WO2016047415A1 - Composition aqueuse de résine uréthane, agent de revêtement et article - Google Patents

Composition aqueuse de résine uréthane, agent de revêtement et article Download PDF

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Publication number
WO2016047415A1
WO2016047415A1 PCT/JP2015/075060 JP2015075060W WO2016047415A1 WO 2016047415 A1 WO2016047415 A1 WO 2016047415A1 JP 2015075060 W JP2015075060 W JP 2015075060W WO 2016047415 A1 WO2016047415 A1 WO 2016047415A1
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Prior art keywords
urethane resin
group
mass
resin composition
coating film
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PCT/JP2015/075060
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English (en)
Japanese (ja)
Inventor
潤一 宮宅
白髪　潤
定 永浜
広義 神成
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Dic株式会社
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Priority to JP2016544491A priority Critical patent/JP6128285B2/ja
Publication of WO2016047415A1 publication Critical patent/WO2016047415A1/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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention relates to an aqueous urethane resin composition that can be used for various applications such as a coating agent and an adhesive.
  • Aqueous urethane resin compositions are generally used in various applications including coating agents and adhesives because they have good adhesion to substrates and can form flexible coatings.
  • aqueous urethane resin composition examples include an aqueous polyurethane dispersion, a) at least one organic aliphatic, alicyclic or aromatic di, tri- or polyisocyanate, b) at least one isocyanate reaction.
  • a polycarbonate diol, triol or polyol c) at least one compound comprising at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group, and d) at least one isocyanate-reactive group and At least one compound comprising at least one dispersed active group, and optionally e) at least one compound comprising at least two isocyanate-reactive groups and having a molecular weight of less than 1000 g / mol, preferably less than 500 g / mol.
  • aqueous polyurethane dispersions which the reaction product obtained is characterized by being obtained by dispersing in water are known (e.g., see Patent Document 1.).
  • aqueous urethane resin composition for example, for the surface coating of optical members such as flexible displays, etc.
  • coating films formed using the aqueous polyurethane dispersion are weather resistant. Insufficient solvent resistance may cause cracking or yellowing when the paint is used outdoors, or may peel off or dissolve when used with an industrial coating agent. Further, since the coating film formed using the aqueous polyurethane dispersion is not sufficient in terms of hardness, for example, when used for a surface coating agent such as a touch panel, the coating film is easily damaged and may cause poor appearance.
  • the problems to be solved by the present invention have excellent coating film hardness, elongation and flexibility, and excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates. It is to provide an aqueous urethane resin composition capable of forming a coating film.
  • a polyol as a raw material for a urethane resin is an alkylene diol having 1 to 5 carbon atoms having two or more polymerizable unsaturated groups (a1- 1) or by using an aqueous urethane resin composition containing a urethane resin (A) using an oxyalkylene diol (a1-2) having 1 to 9 carbon atoms having two or more polymerizable unsaturated groups,
  • A aqueous urethane resin composition containing a urethane resin
  • a1-2 oxyalkylene diol having 1 to 9 carbon atoms having two or more polymerizable unsaturated groups
  • the present invention is a urethane resin (A) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group, and an aqueous urethane resin composition containing an aqueous medium (B),
  • the urethane resin (A) is an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two or more polymerizable compounds represented by the following general formula (2) It is obtained by reacting a polyol (a1) containing an unsaturated group-containing oxyalkylenediol (a1-2), a polyisocyanate (a2), and a silane coupling agent (a3).
  • the present invention relates to an aqueous urethane resin composition.
  • R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of the linear alkylene group having 1 to 9 carbon atoms.
  • R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
  • R 2 is an alkylene having 1 to 5 carbon atoms. Represents a group.
  • the aqueous urethane resin composition of the present invention has excellent coating film hardness, elongation and flexibility, and excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates. Since a coating film can be formed, for example, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / PC resin, polystyrene resin (PS resin), polymethacrylic acid resin (PMMA resin), polyester resin It can be suitably used for a coating agent and an adhesive for a plastic substrate such as (PET resin).
  • ABS resin acrylonitrile-butadiene-styrene resin
  • PC resin polycarbonate resin
  • PS resin polystyrene resin
  • PMMA resin polymethacrylic acid resin
  • polyester resin It can be suitably used for a coating agent and an adhesive for a plastic substrate such as (PET resin).
  • the aqueous urethane resin composition of the present invention is an aqueous urethane resin composition containing a urethane resin (A) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group, and an aqueous medium (B).
  • the urethane resin (A) is an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two represented by the following general formula (2): It is obtained by reacting the polyol (a1) containing the above oxyalkylene diol (a1-2) having a polymerizable unsaturated group, the polyisocyanate (a2), and the silane coupling agent (a3). It is characterized by that.
  • the urethane resin (A) has one or both of a hydrolyzable silyl group and a silanol group.
  • the hydrolyzable silyl group or silanol group can be hydrolyzed by contact with water or the like to form a silanol group in which a hydroxyl group is bonded to a silicon atom.
