester polyol monomer is not particularly limited.
  • a polyester polyol of hydroxycarboxylic acid and diol such as a polyester polyol of 6-hydroxycaproic acid and hexanediol, or a dicarboxylic acid such as polyester polyol of adipic acid and hexanediol.
  • polyester polyol of diol such as polyester polyol of adipic acid and hexanediol.
  • the polyether polyol monomer is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the carbonate ester is not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate.
  • aliphatic carbonates such as dimethyl carbonate and diethyl carbonate
  • aromatic carbonate esters such as diphenyl carbonate
  • cyclic carbonate esters such as ethylene carbonate.
  • phosgene or the like capable of producing a polycarbonate polyol can be used.
  • aliphatic carbonates are preferable and dimethyl carbonate is particularly preferable because of easy production of the polycarbonate polyol.
  • a method for producing a polycarbonate polyol from a polyol monomer and a carbonate ester for example, a carbonate ester and a polyol having an excess number of moles relative to the number of moles of the carbonate ester are added to a reactor, and the temperature is 160 to 200 ° C.
  • An example is a method of reacting at a pressure of about 50 mmHg for 5 to 6 hours and further reacting at 200 to 220 ° C. for several hours at a pressure of several mmHg or less.
  • a catalyst such as titanium tetrabutoxide may be used.
  • Polyester diol is not particularly limited, but for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol Polybutylene sebacate diol, poly- ⁇ -caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid, and the like.
  • the polyether diol is not particularly limited, and specific 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. . Further, a polyether polyester polyol having an ether bond and an ester bond may be used.
  • the low molecular weight diol is not particularly limited, and examples include 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-cyclohexaned
  • the content of the alicyclic structure in the polyol (Ba) is 16 to 70% by weight. If the alicyclic structure content is in this range, the presence of the alicyclic structure makes it easy to obtain a coating film having excellent hardness, and the viscosity at the time of production of the aqueous polyurethane resin dispersion is in an appropriate range, and handling is also easy. Easy.
  • the content of the alicyclic structure is preferably 20 to 65% by weight, and more preferably 30 to 55% by weight.
  • the alicyclic structure content means the weight ratio of the alicyclic group in the polyol (Ba).
  • a cyclohexane residue in the case of 1,4-hexanedimethanol, a portion obtained by removing two hydrogen atoms from cyclohexane
  • an unsaturated heterocyclic residue such as a tetrahydrofuran residue (in the case of tetrahydrofuran dimethanol, This is a calculated value based on the portion obtained by removing two hydrogen atoms from tetrahydrofuran.
  • Polyol (Ba) may be used alone or in combination of two or more.
  • the acidic group-containing polyol (Bb) that can be used in the present invention is not particularly limited as long as it has two or more hydroxyl groups and one or more acidic groups in one molecule.
  • the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • the acidic group-containing polyol (Bb) is preferably one containing a compound having two hydroxyl groups and one carboxy group in one molecule.
  • An acidic group containing polyol (Bb) may be used independently and may use multiple types together.
  • the acidic group-containing polyol (Bb) include dialkanol alkanoic acids including dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid; N, N -Bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acidic group-containing polyether polyol, acidic group-containing polyester polyol, etc. Can be mentioned.
  • dialkanol alkanoic acids including dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid
  • N N -Bishydroxyethylglycine
  • N N-bishydroxyethylalanine
  • 3,4-dihydroxybutanesulfonic acid 3,6-dihydroxy-2-toluenes
  • a dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable, and among the dimethylol alkanoic acids, 2,2-dimethylolpropionic acid is more preferable.
  • the total number of hydroxyl equivalents of the polyol (Ba) and the acidic group-containing polyol (Bb) is preferably 100 to 400.
  • the hydroxyl equivalent is more preferably 150 to 300.
  • the hydroxyl equivalent can be calculated by the above formulas (1) and (2).
  • M is [[number of hydroxyl equivalents of polyol (Ba) ⁇ number of moles of polyol (Ba)] + [number of hydroxyl equivalents of acidic group-containing polyol (Bb) ⁇ The number of moles of the acidic group-containing polyol (Bb)]].
  • the polyol (Ba) is preferably 20 to 85 parts by weight, and the acidic group-containing polyol (Bb) is The amount is preferably 2 to 14 parts by weight.
  • the polyol (Ba) is preferably 25 to 80 parts by weight, more preferably 30 to 75 parts by weight, particularly preferably 35 to 70 parts by weight.
