CN103189408B - Water-based polyurethane resin composition, coating material using said composition, and coated article - Google Patents
Water-based polyurethane resin composition, coating material using said composition, and coated article Download PDFInfo
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- CN103189408B CN103189408B CN201180053502.5A CN201180053502A CN103189408B CN 103189408 B CN103189408 B CN 103189408B CN 201180053502 A CN201180053502 A CN 201180053502A CN 103189408 B CN103189408 B CN 103189408B
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- 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
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- 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
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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- 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
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- 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
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- 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
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
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- 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
Abstract
This water-based polyurethane resin composition is obtained by dispersing, in water by using an anionic group neutralizer (D), a terminal isocyanate group-containing urethane prepolymer obtained by reacting polyol (A), isocyanate (B), and an anionic group-introducing polyol (C) containing a carboxyl group or a sulfonic acid group, and by subjecting the terminal isocyanate group-containing urethane prepolymer to elongation in water. The water-based polyurethane resin composition being characterized in that the essential component of component (A) is a C10-32 long-chain alkylene diol compound (a), wherein the content of component (a) is 1 to 20 mass % in relation to the total amount of components (A), (B) and (C), and the equivalent ratio of the isocyanate group (NCO) in component (B) relative to the total hydroxyl groups (OH) in component (A) and component (C) is 1.3 to 1.9 when NCO/OH. This water-based polyurethane resin composition exerts excellent water and chemical resistance, adhesion to a base material, and coating stability, and is particularly suitable as a coating material since the composition can be suitably used as a coating material for a surface-treated steel plate.
Description
Technical field
The present invention relates to a kind of water system polyurethane resins composition, particularly relate to resistance to chemical reagents and the water system polyurethane resins composition of paint stability excellence, the coating containing this water system polyurethane resins composition of water tolerance and acid resistance, alkali resistance etc. and be coated with application product formed by this water system polyurethane resins composition on the surface at board-like material.
Background technology
Polyurethane resins, owing to having rub resistance, adherence, non-cementability and caoutchouc elasticity, is therefore normally used as coating, solid, bonding agent and coating agent etc. widely.And, in recent years with regard to the security of environmental pollution or labour hygiene etc., there is the report of a lot of water system polyurethane resins composition.
But, time compared with the composition of water system polyurethane resins composition and solvent system or solvent-free system, have the problem of the poor properties such as water tolerance, resistance to chemical reagents, thermotolerance and tensile properties.
Such as, be used in coating during coating surface process steel plate, particularly there is the resistance to chemical reagents of water tolerance, acid resistance and alkali resistance etc. for prerequisite, but in current water system polyurethane resins composition, still there is no to meet these physical property.
In addition, water-repellancy and the grease proofness person of fiber base material is improved, there has been proposed make the fluorinated polymer (patent documentation 1) of the resultant of reaction of polyfunctional isocyanate and fluorinated alohol and the substance reaction containing polyoxyalkylenes.But because the adhesion of this fluorinated polymer and steel plate is poor, it is unsuitable for therefore using as steel plate coating.
In addition, disclosed on side chain containing chain alkyl water system polyurethane resins as water tolerance, resistance to chemical reagents, thermotolerance etc. through improve water system polyurethane resins.But, this water system polyurethane resins, when using short branched diol to carry out amidocarbonic acid esterification as main chain (patent documentation 2 ~ 4), the urethane linkages high due to cohesion energy is close to each other, and the amido formate prepolymer generated condenses, viscosity rises, and cause not easily carrying out water-dispersion.
In addition, disclosed by having aqueous dispersion type polyurethane resins composition (patent documentation 5 and 6) formed by the isocyanate compound of chain alkyl and polyvalent alcohol and water.Now, water tolerance, resistance to chemical reagents and thermotolerance can be improved, but have the problem of the security of coating.
Prior art document
Patent documentation
Patent documentation 1 Japanese Kohyo 11-511814 publication
Patent documentation 2 Japanese Unexamined Patent Publication 2000-007909 publication
Patent documentation 3 Japanese Unexamined Patent Application Publication 2005-510600 publication
Patent documentation 4 Japanese Unexamined Patent Publication 2005-068228 publication
Patent documentation 5WO06/038466 publication
Patent documentation 6 Japanese Unexamined Patent Publication 2009-203316 publication
Summary of the invention
Invent problem to be solved
The present inventor etc. are for solving the shortcoming of described prior art, further investigate the result of discussion repeatedly, find to extend by making the amido formate prepolymer entering a certain amount of long-chain alkane diol compound in amido formate resin matrix give water, the resistance to chemical reagents with excellent water tolerance, acid resistance, alkali resistance etc. can be obtained and with the adhesion of base material etc., and the water system amidocarbonic acid ester resin composition of paint stability excellence, thus complete the present invention.