  • the hydrolyzable silyl group or silanol group can react with a self-condensation reaction or other functional group when forming a coating film. Thereby, it becomes possible to form a coating film excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
  • the hydrolyzable silyl group or silanol group is introduced into the urethane resin (A) by using the silane coupling agent (a3) used when the urethane resin (A) is produced.
  • urethane resin (A) among the urethane resins having a polymerizable unsaturated group, an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or the following A polyol (a1) containing an oxyalkylenediol (a1-2) having two or more polymerizable unsaturated groups represented by the general formula (2), a polyisocyanate (a2), and a silane coupling agent (a3) The one obtained by reacting with is used.
  • R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
  • R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
  • R 2 is an alkylene having 1 to 5 carbon atoms. Represents a group.
  • polyol (a1) used for the production of the urethane resin (A) two or more polymerizable unsaturated groups are present in the side chain with respect to the main chain of the urethane resin (A) in which urethane bonds are mainly present.
  • the polymerizable unsaturated group derived from the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) undergoes radical polymerization when forming a coating film or the like.
  • the coating film which has the outstanding coating-film hardness, elongation, and flexibility can be formed.
  • R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
  • pentaerythritol di (meth) acrylate has a structure in which R 1 in the general formula (1) has two atomic groups containing a polymerizable unsaturated group in the side chain of a propylene group having 3 carbon atoms.
  • alkylene diol (a1-1) those having 2 or more and 5 or less polymerizable unsaturated groups are preferably used, and those having 2 or more and 3 or less polymerizable unsaturated groups are used. It is more preferable to obtain an aqueous urethane resin composition capable of forming a coating film having excellent coating film hardness, elongation and flexibility.
  • alkylene diol (a1-1) examples include pentaerythritol di (meth) acrylate [dimethylolpropane di (meth) acrylate], dimethylolmethane di (meth) acrylate (R 1 in the general formula (1) is , Those having 3 carbon atoms and two atomic groups having a polymerizable unsaturated group), diethylolmethane di (meth) acrylate, and diethylolpropane di (meth) acrylate (general formula (1 R 1 is a group having 5 carbon atoms and having two atomic groups having a polymerizable unsaturated group.), Dipropanolmethane di (meth) acrylate, dipropanolpropanedi (meth) acrylate (formula (1) R 1 in the intended 7 carbon atoms, is an atomic group having a polymerizable unsaturated group as it has two.) Di-butanol methane di (
  • pentaerythritol di (meth) acrylate and dimethylolmethane di (meth) acrylate is an aqueous urethane resin composition capable of forming a coating film having excellent coating film hardness, elongation and flexibility. Since it is obtained, it is more preferable.
  • These alkylene diols (a1-1) can be used alone or in combination of two or more.
  • “(meth) acrylate” refers to either one or both of acrylate and methacrylate.
  • R 1 and R 3 in the general formula (2) have a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
  • R 1 and R 3 in the general formula (2) have a total of two or more structures having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group, preferably in the range of 2 or more and 5 or less, More preferably, it has in the range of 2 or more and 3 or less.
  • R 2 in the general formula (2) represents an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentyl group.
  • Examples of the oxyalkylene diol (a1-2) include bis (3-acryloyloxy-2-hydroxypropoxy) methane (R 1 and R 3 in the general formula (2) are those having 2 carbon atoms and are polymerizable. One having an unsaturated group and R 2 having one carbon atom), 1,2-bis (3-acryloyloxy-2-hydroxypropoxy) ethane (general formula (2 And R 1 and R 3 are those having 2 carbon atoms and having one atomic group having a polymerizable unsaturated group, and R 2 is having 2 carbon atoms.), 1, 3-bis (3-acryloyloxy-2-hydroxypropoxy) propane (in formula (2), R 1 and R 3 have 2 carbon atoms and have one atomic group having a polymerizable unsaturated group) in and, R 2 is the number of carbon atoms Is of.), 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane (formula (2) R 1 and R 3 in the intended 2 carbon atoms, a poly
  • bis (3-acryloyloxy-2-hydroxypropoxy) methane provides an aqueous urethane resin composition capable of forming a coating film having excellent coating hardness, elongation and flexibility. More preferable.
  • These oxyalkylene diols (a1-2) can be used alone or in combination of two or more.
  • the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) are used in a total range of 0.1 to 49% by mass in the total amount of raw materials used in the production of the urethane resin (A).
  • the range of 1 to 15% by mass is more preferable.
  • the total amount of the raw material used for manufacture of the said urethane resin (A) points out the total mass containing it, when a polyol (a1), polyisocyanate (a2), and a chain extender are used.
  • polyol (a1) that can be used in the production of the urethane resin (A), in addition to the alkylene diol (a1-1) and the oxyalkylene diol (a1-2), other polyols may be used in combination as necessary. be able to.
  • Examples of the other polyol include a polyol having a hydrophilic group for the purpose of imparting excellent water dispersion stability to the urethane resin (A).
  • polyol having a hydrophilic group examples include a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group. Of these, polyols having an anionic group are preferred.
  • polyol having an anionic group examples include a polyol having a carboxyl group and a polyol having a sulfonic acid group.