  • the acidic group-containing polyol (Bb) is preferably 2.5 to 12 parts by weight, more preferably 3.0 to 10 parts by weight, and particularly preferably 3.5 to 8 parts by weight.
  • the number of isocyanato groups per molecule of the polyisocyanate is usually two, but a polyisocyanate having three or more isocyanato groups such as triphenylmethane triisocyanate is also used as long as the polyurethane resin in the present invention does not gel. be able to.
  • polyisocyanates 4,4′-diphenylenemethane diisocyanate (MDI), isophorone diisocyanate (IPDI), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) are used from the viewpoint of controlling reactivity and imparting strength.
  • Isophorone diisocyanate (IPDI) and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) are more preferable, and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) is more preferable because the content of the alicyclic structure is easily increased. Further preferred.
  • These polyisocyanates may be used alone or in combination of two or more.
  • the ratio of the number of moles of isocyanate groups of the polyisocyanate (Bc) to the number of moles of all hydroxyl groups of the polyol (Ba) and the acidic group-containing polyol (Bb) is 1.1 to 2.5 is preferred. Within this range, the problem of a long reaction time due to too few moles of hydroxyl groups can be easily avoided, and a large amount of unreacted polyol (Ba) and acidic group-containing polyol (Bb) remain. In addition, it is easy to avoid the problem that the storage stability is lowered.
  • the ratio of the number of moles of isocyanate groups of the polyisocyanate (Bc) to the number of moles of all hydroxyl groups in the polyol component is preferably 1.2 to 2.2, particularly preferably 1.3 to 2.0.
  • the chain extender (Bd) is not particularly limited as long as it is a compound reactive with an isocyanato group, and examples thereof include ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, , 4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylene diene Amine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, amine compounds such as diethylenetriamine, triethylenetetramine, diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol Compound, polyethylene glycol Polyalkylene glycols
  • the amount of the chain extender (Bd) added is preferably equal to or less than the equivalent of the isocyanato group serving as the chain extension origin in the urethane prepolymer to be obtained, and more preferably 0.7 to 0.99 equivalent of the isocyanate group. . If it is this range, it can avoid easily that the molecular weight of the urethane polymer by which the chain
  • the chain extender (Bd) may be added after the urethane prepolymer is dispersed in water, or may be added during the dispersion. Chain elongation can also be carried out with water. In this case, water as a dispersion medium also serves as a chain extender.
  • the polyurethane resin (B) may be used in a form dispersed in an aqueous medium.
  • the aqueous medium include water and a mixed medium of water and a hydrophilic organic solvent.
  • Examples of water include clean water, ion exchange water, distilled water, and ultrapure water.
  • ion-exchanged water is preferable in consideration of easy availability and the fact that particles become unstable due to the influence of salt.
  • hydrophilic organic solvents examples include lower monohydric alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol and glycerin; aprotic groups such as N-methylmorpholine, dimethyl sulfoxide, 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 acid value of the polyurethane resin (B) is preferably 10 to 55 mgKOH / g.
  • the acid value is more preferably 12 to 42 mgKOH / g, and still more preferably 14 to 35 mgKOH / g.
  • the acid value of the polyurethane resin (B) excludes a solvent optionally used in producing the polyurethane resin (B) and a neutralizing agent optionally used for dispersing the polyurethane resin (B) in the aqueous medium. It is the average content of acidic groups in the so-called solid content, and can be derived from the following formula (3 ′).
  • [Acid Value of Polyurethane Resin (B)] [Mole Number of Acid Group of Acid Group-Containing Polyol (Bb)] ⁇ 56.11 / [Polyol (Ba), Acid Group-Containing Polyol (Bb), Polyisocyanate (Bc) And the total weight of the chain extender (Bd)] (3 ′)
  • a polyol (Ba), a polyisocyanate (Bc), and an acidic group-containing polyol (Bb) are reacted to obtain a prepolymer, which is then dispersed in an aqueous medium and subjected to chain extension with a chain extender (Bd) to form a polyurethane.
  • the acid value is synonymous with the acid value of the prepolymer.
  • the manufacturing method of a polyurethane resin (B) is demonstrated.