Therefore, the object of this invention is to provide and a kind ofly there is excellent water tolerance, resistance to chemical reagents (acid resistance, alkali resistance) and with the adhesion of base material etc. there is being applicable to being used in the water system amidocarbonic acid ester resin composition of surface treated steel plate coating applications, the coating containing this water system polyurethane resins and being coated with the tabular application product of this coating of excellent paint stability.The technological method of dealing with problems
In other words, the present invention relates to a kind of water system polyurethane resins composition, coating containing this water system polyurethane resins composition, and on board-like material, be coated with the application product of this coating, described water system polyurethane resins composition is by by polyvalent alcohol (A), isocyanic ester (B), and the polyvalent alcohol (C) containing carboxyl and/or sulfonic importing anionic property base reacts the amido formate prepolymer at end with isocyanate group of gained, be scattered in water with the neutralizing agent (D) with anionic property base, give the water system polyurethane resins composition that water extends, it is characterized in that, described (A) composition with long-chain alkane diol compound (a) of carbonatoms 10 ~ 32 for neccessary composition, and the blended amount of described (a) composition is (A), and 1 ~ 20 quality % of the total amount of (C) composition (B), the equivalence ratio (NCO/OH) of whole hydroxyls (OH) of the isocyanate group (NCO) of described (B) composition and described (A) composition and described (C) composition is 1.3 ~ 1.9.
Described (a) compound is preferred with the long-chain alkane diol compound of carbonatoms 12 ~ 18.The blended amount of the polyvalent alcohol (C) of described importing anionic property base is preferably 0.1 ~ 30 quality % of total amount of described (A), (B) and (C) composition.
And coating of the present invention, is applicable to coating surface treated steel plate.
The effect of invention
By water system polyurethane resins composition of the present invention, the coating with excellent stability can be obtained.And, by by coatings of the present invention on surface treated steel plate, the application product with the excellent film such as water tolerance and resistance to chemical reagents can be obtained.
Embodiment
Water system polyurethane resins composition of the present invention is the amido formate prepolymer containing isocyanate group at end by being reacted gained by polyvalent alcohol (A), isocyanic ester (B) and the polyvalent alcohol (C) containing the importing anionic property base being selected from carboxyl and sulfonic anionic property base, be scattered in water with the neutralizing agent composition (D) with anionic property base, give the water system polyurethane resins composition that water extends.
Described (A) composition with long-chain alkane diol compound (a) of carbonatoms 10 ~ 32 for neccessary composition.Now, should the blended amount of (a) composition be 1 ~ 20 quality % of total amount of (A), (B) and (C) composition, preferably 1.5 ~ 15 quality %, be more preferably 2 ~ 10 quality %.
When the blended amount of described (a) composition is lower than 1 quality %, the water tolerance of water system polyurethane resins composition and resistance to chemical reagents reduce, and during more than 20 quality %, amido formate prepolymer reduces the dispersiveness of water, and become not easily manufacture water system polyurethane resins, the stability of coating reduces, therefore not preferred.
Carbonatoms be 10 ~ 32 long-chain alkane diol compound can enumerate, such as decanediol, undecane, dodecanediol, tridecane diols, tetradecane diols, pentadecane diols, hexadecane diol, heptadecane diols, octadecandiol, nonadecane glycol, icosane diols, heneicosandiol, docosane glycol, tricosane glycol, tetracosane glycol, pentacosane glycol, hexacosane glycol, heptacosane glycol, octacosane glycol, nonacosane glycol, triacontane glycol, hentriacontane glycol, the straight or branched glycol of laccerane glycol etc.
In these, with regard to the water system polyurethane resins composition that can obtain water tolerance and resistance to chemical reagents excellence, (a) composition is preferably the long alkanediol that carbonatoms is 12 ~ 18, is more preferably 1,12-dodecanediol or 1,12-octadecandiol.
Polyvalent alcohol (A) beyond described (a) composition has no particular limits, such as can use polyether polyols alcohols, polyester polyols alcohols, polyester polycarbonate polyols class, crystallinity or amorphism polycarbonate polyol class, number average molecular weight lower than 200 low molecular polylol class etc.
Described polyether polyols alcohols can enumerate 1,2-PD, 1,3-PD; Except the described low molecular polylol of TriMethylolPropane(TMP), glycerol, polyglycerol, tetramethylolmethane etc., the ethylene oxide of the amine compound of dihydroxyphenyl propane, quadrol etc. etc. and/or propylene oxide adduct; Polytetramethylene ether glycol etc.