  • polyol having a carboxyl group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Among them, 2,2-dimethylol is preferable. Propionic acid is preferred. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group, and various polycarboxylic acids react can also be used.
  • polyol having a sulfonic acid group examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof; Polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol and the like, and the polyester polyol and ⁇ -butyrolactone And polyester polyols obtained by reacting cyclic ester compounds such as ⁇ -valerolactone and ⁇ -caprolactone.
  • dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and
  • the anionic groups are preferably partially or wholly neutralized with a basic compound or the like because good water dispersibility can be expressed.
  • Examples of basic compounds that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine; sodium hydroxide, water Examples thereof include metal hydroxides including potassium oxide and lithium hydroxide.
  • examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specific examples include N-methyl-diethanolamine and polyols obtained by reacting a compound having two epoxies with a secondary amine.
  • the cationic group is preferably partially or completely neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid or the like.
  • an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid or the like.
  • the tertiary amino group as the cationic group is preferably partly or entirely quaternized.
  • the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like, and dimethyl sulfate is preferable.
  • examples of the polyol having a nonionic group include polyalkylene glycol having a structural unit derived from ethylene oxide.
  • the polyol having a hydrophilic group is preferably used in the range of 1 to 20% by mass in the total amount of raw materials used in the production of the urethane resin (A), and further has excellent coating film hardness and elongation.
  • an aqueous urethane resin composition capable of forming a coating film having flexibility is obtained, it is more preferably used in the range of 1 to 10% by mass.
  • examples of the other polyol include polyester polyol, polycarbonate polyol, and polyether polyol.
  • polyester polyols and polycarbonate polyols are preferable because a coating film having even better coating film hardness, elongation, and flexibility can be formed.
  • polyester polyol examples include a polyester polyol obtained by reacting a low molecular weight polyol and a polycarboxylic acid; a polyester polyol obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone; Examples include polyester polyols obtained by polymerization.
  • low molecular weight polyol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol and the like having a molecular weight of about 50 to 300.
  • Aliphatic polyols such as cyclohexane dimethanol, and polyols having an aromatic structure such as bisphenol A and bisphenol F. Of these, 1,6-hexanediol and neopentyl glycol are preferable.
  • polycarboxylic acid examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. And aromatic polycarboxylic acids such as anhydrides or esterified products thereof.
  • polycarbonate polyol examples include diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and cyclohexanedimethanol, carbonate esters such as dimethyl carbonate and diethyl carbonate, and phosgene. And the like obtained by reacting with the above.
  • polyester polyol, polyether polyol and polycarbonate polyol are preferably used in the range of 1 to 70% by mass, and in the range of 15 to 45% by mass, based on the total amount of raw materials used for the production of the urethane resin (A). It is more preferable to use in the case of being able to form a coating film having even better coating film hardness, elongation and flexibility.
  • polyisocyanate (a2) used in the production of the urethane resin (A) examples include polyisocyanates having an aliphatic cyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; 4,4′-diphenylmethane Aromatic polyisocyanates such as diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Aliphatic polyiso, such as isocyanate Aneto and
  • polyisocyanate (a2) dicyclohexylmethane diisocyanate or isophorone diisocyanate is preferable because it can form a coating film having excellent coating film hardness, elongation and flexibility.
  • these polyisocyanates (a2) can be used alone or in combination of two or more.
  • silane coupling agent (a3) used for the production of the urethane resin (A) those having a reactive group can be used.
  • a part or all of the hydrolyzable silyl group of the silane coupling agent (a3) may be hydrolyzed to form a silanol group.
  • Examples of the reactive group include an amino group, an isocyanate group, a (meth) acrylate group, a vinyl group, a mercapto group, and an epoxy group.
  • (meth) acrylate group refers to either one or both of an acrylate group and a methacrylate group.
  • silane coupling agent (a3) examples include vinyl silanes such as vinyl tris ( ⁇ -methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, and (meth) acryl silane such as ⁇ -methacryloxypropyl trimethoxy silane.
  • N-2- (aminoethyl) -3-aminopropyltriethoxysilane is a coating film with excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance, and adhesion to various substrates. Can be formed.
  • These silane coupling agents can be used alone or in combination of two or more.
  • the silane coupling agent (a3) should be used in a range of 0.1 to 10% by mass in the total amount of raw materials used in the production of the urethane resin (A), corrosion resistance, hot water resistance, chemical resistance, It is preferable because it can form a coating film excellent in solvent resistance and adhesion to various substrates, and more preferably in the range of 2 to 7% by mass.
  • the urethane resin (A) is a step of producing a urethane resin (A ′) having an isocyanate group or a hydroxyl group at a terminal by reacting the polyol (a1) with the polyisocyanate (a2) [ 1] and the step [2] of reacting the urethane resin (A ′) with the silane coupling agent (a3).
  • the silane coupling agent (a3) is a silane coupling agent having two or more reactive groups selected from the group consisting of an amino group and an isocyanate group
  • the urethane (A) is the polyol (a1).