  • the aqueous dispersion is A step (B ⁇ ) of obtaining a polyurethane prepolymer by reacting at least the polyol (Ba), the acidic group-containing polyol (Bb), and the polyisocyanate (Bc); A step of neutralizing acidic groups of the urethane prepolymer (B ⁇ ); A step (B ⁇ ) of dispersing the urethane prepolymer in an aqueous medium; A step (B ⁇ ) of reacting the urethane prepolymer with a chain extender (Bd); It can obtain by the manufacturing method containing.
  • the step of obtaining the urethane prepolymer (B ⁇ ) can be carried out at 0 to 120 ° C., preferably 40 to 100 ° C.
  • a catalyst can also be used, and examples thereof include a catalyst such as a tin (tin) catalyst mentioned in the production of the polyurethane resin (A). Moreover, it may carry out by adding an organic solvent without a solvent, and in this case, the organic solvent mentioned in manufacture of a polyurethane resin (A) is mentioned as an organic solvent.
  • Examples of the acid group neutralizing agent that can be used in the step of neutralizing the acid group of the urethane prepolymer (B ⁇ ) include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, Organic amines such as dimethylethanolamine, diethylethanolamine, N-methylmorpholine and pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; ammonia and the like. Among these, organic amines can be preferably used, more preferably tertiary amines can be used, and most preferably triethylamine can be used.
  • the acidic group of the urethane prepolymer means a carboxylic acid group, a sulfonic acid group or the like.
  • the amount of the acidic group neutralizing agent used is preferably 0.8 to 1.5 in terms of moles relative to the acidic group of the urethane prepolymer.
  • the usage-amount of an acidic group neutralizing agent is less than this quantity, the dispersibility to the water of a urethane prepolymer may fall, or the storage stability of a polyurethane resin aqueous dispersion may fall. If the amount of the acidic group neutralizing agent used is larger than this amount, the odor of the polyurethane resin aqueous dispersion may become strong.
  • the urethane prepolymer in the aqueous medium (B ⁇ ) in the step of dispersing the urethane prepolymer in the aqueous medium (B ⁇ ), as long as the urethane prepolymer can be dispersed in the aqueous medium, its method and operation order are not particularly limited. Examples thereof include a method of dispersing by adding in an aqueous medium and a method of adding and dispersing in an aqueous medium to a urethane prepolymer.
  • the step (B ⁇ ) of reacting the urethane prepolymer with the chain extender (Bd) is not particularly limited as long as the isocyanate prepolymer and the chain extender of the urethane prepolymer react with each other. , (B ⁇ ), (B ⁇ ), (B ⁇ ) in any order, then (B ⁇ ), (B ⁇ ), (B ⁇ ) in any order, (B ⁇ ), Further, a method of performing (B ⁇ )), a method of performing (B ⁇ ) after performing (B ⁇ ), and further performing (B ⁇ ) and (B ⁇ ) in any order.
  • a stirring device such as a homomixer or a homogenizer can be used.
  • the hydrophilic organic solvent, water or the like can be added to the polyurethane resin (B) in advance before mixing in order to adjust viscosity, improve workability, and improve dispersibility.
  • the proportion of the polyurethane resin in the aqueous dispersion of the polyurethane resin (B) is preferably 5 to 60% by weight, more preferably 15 to 50% by weight, and further preferably 25 to 40% by weight.
  • the number average molecular weight is preferably 1,000 to 1,000,000.
  • the polyurethane resin (B) has an alicyclic structure content of 16 to 70% by weight. If it is this range, the adhesiveness of a favorable coating film and tack-free property will be obtained, and the dispersibility to the water of a polyurethane resin (B) will be favorable, and it can avoid that storage stability falls.
  • the alicyclic structure content is more preferably 29 to 60% by weight, and still more preferably 39 to 50% by weight.
  • the alicyclic structure content is calculated as follows.
  • the cyclohexane ring has an alicyclic structure, and the weight (molecular weight) of the cyclohexane residue obtained by removing two hydrogen atoms from cyclohexane is polyurethane. It is the ratio in the weight (number average molecular weight) of the resin.
  • the present invention relates to an aqueous polyurethane resin dispersion in which a polyurethane resin (A) and a polyurethane resin (B) are dispersed in an aqueous medium, and the aqueous polyurethane resin dispersion in which the polyurethane resin (A) is dispersed in an aqueous medium. It is preferable to produce an aqueous polyurethane resin dispersion in which the polyurethane resin (B) is dispersed in an aqueous medium, and then mix these aqueous polyurethane resin dispersions.