Described polyester polyols alcohols can enumerate such as by with the polyvalent alcohol of described low molecular polylol etc., to carry out direct esterification reaction or transesterification reaction with the ester formative derivative of the polycarboxylic acid more a small amount of compared with its chemical stoichiometric or its ester, acid anhydrides, carboxylic acid halide etc. and the polyester polyol that obtains; And the polyester polyol being reacted by described polyvalent alcohol, the direct esterification of reacting the hydroxycarboxylic acid of gained with lactone or its hydrolysis and obtain.
Above-mentioned polycarboxylic acid can enumerate such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyl hexanodioic acid, 3-methyl hexanodioic acid, 3-methylglutaric acid, 2-methyl suberic acid, 3, the aliphatic dicarboxylic acid class of 8-dimethyl sebacic acid, 3,7-dimethyl sebacic acid, hydrogenated dimer acids, dimeracid etc.; The aromatic dicarboxylic acid class of phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids etc.; The ester ring type omega-dicarboxylic acids of the ester ring type dicarboxylic acid of cyclohexane dicarboxylic acid etc. etc.; The tricarboxylic acids of the trimer of trimellitic acid, trimesic acid, Castor Oil Fatty Acid etc.; The carboxylic acid of more than 4 yuan of Pyromellitic Acid etc.
The ester formative derivative of described polycarboxylic acid can enumerate the acid anhydrides of polycarboxylic acid as escribed above or the carboxylic acid halide of muriate, bromide etc.; The lower aliphatic ester etc. of the methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, pentyl ester etc. of above-mentioned polycarboxylic acid.
Described lactone can enumerate the lactone of such as γ-hexalactone, δ-caprolactone, 6-caprolactone, dimethyl-E-caprolactone, δ-valerolactone, γ-valerolactone, gamma-butyrolactone etc.
Described polyester polycarbonate polyols class can enumerate the resultant of reaction that the resultant of reaction of the resultant of reaction of the polyester glycol of such as polycaprolactone polyol etc. and carbonic acid alkane diester, ethylene carbonate and polyvalent alcohol and organic dicarboxylic acid react gained.
In addition, described crystallinity or noncrystalline polycarbonate polyol class can enumerate such as 1, ammediol, 1, the glycol of 4-butyleneglycol, 1,6-hexylene glycol, Diethylene Glycol, polypropylene glycol and/or poly-four methylene glycols etc. and the resultant of reaction etc. of phosphine, diaryl carbonate (such as diphenyl carbonate) or ring type carbonic ether (such as propylene carbonate).
The number average molecular weight of described polyether polyols alcohols, polyester polyols alcohols, polyester polycarbonate polyols class, crystallinity or noncrystalline polycarbonate polyol class is preferably 300 ~ 5000, is more preferably 500 ~ 3000.
Described number average molecular weight can enumerate such as ethylene glycol lower than the low molecular polylol class of 200, 1, 2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, Diethylene Glycol, triethylene glycol, 2-butyl-2-ethyl-1, ammediol, 1, 4-butyleneglycol, neopentyl alcohol, 3-methyl-2, 4-pentanediol, 2, 4-pentanediol, 1, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexylene glycol, 1, 7-heptanediol, 3, 5-heptanediol, 1, 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, the aliphatic diol of 9-nonanediol etc., cyclohexanedimethanol, the ester ring type glycol such as cyclohexane diol, polyvalent alcohols more than 3 valencys of trimethylolethane, TriMethylolPropane(TMP), hexose alcohols, pentose alcohols, glycerol, polyglycerol, tetramethylolmethane, Dipentaerythritol, tetra methylol propane etc.
Isocyanic ester (B) has no particular limits, and can use vulcabond and in 1 molecule, have the polymeric polyisocyanate etc. of more than 3 isocyanate group.
Vulcabond can enumerate such as toluene di-isocyanate (TD.I) diester, ditan-4,4 '-vulcabond, p-bis-isocyanic acid benzene diester, two isocyanic acid dimethylbenzene diester, two isocyanic acids 1,5-naphthalene diester, 3, the aromatic diisocyanate class of 3 '-dimethyl diphenyl-4,4'-vulcabond, two isocyanic acid two methyl oxyaniline esters, isocyanic acid tetramethyl xylene diester etc.; The ester ring type diisocyanates of different Buddhist ketone vulcabond, dicyclohexyl methyl hydride-4,4'-vulcabond, trans and/or cis-Isosorbide-5-Nitrae-cyclohexyl diisocyanate, the former bornene ester of two isocyanic acids etc.; 1,6-hexamethylene diisocyanate, 2,2,4-and/or (2,4,4)-trimethyl hexamethylene diisocyanate, rely the aliphatic diisocyanate class of amino acid vulcabond etc.; And their mixture.