  • the polyisocyanate (a2) and the silane coupling agent (a3) can be mixed and reacted.
  • the reaction of the polyol (a1) and the polyisocyanate (a2) in the step [1] constituting the production process of the urethane resin (A) is performed, for example, in the absence of a solvent or in the presence of an organic solvent.
  • (A1) and the polyisocyanate (a2) can be mixed and carried out at a reaction temperature in the range of about 50 to 150 ° C.
  • the reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, such that the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5. It is preferably carried out in the range, more preferably in the range of 0.9 to 1.5.
  • urethane resin (A ′) having an isocyanate group at the terminal manufactured in the step [1] it is possible to form a coating film having even more excellent coating film hardness, elongation and flexibility.
  • a chain extender can be used as necessary.
  • chain extender that can be used for producing the urethane resin (A ′)
  • polyamine, hydrazine compound, other active hydrogen atom-containing compounds, and the like can be used.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. Moreover, these polyamines can be used alone or in combination of two or more.
  • hydrazine compound examples include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; ⁇ -semicarbazide And propionic acid hydrazide.
  • these hydrazine compounds can be used alone or in combination of two or more.
  • Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, Glycols such as methylene glycol, glycerin and sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, phenol such as hydroquinone, and water
  • the urethane resin composition of the present invention can be used alone or in combination of two or more within the range in which the storage stability does not deteriorate.
  • Examples of the organic solvent that can be used when the urethane resin (A ′) is produced by the step [1] include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; ethyl acetate and butyl acetate. And nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
  • the said organic solvent when used when manufacturing the said urethane resin (A), in order to reduce the load with respect to safety
  • the said process [2] which comprises the manufacturing process of the said urethane resin (A) mixes the said urethane resin (A ') obtained by the said process [1], and the said silane coupling agent (a3).
  • This is a reaction step.
  • the step [2] is preferably performed, for example, at a reaction temperature of 20 to 80 ° C.
  • the aqueous urethane resin composition of the present invention neutralizes part or all of the hydrophilic group of the urethane resin (A) such as the urethane resin (A-1) obtained by the above method, It can manufacture by mixing a neutralized material and an aqueous medium (B).
  • Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof.
  • the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone.
  • only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
  • the aqueous medium (B) is preferably water alone or a mixture of water and an organic solvent miscible with water, particularly water alone, from the viewpoint of safety and environmental burden.
  • the ratio of the aqueous medium (B) is preferably in the range of 10 to 90% by mass and more preferably in the range of 30 to 70% by mass with respect to the total amount of the aqueous urethane resin composition.
  • the urethane resin (A) obtained by the above method has a weight average molecular weight in the range of 10,000 to 500,000 because it can form a coating film having even better coating film hardness, elongation and flexibility. It is preferable to use those having a weight average molecular weight in the range of 20,000 to 200,000, more preferably using a weight average molecular weight in the range of 40,000 to 100,000. preferable.
  • the urethane resin (A) it is possible to form a coating film having further excellent coating film hardness, elongation and flexibility, and excellent chemical resistance and solvent resistance. It is preferable to use what has.
  • urethane resin (A) use of a resin having a urea bond equivalent in the range of 500 to 50,000 has even more excellent coating film hardness, elongation and flexibility, and chemical resistance. It is preferable because a coating film having excellent properties and solvent resistance can be formed.
  • the urethane resin (A) preferably contains the urethane resin (A) in the range of 5 to 85% by mass in the total amount of the aqueous urethane resin composition, and is in the range of 15 to 50% by mass. It is preferable that it is contained.
  • an emulsifier or the like When dispersing the urethane resin (A) in an aqueous medium, an emulsifier or the like may be used as necessary.
  • emulsifier examples include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • Fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
  • anionic emulsifiers such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
  • anionic emulsifiers such as sodium oleate, alkyl sulfate esters, alkylbenzene
  • polysiloxane (X) can be used in the aqueous urethane resin composition of the present invention.
  • polysiloxane (X) for example, condensates of various alkoxysilanes can be used.
  • alkoxysilane examples are commercially available as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, “MEK-ST” and “IPA-ST” (manufactured by Nissan Chemical Industries, Ltd.).
  • Tetraalkoxysilane methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, which are represented by organosilica sol N-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Cycloalkenyl trimethoxysilane, trialkoxysilane such as phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl dimethoxysilane, and di-alkoxysilanes such as diethyl diethoxy silane.
  • polysiloxane (X) a polymer in which a segment composed of a vinyl polymer and a segment composed of a polysiloxane are bonded can also be used.
  • Examples of the polymer include vinyl monomers such as methyl (meth) acrylate and ethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, and (meth) acryloxypropyltriethoxysilane.
  • Examples thereof include a polymer obtained by polymerizing with a silane compound having a polymerizable unsaturated group such as a vinyl polymer having a hydrolyzable silyl group obtained by condensing the alkoxysilane with the polymer.
  • the alkoxysilane is sequentially or collectively supplied into an organic solvent solution of a vinyl polymer having a hydrolyzable silyl group and the like, and the polymer is stirred for 0.5 hour in the range of 20 to 120 ° C.