  • the mixing method of these aqueous polyurethane resin dispersions is not particularly limited. For example, when one of the aqueous polyurethane resin dispersions is being stirred, another aqueous polyurethane resin dispersion is added little by little. Is preferred.
  • the aqueous polyurethane resin dispersion of the present invention includes other polyurethane resins, viscosity modifiers, stabilizers, antioxidants, antiseptics, fungicides, pH adjusters. Additives such as formulations and wettability improvers can be contained.
  • the aqueous polyurethane resin dispersion of the present invention is not Contains a saturated compound (Ae).
  • the mixing ratio of the polyurethane resin (A) and the polyurethane resin (B) is not particularly limited, but is a weight ratio (polyurethane resin (A): polyurethane resin (B), solid content). It is preferably 90:10 to 50:50.
  • the mixing ratio of the polyurethane resin (A) and the polyurethane resin (B) if the ratio of the polyurethane resin (A) is too small, the hardness of the resulting coating film may be lowered or the adhesion may be lowered.
  • the ratio of the polyurethane resin (A) is too large, tack-free property may be lowered or adhesion may be lowered. More preferably, it is 80:20 to 60:40.
  • the aqueous polyurethane resin dispersion of the present invention includes an aqueous polyurethane resin dispersion (A) in which the polyurethane resin (A) is dispersed in an aqueous medium, and an aqueous polyurethane resin dispersion in which the polyurethane resin (B) is dispersed in an aqueous medium.
  • the aqueous polyurethane resin dispersion (A): the aqueous polyurethane resin dispersion (B) is preferably 80:20 to 30:70 by weight, More preferably, it is 80:20 to 50:50.
  • a photopolymerization initiator can also be added to the aqueous polyurethane resin dispersion of the present invention.
  • the photopolymerization initiator those generally used can be used, for example, photocleavage type and / or hydrogen abstraction type that can be easily cleaved to form two radicals by ultraviolet irradiation, or a mixture thereof. can do.
  • photopolymerization initiators 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-1 Phenylpropan-1-one, 2,4,6, - trimethyl benzophenone
  • the addition amount of the photopolymerization initiator is preferably 0.5 to 5% by weight with respect to the total solid content of the aqueous polyurethane resin dispersion.
  • the aqueous polyurethane resin dispersion of the present invention includes a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, a sedimentation as necessary. Additives such as inhibitors can also be added. An additive may be used independently and may use multiple types together.
  • the aqueous polyurethane resin dispersion of the present invention preferably contains substantially no protective colloid, emulsifier, or 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 agent composition containing the aqueous polyurethane resin dispersion.
  • other resins may be added to the coating composition and the coating agent composition of the present invention.
  • the other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, and polyolefin resins. These may be used alone or in combination of two or more.
  • the other resin preferably has one or more hydrophilic groups.
  • hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, and a polyethylene glycol group.
  • the other resin is preferably at least one selected from the group consisting of a polyester resin, an acrylic resin, and a polyolefin resin.
  • the polyester resin can be usually produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component.
  • an acid component the compound normally used as an acid component at the time of manufacture of a polyester resin 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 mgKOH / g, more preferably about 50 to 250 mgKOH / g, and still more preferably about 80 to 180 mgKOH / g.
  • the acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, and further preferably about 25 to 60 mgKOH / 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.
  • Hydroxyl group-containing acrylic resin is a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in a solution polymerization method in an organic solvent, in water It can manufacture by making it copolymerize by known methods, such as an emulsion polymerization method.
  • the hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one 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, etc., and 2 to 8 carbon atoms.
  • the hydroxyl group-containing acrylic resin preferably has an anionic functional group.
  • a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is used as one kind of the polymerizable unsaturated monomer. It can be manufactured by using.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g, more preferably about 2 to 100 mgKOH / g, from the viewpoint of storage stability of the aqueous polyurethane resin dispersion and water resistance of the resulting coating film.
  • the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g from the viewpoint of the water resistance of the resulting coating film, and 2 to 150 mgKOH / g. g is more preferable, and about 5 to 100 mgKOH / 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 within the range of 3,000 to 50,000. is there.
  • polyether resin examples include polymers or copolymers having an ether bond, and examples include aromatics such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F. And polyethers derived from group polyhydroxy compounds.
  • polycarbonate resin examples include polymers produced from bisphenol compounds, such as bisphenol A / polycarbonate.