Described polymeric polyisocyanate can enumerate such as triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, dimethyl triphenyl methane tetraisocyanate, they mixture etc. 3 officials can above isocyanic ester, these 3 officials can the carbonyl imide modification of above isocyanic ester, isocyanate-modified, biuret modified etc. modifier, with various block agent, they are given the isocyanic ester (trimer) and biuret trimer etc. of blocked blocked isocyanate, described vulcabond.
In them, with regard to easily obtaining, can obtain with regard to the excellent water system polyurethane resins composition such as weathering resistance and intensity, be preferably and use aliphatic diisocyanate or ester ring type vulcabond, it is particularly preferably use 1,6-hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4'-vulcabond, different Buddhist ketone vulcabond.
(C) polyvalent alcohol of anionic property base is imported for containing carboxyl and/or sulfonic polyalcohols, that can enumerate the carboxylic polyalcohols of such as dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid etc., Isosorbide-5-Nitrae-butanediol-2-sulfonic acid etc. contains sulfonic polyalcohols.
In them, with regard to easily obtaining, be preferably the polyalcohols used containing carboxylic acid group, particularly preferably for using dimethylol propionic acid.
In addition, (C) blended amount of the polyvalent alcohol of anionic property base is imported, for the total amount of described (A), (B) and (C) composition, be preferably the amount of the scope of 0.1 ~ 30 quality %, be more preferably the amount of 0.5 ~ 20 quality %, most preferably be the amount of 0.1 ~ 10 quality %.(C) when the blended amount of composition is lower than 0.1 quality %, because the water dispersible of polyurethane is poor, have the situation of the storage stability of water system polyurethane resins or the stability reduction of coating, and during more than 30 quality %, have with the cohesion energy increase of urethane linkages and cause the viscosity of amido formate prepolymer to rise, and becoming the problem of not easily carrying out water-dispersion etc.
In addition, described polyvalent alcohol (A), polymeric polyisocyanate (B) and (C) import the blended amount of the polyvalent alcohol of anionic property base, in the stage of reacting making them, the polyvalent alcohol (C) of described polyvalent alcohol (A) and importing anionic property base is for whole hydroxyl 1 equivalent, the equivalence ratio (NCO/OH) of the isocyanate group (NCO) of isocyanic ester (B) is the amount of 1.3 ~ 1.9, be preferably the amount of 1.4 ~ 1.8, be more preferably the amount of 1.5 ~ 1.7.
NCO/OH than lower than 1.3 time, due to amido formate prepolymer be higher molecular quantize, therefore have the tendency that the water dispersible of amido formate prepolymer reduces, have the situation of the storage stability of water system polyurethane resins or the bad stability of coating.In addition, when NCO/OH ratio is more than 1.9, when prepolymer carries out water-dispersion, foam because isocyanate group and water react the carbonic acid gas fierceness generated, thus can produce obstacle when manufacturing resin combination, and the effect of the water tolerance of resin, acid resistance etc. reduces.
When manufacturing water system polyurethane resins composition of the present invention, first can use as required in reaction and be inertia and the solvent large with the affinity of water, make polyvalent alcohol (C) reaction of polyvalent alcohol (A), isocyanic ester (B) and importing anionic property base, synthesis terminal isocyanate amido formate prepolymer.
Be inertia in described reaction and the solvent large with the affinity of water, preference is as acetone, methyl ethyl ketone, dioxan, tetrahydrofuran (THF), METHYLPYRROLIDONE etc.These solvents, usually use 3 ~ 100 mass parts for total amount 100 mass parts of the described raw material used when manufacturing prepolymer.When these solvents use the solvent of boiling point less than 100 DEG C, preferably after integrated drainage polyurethane resins, remove this solvent by underpressure distillation etc.
The method making terminal isocyanate amido formate prepolymer carry out water-dispersion can enumerate the prepolymer hybrid system such as having (1) to add prepolymer in water to be disperseed, and (2) add the phase conversion method etc. that water is disperseed in prepolymer.The anionic property base neutralizing agent (D) used during water-dispersion is the anionic property base neutralizing agent that the base of the anionic property be present in dispersed system is neutralized, and can be added in any one in prepolymer and water.