  • the reaction can be carried out for about 24 hours by subjecting the hydrolyzable silyl group of the vinyl polymer and the hydrolyzable silyl group of the alkoxysilane to a hydrolytic condensation reaction.
  • the polysiloxane (X) Since the polysiloxane (X) has a hydrolyzable silyl group or silanol group, it causes a hydrolytic condensation reaction with the hydrolyzable silyl group or silanol group of the urethane resin (A) and is strong.
  • a polysiloxane-polyurethane structure By forming a polysiloxane-polyurethane structure, it is possible to form a coating film excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
  • polysiloxane (X) a strong polysiloxane-polyurethane structure having a higher crosslinking density is formed, thereby providing corrosion resistance, hot water resistance, chemical resistance, solvent resistance, and adhesion to various substrates. It is preferable to use one having a polymerizable unsaturated group because a coating film excellent in the thickness can be formed.
  • the polysiloxane (X) having a polymerizable unsaturated group is, for example, a silane compound having a polymerizable unsaturated group such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane. It can be obtained by producing as a raw material for the condensate of alkoxysilane obtained using
  • the polymerizable unsaturated group is preferably contained in the polysiloxane (X) in a range of 0.2 to 3 mmol / g.
  • aqueous urethane resin composition of the present invention it is preferable to use a polymerization initiator in order to promote radical polymerization of the polymerizable unsaturated group of the urethane resin (A).
  • the polymerization initiator for example, benzophenone, benzyl, Michler ketone, thioxanthone, anthraquinone, benzoin, dialkoxyacetophenone, acyl oxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like can be used.
  • the photopolymerization initiator may be used in combination with a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine, or tributylamine as necessary.
  • polymerization initiator examples include 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 4,4′-azobis (4-cyano) valeric acid, 2,2′-azobis (2- Thermal polymerization initiators such as peroxides such as amidinopropane) dihydrochloride, benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide can also be used.
  • the polymerization initiator is preferably used in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the urethane resin (A).
  • the water-based urethane resin composition of the present invention may contain additives as necessary within a range that does not impair the object of the present invention.
  • the additive include a compound having a polymerizable unsaturated group, a film forming aid, a filler, a thixotropic agent, a tackifier, a pigment, an antibacterial agent, and the like.
  • Examples of the compound having a polymerizable unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meta ) Acrylate, 1-adamantyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, di
  • the film forming aid examples include an anionic surfactant (dioctylsulfosuccinate ester soda salt, etc.), a hydrophobic nonionic surfactant (sorbitan monooleate, etc.), silicone oil, and the like.
  • thixotropy-imparting agent examples include fatty acid, fatty acid metal salt, fatty acid ester, paraffin, resin acid, surfactant, polyacrylic acid and the like surface-treated filler, polyvinyl chloride powder, hydrogenated castor oil, Fine powder silica, organic bentonite, sepiolite and the like can be mentioned.
  • pigment known and commonly used inorganic pigments and organic pigments can be used.
  • the inorganic pigment for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, graphite and the like can be used.
  • organic pigment examples include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, Organic pigments such as quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used. Two or more kinds of these pigments can be used in combination. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.
  • antibacterial agent for example, silver chloride, trifuranide, dichlorofluanide, fluorophorpet, zinc pyrithione, methyl 2-benzimidazole carbanate, 2- (4-thiazolyl) benzimidazole and the like can be used.
  • reaction accelerators metal reaction accelerators, metal salt reaction accelerators, amine reaction accelerators, etc.
  • stabilizers ultraviolet absorbers, antioxidants, heat stabilizers, etc.
  • various additives such as moisture removing agents (4-paratoluenesulfonyl isocyanate, etc.), adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion-imparting agents, antifoaming agents, leveling agents and the like.
  • the aqueous urethane resin composition of the present invention is obtained by dispersing the urethane resin (A) and the acrylic resin (B) in the aqueous medium (B). At this time, it is preferable that the urethane resin (A) and the acrylic resin (B) are present as separate resin particles in the aqueous medium (B).
  • aqueous urethane resin composition of the present invention can be suitably used, for example, as a coating agent that can impart surface protection and design properties of various substrates.
  • Examples of the substrate on which the coating agent can be applied to form a coating film include a glass substrate, a metal substrate, a plastic substrate, paper, a wood substrate, and a fibrous substrate.
  • the base material of porous body structures such as a urethane foam, can also be used.
  • plastic substrates include polycarbonate substrates, polyester substrates, acrylonitrile-butadiene-styrene substrates, polyacryl substrates, polystyrene substrates, polyurethane substrates, epoxy resin substrates, polyvinyl chloride substrates, and polyamide groups. Material can be used.
  • a plated steel plate such as a galvanized steel plate or an aluminum-zinc alloy steel plate, an iron plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate, or the like can be used.
  • the base material may be a planar material made of the material or may have a curved portion, or may be a base material made of fibers such as a nonwoven fabric.
  • the coating agent of the present invention has, for example, the urethane resin (A) after being applied directly to the surface of the base material or the surface of the base material on which a primer layer or the like has been previously provided and then dried.