  • polyurethane resin examples include resins having a urethane bond obtained by reacting various polyol components such as acrylic, polyester, polyether, and polycarbonate with polyisocyanate.
  • Examples of the epoxy resin include a resin obtained by a reaction between a bisphenol compound and epichlorohydrin.
  • Examples of bisphenol 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 and fats (soybean oil, linseed oil, coconut oil, stearic acid, etc.) Alkyd resin obtained by reacting a modifier such as
  • the polyolefin resin a polyolefin resin obtained by polymerizing or copolymerizing an olefin monomer with another monomer in accordance with a normal polymerization method is dispersed in water using an emulsifier, or the olefin monomer is appropriately replaced with another monomer. And a resin obtained by emulsion polymerization. In some cases, a so-called chlorinated polyolefin-modified resin in which the polyolefin resin is chlorinated may be used.
  • 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-hexene, Examples include ⁇ -olefins such as decene and 1-dodecene; conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrenes, and the like, and these monomers are used alone. It may also be used in combination.
  • Examples of other monomers copolymerizable with olefinic monomers include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, and the like. May be used alone or in combination of two or more.
  • the coating film or multilayer coating film using the coating composition or coating agent composition, the water resistance of the coating film, etc. are improved. Can do.
  • curing agent for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like can be used. Only one type of curing agent may be used, or a plurality of types may be used in combination.
  • Examples of the amino resin include a partial or completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component.
  • Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like.
  • Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like.
  • polyisocyanate examples include compounds having two or more isocyanato groups in one molecule, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
  • Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the polyisocyanate group of the aforementioned polyisocyanate.
  • Examples of the blocking agent include phenols such as phenol and cresol, methanol, ethanol and the like.
  • Fatty alcohols active methylenes such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetate amide, lactams such as ⁇ -caprolactam and ⁇ -valerolactam, Blocking agents such as acid imides, acid imides such as maleic imides, oximes such as acetaldoxime, acetone oxime, methyl ethyl ketoxime, amines such as diphenylaniline, aniline and ethyleneimine It is.
  • active methylenes such as dimethyl malonate and acetylacetone
  • mercaptans such as butyl mercaptan and dodecyl mercaptan
  • acid amides such as acetanilide and acetate amide
  • lactams such as ⁇ -caprolactam and ⁇ -valerol
  • methylol melamines such as dimethylol melamine and trimethylol melamine
  • alkyl etherified products or condensates of these methylol melamines condensates of alkyl etherified products of methylol melamine, and the like.
  • Coloring pigments, extender pigments, and glitter pigments can be added to the coating composition and coating agent composition of the present invention.
  • the color pigment include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. 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 the color pigment.
  • extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. These may be used alone or in combination of two or more.
  • barium sulfate and / or talc are preferably used as extender pigments, and barium sulfate is more preferably used.
  • 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, or the like may be used. it can.
  • the coating composition and coating composition of the present invention include a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, an anti-settling agent, etc., if necessary.
  • Usual paint additives can be contained. These may be used alone or in combination of two or more.
  • the manufacturing method in particular of the coating composition and coating agent composition of this invention is not restrict
  • the coating composition and the coating 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.
  • Examples of the coating material of the coating composition or the coating material of the coating agent composition include metals, plastics, inorganic materials, and wood.
  • the coating composition and the coating agent composition of the present invention have high adhesion to plastic, and particularly high adhesion to ABS resin. For this reason, as the material to be coated and the material to be coated, ABS resin is preferable.
  • Examples of the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, and immersion coating.
  • the aqueous polyurethane resin dispersion, coating composition and coating composition of the present invention are coated or coated, applied or painted or coated on a desired substrate, and heated or unheated, at least in an aqueous medium. It is preferable to cure by irradiating an active energy ray after a part is evaporated.
  • the active energy rays include ionizing radiation such as electron beams, ultraviolet rays, and ⁇ rays, and among them, ultraviolet rays are preferable.
  • the ultraviolet light source is not particularly limited as long as it emits light in the ultraviolet region.
  • a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like can be used.
  • the irradiation time can be appropriately changed depending on conditions such as the type of the compound having a polymerizable unsaturated bond, the type of the photopolymerization initiator, the film thickness, and the ultraviolet ray source. From the viewpoint of workability, it is preferable to irradiate for 1 to 60 seconds. Further, for the purpose of completing the curing reaction, heat treatment can also be performed after irradiation with ultraviolet rays.
  • the irradiation amount of ultraviolet rays used for curing the aqueous polyurethane resin dispersion, coating composition, coating agent composition and the like of the present invention is 300 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability. Is preferred.
  • an electron beam or the like can also be used for curing.
  • an electron beam accelerator having an energy of 100 to 500 eV.
  • the thickness of the cured coating is not particularly limited and is preferably 1 to 100 ⁇ m. More preferably, a cured film having a thickness of 3 to 50 ⁇ m is formed.
  • Production Examples 1 to 3 are production examples of an aqueous dispersion of a polyurethane resin (A), and Production Examples 4 to 9 are production examples of an aqueous dispersion of a polyurethane resin (B).
  • ETERNACOLL registered trademark
  • dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, the ratio of dipentaerythritol pentaacrylate is 50 to 60 mol%, hydroxyl value 95 mgKOH / g, 181 g) was added and heated at 90 ° C. for 7 hours. .
  • the NCO group content at the end of the urethanization reaction was 0.23% by weight.
  • reaction mixture 48.3 g was extracted, cooled to 70 ° C., and ethylene oxide-modified pentaerythritol pentaacrylate (EOPETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol, 10.8 g). And triethylamine (2.3 g) were added and mixed. The reaction mixture was cooled to 45 ° C. and water (107 g) was slowly added with stirring to obtain an aqueous polyurethane resin dispersion.
  • EOPETA ethylene oxide-modified pentaerythritol pentaacrylate
  • ETERNACOLL registered trademark
  • ETERNACOLL registered trademark
  • a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, the ratio of dipentaerythritol pentaacrylate is 50 to 60 mol%, hydroxyl value 95 mgKOH / g, 181 g) was added and heated at 90 ° C. for 7 hours. .
  • the NCO group content at the end of the urethanization reaction was 0.23% by weight. 60.4 g was extracted from the reaction mixture, and triethylamine (2.9 g) was added and mixed.
  • the reaction mixture was cooled to 45 ° C. and water (111 g) was slowly added while stirring to obtain an aqueous polyurethane resin dispersion.
  • Polycarbonate diol 85.0 g
  • PTMG number average molecular weight 2,030, 14.9 g
  • 2,2-dimethylolpropionic acid (12.1 g)
  • hydrogenated MDI 91.1 g
  • N-ethylpyrrolidone 146 g
  • dibutyltin dilaurate 0.2 g
  • the reaction mixture was cooled to 80 ° C., and 239 g was extracted from the mixture in which triethylamine (8.9 g) was added and mixed, and added to water (310 g) under strong stirring.
  • 2-methyl-1,5-pentanediamine aqueous solution 41.0 g was added to obtain an aqueous polyurethane resin dispersion.
  • reaction mixture was cooled to 80 ° C., and triethylamine (149 g) was added and mixed thereto. 4360 g was extracted from the reaction mixture and added to water (6900 g) under vigorous stirring. Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (626 g) was added to obtain an aqueous polyurethane resin dispersion.
  • ETERNACOLL registered trademark
  • UM90 3: 1 polycarbonate diol obtained by reacting a polyol mixture with carbonate ester (175 g), 2,2-dimethylolpropionic acid (26.0 g), and isophorone Diisocyanate (142 g) was heated in N-methylpyrrolidone (137 g) in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C.
  • reaction mixture was cooled to 80 ° C., and 404 g was extracted from the mixture in which triethylamine (19.6 g) was added and mixed, and added to water (535 g) with vigorous stirring. Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (60.9 g) was added to obtain an aqueous polyurethane resin dispersion.
  • reaction mixture was cooled to 80 ° C., and triethylamine (14.9 g) was added and mixed thereto. 436 g was extracted from the reaction mixture and added into water (690 g) under vigorous stirring. Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (62.6 g) was added to obtain an aqueous polyurethane resin dispersion.
  • reaction mixture was cooled to 80 ° C., and triethylamine (8.8 g) was added to and mixed with the mixture. 230 g of this mixture was extracted and added to water (382 g) with vigorous stirring. Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (5.8 g) was added to obtain an aqueous polyurethane resin dispersion.
  • reaction mixture was cooled to 80 ° C., and 506 g was added to water (816 g) under vigorous stirring, among which triethylamine (12.0 g) was added and mixed. Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (31.3 g) was added to obtain an aqueous polyurethane resin dispersion.