  • a coating film can be formed by advancing radical polymerization of a polymerizable unsaturated double group.
  • a coating film is formed on the surface of the release paper by applying the coating agent on the release paper, then drying and curing, and a non-woven fabric obtained by applying an adhesive or an adhesive on the coating film.
  • a film formed using the coating agent can be laminated on the surface of a desired substrate by laminating the substrate made of such fibers and peeling the release paper.
  • Examples of the method for applying the coating agent on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
  • examples of the method for curing the coating agent include a heating method and a method of irradiating active energy rays such as ultraviolet rays.
  • the heating method varies depending on the type of radical polymerization initiator to be used. For example, by performing the heating at a temperature of about 100 to 150 ° C. for about 10 to 30 minutes, the radical polymerization can be advanced and cured. .
  • a method using a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED lamp is used.
  • a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED lamp.
  • the exposure dose of the actinic energy ray is preferably in the range of 0.05 ⁇ 5J / cm 2, more preferably in the range of 0.1 ⁇ 3J / cm 2, 0.1 ⁇ 1J / cm 2 It is particularly preferable that the range is
  • the above-mentioned ultraviolet irradiation amount is based on values measured in a wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).
  • the thickness of the coating film that can be formed using the coating agent of the present invention can be appropriately adjusted according to the use of the substrate, but is preferably about 0.1 to 100 ⁇ m.
  • articles provided with a coating film formed using the coating agent on the substrate are optical members such as liquid crystal displays and flexible displays, mobile phones, various plastic products including home appliances, It can be used as metal products such as automobile exteriors and building materials.
  • a vinyl polymer (Y-1) having a trimethoxysilyl group was prepared.
  • the temperature of the reaction vessel was adjusted to 80 ° C., and 131 parts by mass of methyltrimethoxysilane (MTMS), 226 parts by mass of 3-acryloyloxypropyltrimethoxysilane (APTS), and 116 parts by mass of dimethyldimethoxysilane (DMDMS) were added.
  • MTMS methyltrimethoxysilane
  • APTS 3-acryloyloxypropyltrimethoxysilane
  • DDMS dimethyldimethoxysilane
  • Example 1 Aqueous urethane resin composition (1)
  • a heating device a stirrer, a thermometer and a reflux condenser
  • 88.8 parts by mass of methyl ethyl ketone, polycarbonate polyol (1,6-hexanediol, 1,5-pentanediol and diethyl carbonate were added.
  • aqueous urethane resin composition (1) having a nonvolatile content of 33% by mass was obtained by adding 47.5 parts by mass of an aqueous piperazine solution, causing a chain extension reaction at 40 ° C., and distillation under reduced pressure.
  • Example 2 Aqueous urethane resin composition (2)
  • a urethane resin composition (2) was obtained.
  • Example 3 Aqueous urethane resin composition (3)
  • the urethane resin (I-1) organic solvent solution 278.1 parts by mass of the polysiloxane (X-1) obtained in Production Example 1, and 8.9 parts by mass of dimethylethanolamine, 1207.1 parts by mass of exchange water was added and stirred sufficiently, 47.5 parts by mass of a 10% by mass piperazine aqueous solution was added, a chain elongation reaction was carried out at 40 ° C., and distillation under reduced pressure was carried out.
  • a urethane resin composition (3) was obtained.
  • Example 4 Aqueous urethane resin composition (4)
  • a heating device a stirrer, a thermometer and a reflux condenser
  • 89.2 parts by mass of methyl ethyl ketone, polycarbonate polyol (1,6-hexanediol, 1,5-pentanediol and diethyl carbonate were added.
  • the total amount of the organic solvent solution of the urethane resin (I-2) was mixed with 303.6 parts by mass of the polysiloxane (X-1) obtained in Production Example 1 and 8.9 parts by mass of dimethylethanolamine. Thereafter, 1368.2 parts by mass of ion-exchanged water was added, and the mixture was sufficiently stirred and distilled under reduced pressure to obtain an aqueous urethane resin composition (4) having a nonvolatile content of 45% by mass.
  • Example 5 Aqueous urethane resin composition (5)
  • Example 6 Aqueous urethane resin composition (6)
  • 836.3 parts by mass of ion-exchanged water was added and stirred sufficiently, 47.5 parts by mass of a 10% by mass piperazine aqueous solution was added, and a chain elongation reaction was performed at 40 ° C., followed by distillation under reduced pressure.
  • an aqueous urethane resin composition (6) having a nonvolatile content of 45% by mass was obtained.
  • Example 7 Aqueous urethane resin composition (7)
  • a 2-liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was added to 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane (R 1 and R in the general formula (2)). 3 has 2 carbon atoms and has one atomic group having a polymerizable unsaturated group, and R 2 has 4 carbon atoms.) 35.9 parts by mass, methylhydroquinone 007 parts by mass and 0.07 parts by mass of 2,6-tert-butyl-p-cresol were charged and adjusted at 50 ° C. with stirring.
  • aqueous urethane resin composition (7) having a nonvolatile content of 33% by mass was obtained by adding 47.5 parts by mass of piperazine aqueous solution, causing chain extension reaction at 40 ° C., and distillation under reduced pressure.
  • Example 8 Aqueous urethane resin composition (8)
  • a urethane resin composition (8) was obtained.
  • Aqueous urethane resin composition (C1) Polyester polyol (number average molecular weight 2,000) obtained by reacting 1,6-hexanediol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer ) 100 parts by weight, 7 parts by weight of 1,4-cyclohexanedimethanol, 5.5 parts by weight of 2,2-dimethylolpropionic acid, 1 part by weight of trimethylolpropane, and 60 parts by weight of dicyclohexylmethane diisocyanate, It mixed with 58 mass parts of methyl ethyl ketone, and was made to react on the conditions of the temperature of 80 degreeC in the said reaction container, and the organic solvent solution of the urethane prepolymer which has an isocyanate group at the terminal was obtained.
  • an organic solvent solution of the urethane prepolymer and 3 parts by mass of 2-hydroxyethyl acrylate are mixed and reacted under the conditions of a temperature of 80 ° C. in the reaction vessel, whereby the side chain has no polymerizable property.
  • An organic solvent solution of a urethane resin having a saturated bond and having an isocyanate group at the end of the main chain was obtained.
  • an organic solvent solution of the urethane resin 5 parts by mass of N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, and 163 parts by mass of methyl ethyl ketone are mixed, and the temperature in the reaction vessel is set to 50.
  • An organic solvent solution of a urethane resin (II-1) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group was obtained by adjusting the reaction to ° C.
  • aqueous urethane resin composition (C1) having a nonvolatile content of 30% by mass was obtained by adding part by mass, causing a chain elongation reaction at 40 ° C., and distillation under reduced pressure.
  • Aqueous urethane resin composition (C2) A total amount of the organic solvent solution of the urethane resin (II-1), 181 parts by mass of the polysiloxane (X-1) obtained in Production Example 1 and 4 parts by mass of dimethylethanolamine were mixed, and then ion-exchanged water 774 was used.
  • An aqueous urethane resin composition (C2) having a non-volatile content of 45% by mass is prepared by adding 46 parts by mass of a 10% by weight piperazine aqueous solution, subjecting it to chain elongation at 40 ° C., and distillation under reduced pressure. Got.
  • the obtained compounded liquid was apply
  • the hardness of the coating film constituting the article was measured by a method based on a JIS test method (JIS K-5600-5-4: 1999) scratch hardness (pencil method).
  • the measurement of the elongation of the test film was performed using “Autograph AG-Xplus 1 kN (between chucks; 50 mm, tensile speed 50 mm / min)” manufactured by Shimadzu Corporation, and was based on the elongation of the test film before the tensile test. Evaluation was performed according to the following evaluation criteria.
  • A The length of the test film after the tensile test was increased by 100% or more with respect to the length of the test film before the tensile test.
  • ⁇ The length of the test film after the tensile test was extended by 50% or more and less than 100% with respect to the length of the test film before the tensile test.
  • delta The length of the test film after a tensile test extended
  • X The length of the test film after the tensile test was elongated within a range of less than 10% with respect to the length of the test film before the tensile test.
  • the obtained compounded liquid was apply
  • the flexibility of the coating film constituting the article was measured by a method based on the JIS test method (JIS K-5600-5: 1999) flex resistance test method (mandrel diameter 2 mm), and the measurement result was In addition, the evaluation was made according to the following evaluation criteria.
  • ⁇ Cracks, wrinkles and whitening of the coating film were not observed at the bent part of the coating film. ⁇ : Some cracks in the coating film or white wrinkles were observed at the bent portion of the coating film. X: Remarkable cracks of the coating film were observed in the entire bent part of the coating film.
  • a photopolymerization initiator a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone
  • ⁇ Generation of cracks and yellowing is not observed on the coating film surface. ⁇ : Some cracks and yellowing are observed in a very small part of the coating surface. X: Generation
  • the obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 ⁇ m, and a dryer with an atmospheric temperature of 100 ° C.
  • the film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece.
  • the surface of the coating film constituting the test piece is scratched with a cutter knife to a depth reaching the base material (cross cut part), and a salt spray test is performed with a salt spray tester manufactured by Suga Test Instruments Co., Ltd.
  • the rust generation area after 240 hours was visually evaluated and evaluated. The evaluation was performed separately for a flat portion not damaged by the cutter knife and a peripheral portion of the cross cut portion.
  • ⁇ Plane> The area where the generation
  • ⁇ The area where the occurrence of rust and the swelling or peeling of the coating film due to rust occurred was 5% or more and less than 30% with respect to the entire plane portion.
  • delta The area where the generation
  • X The area where the occurrence of rust and the swelling and peeling of the coating film due to rust occurred was 60% or more with respect to the entire plane portion.
  • the peripheral part of the crosscut part> (Double-circle): Generation
  • ⁇ A very small amount of rust was observed in the periphery of the crosscut part, but no peeling or swelling of the coating film due to it was observed.