  • Example preparation for pencil hardness and adhesion evaluation The aqueous polyurethane resin dispersions of Production Examples 1 to 3 and the aqueous polyurethane resin dispersions of Production Examples 4 to 9 were mixed so as to have a weight ratio shown in Table 1.
  • a polymerization initiator (IRGACURE500, manufactured by Ciba Specialty Chemicals) was added at 5 wt% / solid content, and stirred well to obtain a coating composition. This was uniformly coated on the PMMA 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 dried coating film was subjected to a tack-free test.
  • the coating film obtained in the same manner was passed under a high-pressure mercury lamp (one irradiation, ultraviolet irradiation amount 1000 mJ / cm 2 ) to obtain an ultraviolet curable coating film.
  • the obtained polyurethane resin coating film was subjected to pencil hardness measurement and adhesion test evaluation. The results are shown in Table 1.
  • the finger was pressed against the coating film obtained above (before UV irradiation), and the state of the coating film was observed.
  • the state of the coating film was evaluated in the following four stages. ⁇ : The coating film is in hand, ⁇ : The coating film has a fingerprint, ⁇ : The coating film has almost no fingerprint, ⁇ , The coating film has no fingerprint
  • the polyurethane resin coating film of PMMA resin obtained above was evaluated by a cross-cut peeling method. That is, 25 squares of 4 mm 2 were prepared on a test piece with a cutter, and peelability was examined with a cellophane tape.
  • the mixing ratio of the polyurethane resin (A) and the polyurethane resin (B) is the mixing ratio of the aqueous polyurethane resin dispersion obtained in each of Production Examples 1 to 9.
  • Examples 1 to 9 corresponding to the composition of the present invention provide a coating film having excellent tack-free property before curing by irradiation with active energy rays and high adhesion to various plastics after curing by irradiation with active energy rays. I understand that. In particular, when Examples 1 to 6 using the same amount of the same polyurethane resin (A) are compared, Examples 1 to 5 in which the polyurethane resin (B) has an alicyclic structure content of 29 to 60% by weight are compared.
  • Examples 1 to 4 using a polycarbonate polyol having an alicyclic structure content of 20 to 65% by weight as a raw material of the polyurethane resin (B) are as follows: It turns out that it is excellent also in tack-free property. On the other hand, Comparative Example 1 lacking the polyurethane resin (B) is remarkably inferior in tack-free properties, and Comparative Example 2 lacking the polyurethane resin (A) is remarkably inferior in terms of hardness and adhesion after curing.
  • Comparative Example 3 includes (A) and (B), but the alicyclic structure ratio of the polyurethane resin (B) falls below the range of the present invention, and extends to the examples of the present invention in both tack-free properties and adhesiveness. There wasn't.
  • the aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for paints and coating agent compositions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une dispersion aqueuse de résine de polyuréthane qui fournit un film de revêtement montrant d'excellentes propriétés de non-pégosité avant durcissement au moyen d'une irradiation par une rayonnement d'énergie active, ledit film de revêtement montrant une haute adhérence vis-à-vis de divers plastiques après durcissement au moyen d'une irradiation par un rayonnement d'énergie active. Selon l'invention, une dispersion aqueuse de résine de polyuréthane est obtenue par la dispersion d'au moins une résine (A) de polyuréthane qui présente une liaison insaturée polymérisable et une résine (B) de polyuréthane qui ne présente pas de liaison insaturée polymérisable dans un milieu aqueux. Cette dispersion aqueuse de résine de polyuréthane est caractérisée en ce que : la résine (B) de polyuréthane est obtenue par réaction d'au moins un polyol (Ba), d'un polyol (Bb) contenant un groupe acide, d'un polyisocyanate (Bc) et d'un agent d'allongement de chaîne (Bd); et la résine (B) de polyuréthane présente une teneur en structure alicyclique de 16-70 % en poids. Une composition photodurcissable qui contient cette dispersion aqueuse de résine de polyuréthane et un initiateur de photopolymérisation; et une composition de matériau de revêtement ou une composition d'agent de revêtement, qui contient cette dispersion aqueuse de résine de polyuréthane sont décrites.
PCT/JP2012/079752 2011-11-24 2012-11-16 Dispersion aqueuse de résine de polyuréthane et son utilisation WO2013077260A1 (fr)

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JP2015004040A (ja) * 2013-06-24 2015-01-08 宇部興産株式会社 光及び熱硬化性水性樹脂分散体及びエラストマー積層体
JP2015067699A (ja) * 2013-09-27 2015-04-13 株式会社日本触媒 硬化性樹脂組成物及びその用途
JP2015078274A (ja) * 2013-10-15 2015-04-23 宇部興産株式会社 水性樹脂分散体組成物及びその使用
JP2016027111A (ja) * 2014-06-20 2016-02-18 三菱化学株式会社 ポリカーボネートジオールおよびその製造方法並びにそれを用いたポリウレタン
JP2019518092A (ja) * 2016-04-20 2019-06-27 オールネックス オーストリア ゲーエムベーハー 水性ポリウレタン分散物
JP2019131689A (ja) * 2018-01-31 2019-08-08 宇部興産株式会社 ポリカーボネートポリオール、及び水性ポリウレタン樹脂分散体
CN110713705A (zh) * 2019-10-17 2020-01-21 广东工业大学 一种互穿网络结构的水性聚氨酯乳液及其制备方法和应用
CN112041360A (zh) * 2018-05-16 2020-12-04 宇部兴产株式会社 光固化性树脂组合物及使用其的粘合粘接剂
CN114349930A (zh) * 2022-01-17 2022-04-15 万华化学集团股份有限公司 一种水性聚氨酯树脂乳液及制备方法，一种耳机套革

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WO2011058937A1 (fr) * 2009-11-10 2011-05-19 宇部興産株式会社 Dispersion aqueuse de résine polyuréthane, son procédé de production, et son utilisation
WO2011122519A1 (fr) * 2010-03-30 2011-10-06 宇部興産株式会社 Dispersion aqueuse photodurcissable de résine de polyuréthane et son procédé de production
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JP2015004040A (ja) * 2013-06-24 2015-01-08 宇部興産株式会社 光及び熱硬化性水性樹脂分散体及びエラストマー積層体
JP2015067699A (ja) * 2013-09-27 2015-04-13 株式会社日本触媒 硬化性樹脂組成物及びその用途
JP2015078274A (ja) * 2013-10-15 2015-04-23 宇部興産株式会社 水性樹脂分散体組成物及びその使用
JP2016027111A (ja) * 2014-06-20 2016-02-18 三菱化学株式会社 ポリカーボネートジオールおよびその製造方法並びにそれを用いたポリウレタン
JP7010841B2 (ja) 2016-04-20 2022-01-26 オールネックス オーストリア ゲーエムベーハー 水性ポリウレタン分散物
JP2019518092A (ja) * 2016-04-20 2019-06-27 オールネックス オーストリア ゲーエムベーハー 水性ポリウレタン分散物
JP7102751B2 (ja) 2018-01-31 2022-07-20 Ｕｂｅ株式会社 ポリカーボネートポリオール、及び水性ポリウレタン樹脂分散体
JP2019131689A (ja) * 2018-01-31 2019-08-08 宇部興産株式会社 ポリカーボネートポリオール、及び水性ポリウレタン樹脂分散体
CN112041360A (zh) * 2018-05-16 2020-12-04 宇部兴产株式会社 光固化性树脂组合物及使用其的粘合粘接剂
KR20200139750A (ko) * 2018-05-16 2020-12-14 우베 고산 가부시키가이샤 광경화성 수지 조성물 및 그것을 사용한 점접착제
EP3795599A4 (fr) * 2018-05-16 2022-01-26 Ube Industries, Ltd. Composition de résine photodurcissable et adhésif l'utilisant
KR102484271B1 (ko) * 2018-05-16 2023-01-03 유비이 가부시키가이샤 광경화성 수지 조성물 및 그것을 사용한 점접착제
CN112041360B (zh) * 2018-05-16 2023-08-04 Ｕｂｅ株式会社 光固化性树脂组合物及使用其的粘合粘接剂
CN110713705A (zh) * 2019-10-17 2020-01-21 广东工业大学 一种互穿网络结构的水性聚氨酯乳液及其制备方法和应用
CN114349930A (zh) * 2022-01-17 2022-04-15 万华化学集团股份有限公司 一种水性聚氨酯树脂乳液及制备方法，一种耳机套革
CN114349930B (zh) * 2022-01-17 2023-07-04 万华化学集团股份有限公司 一种水性聚氨酯树脂乳液及制备方法，一种耳机套革

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