  • ⁇ Rust was widely observed in the periphery of the crosscut portion, and although peeling or swelling of the coating film was observed due to this, no flow rust was observed.
  • Rust was widely generated in the periphery of the crosscut part, and peeling and swelling of the coating film due to the rust were observed. Further, contamination of the coating film due to flowing rust was observed.
  • the obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 ⁇ m, and a dryer with an atmospheric temperature of 100 ° C.
  • the film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece. 1N hydrochloric acid was spotted on the surface of the coating film constituting the test piece, and the deterioration state of the coating film after standing for 180 minutes was observed.
  • the surface of the obtained coating film was rubbed 20 times back and forth on the cured coating film with a felt soaked with toluene and ethanol.
  • the state of the coating film before rubbing and after rubbing was judged by finger touch and visual observation.
  • the evaluation criteria are as follows.
  • the obtained compounded liquid was applied on each substrate shown below using a 3 mil applicator, dried at 60 ° C. for 30 minutes, further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp, and then 25 ° C.
  • a coating film cured for 2 days was prepared.
  • the surface of the obtained coating film was subjected to a cellophane (registered trademark) peeling test of 100 squares of 1 mm square according to JIS K-5400.
  • the number of grids not peeled was measured and evaluated according to the following criteria.
  • the substrate a substrate made of polyethylene terephthalate resin and a glass substrate were used.
  • A The number of grids not peeled is 90 or more.
  • ⁇ The number of grids not peeled is 60 or more and less than 90.
  • ⁇ The number of grids not peeled is 40 to less than 60.
  • X The number of grids which do not peel is less than 40.
  • Table 1 shows the compositions of the aqueous urethane resin compositions (1) to (8) obtained in Examples 1 to 8 and the above evaluation results.
  • the composition (blending amount) in Table 1 is shown as a nonvolatile content.
  • Table 2 shows the compositions and evaluation results of the aqueous urethane resin compositions (C1) and (C2) obtained in Comparative Examples 1 and 2.
  • the composition (blending amount) in Table 2 is expressed as a nonvolatile content.
  • the coating film obtained using the aqueous urethane resin composition of the present invention has excellent coating film hardness, elongation and flexibility, and It was confirmed that it was excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
  • Comparative Examples 1 and 2 are examples of a urethane resin using a polyol other than the polyol defined in the present invention as a polyol which is a raw material of the urethane resin.
  • the coating film obtained using the aqueous urethane resin composition of Comparative Example 1 is excellent in elongation and flexibility, the weather resistance, corrosion resistance, and adhesion to the polyethylene terephthalate substrate are insufficient, and solvent resistance It was confirmed that the property was extremely bad.
  • the coating film obtained using the aqueous urethane resin composition of Comparative Example 2 has insufficient corrosion resistance and hot water resistance, and also has extremely poor solvent resistance and adhesion to a polyethylene terephthalate substrate.
  • a coating film having both coating film hardness, elongation and flexibility, corrosion resistance, warm water resistance, chemical resistance and solvent resistance cannot be formed. It was.

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Abstract

La présente invention concerne une composition aqueuse de résine uréthane qui contient un milieu aqueux et une résine uréthane comportant un groupe silyle hydrolysable ou un groupe silano et un groupe insaturé polymérisable, et qui est caractérisée en ce que la résine uréthane est obtenue en faisant réagir des polyols, un polyisocyanate et un agent de couplage au silane, lesdits polyols contenant un alkylènediol comportant deux groupes insaturés polymérisables ou plus représenté par la formule générale (1) ou un oxyalkylènediol comportant deux groupes insaturés polymérisables ou plus représenté par la formule générale (2). Cette composition aqueuse de résine uréthane peut former une pellicule protectrice qui présente d'excellentes propriétés de dureté, d'allongement et de souplesse de la pellicule protectrice et qui présente d'excellentes propriétés de résistance à la corrosion, de résistance à l'eau chaude, de résistance chimique, de résistance aux solvants, et d'adhérence à divers substrats.
PCT/JP2015/075060 2014-09-26 2015-09-03 Composition aqueuse de résine uréthane, agent de revêtement et article WO2016047415A1 (fr)

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WO2019116851A1 (fr) * 2017-12-13 2019-06-20 Dic株式会社 Composition de résine thermofusible d'uréthane durcissable à l'humidité, et produit stratifié
WO2019225148A1 (fr) * 2018-05-24 2019-11-28 Dic株式会社 Composition de résine thermofusible d'uréthane durcissable à l'humidité, et corps stratifié
JP2020094125A (ja) * 2018-12-12 2020-06-18 Dic株式会社 湿気硬化型ウレタンホットメルト樹脂組成物、及び、積層体
JPWO2021084955A1 (ja) * 2019-10-28 2021-11-25 Dic株式会社 ウレタン樹脂組成物、接着剤、及び、合成皮革
CN114805724A (zh) * 2022-05-13 2022-07-29 湘潭大学 一种对非极性表面具有优异附着力的水性聚氨酯及其制备方法

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