After so making terminal isocyanate amido formate prepolymer give water-dispersion, extending by giving water in water, synthesizing water system polyurethane resins composition of the present invention.
Described anionic property base neutralizing agent (D) can enumerate three alkanamine classes, the N of such as Trimethylamine 99, triethylamine, Tributylamine etc., N-dimethylethanolamine, N, N-dimethyl propanol amine, N, the N of N-dipropylethanolamine, 1-dimethyl amido-2-methyl-2-propanol etc., 3 grades of amine compound of the trialkanolamine class of N-dialkylalkanolamine class, N-alkyl-N, N-bis-alkanolamine, trolamine etc.; The basic cpd of ammonium, hydroxide Trimethylamine 99, sodium hydroxide, potassium hydroxide, lithium hydroxide etc.
The usage quantity of these neutralizing agents, for anionic property base 1 equivalent had in described (C) composition, is preferably the amount of 0.5 ~ 2.0 equivalent, is more preferably the amount of 0.8 ~ 1.5 equivalent.When the usage quantity of neutralizing agent is too not enough, have the problem reduced by the physical property of the water tolerance, intensity, extensibility etc. of the film of water system polyurethane resins gained etc.
Carry out described water extend time, be preferably temperature be 30 ~ 75 DEG C carry out stirring and give water extend, temperature is more preferably 40 ~ 65 DEG C.
When temperature is lower than 30 DEG C, then because production efficiency when needs react for a long time reduces, during more than 75 DEG C, then can produce with producing carbonic acid gas and the foamed phenomenon that causes because water lengthening reaction fierceness, and when producing the problem in manufacture containing during low boiling point solvent etc.
Observe the method for reaction end when described water extends, confirm that owing to using IR (infrared spectrophotometry luminance meter) method that isocyanate group disappears is simple, therefore preferably.
When manufacturing water system polyurethane resins composition of the present invention, also emulsifying agent can be used when polyurethane carries out water-dispersion.Emulsifying agent can enumerate the cationic surfactant of such as general anionic surfactant and nonionic surfactant and one-level amine salt, secondary amine salt, tertiary amine salt, level Four amine salt and pyrrole ingot salt etc., and the known emulsifying agent such as the amphoterics of betaine type, sulfuric acid ester type and sulfonic acid type etc.
Described anionic surfactant can enumerate the alkylsurfuric acid salt of such as sodium lauryl sulphate, dodecyl sulphate potassium, ammonium lauryl sulfate etc.; The polyoxyethylene alkene ether sulphate class of Brij-35 sodium sulfate, polyoxyethylene alkane ether ammonium sulfate etc.; Natrium sulforicinoleicum; The alkylsulfonate of an alkali metal salt of sulfone paraffinic hydrocarbons, the ammonium salt of sulfone paraffinic hydrocarbons etc.; The soap of sodium laurate, triethanolamine oleate, trolamine sylvate etc.; The alkylaryl sulphonate of the alkali metal sulfates of benzene sulfonic acid sodium salt, alkali phenolic hydroxy ethene etc.; High sulfonated alkyl naphathalene; Naphthalene sulfonic acidformaldehyde condensation product; Dialkyl sulfosuccinates; Polyoxyethylene alkyl-sulphate; Polyoxyethylene alkyl aryl sulfate; Polyoxyethylene ether phosphate; Polyoxyethylene alkane ether acetate; N-acyl group amido hydrochlorate; N-acyl methyl taurine salt etc.
Described nonionic surfactant can enumerate the fatty acid part ester class of the polyvalent alcohol of such as Span-20, sorbitan monooleate etc.; Polyoxyethylene glycol fatty acid ester class; Polyglycerol fatty acid ester; The ethylene oxide of the alcohol of carbon number 1 ~ 18 and/or propylene oxide adduct; The ethylene oxide of alkylphenol and/or propylene oxide adduct; The ethylene oxide of alkane glycol and/or alkane diamines and/or propylene oxide adduct etc.Form the alcohol of the carbon number 1 ~ 18 of these nonionic surfactants, such as methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, 2-butanols, 3-butanols, amylalcohol, primary isoamyl alcohol, 3-amylalcohol, hexanol, octanol, decyl alcohol, lauryl alcohol, Rou tetradecyl alcohol, palmityl alcohol, stearyl alcohol etc. can be enumerated.
Described alkylphenol can enumerate such as phenol, methylphenol, 2,4-bis--3-butylphenol, 2,5-bis--3-butylphenol, 3,5-bis--3-butylphenol, 4-(1,3-tetramethyl butyl) phenol, 4-isooctyl phenol, 4-nonylphenol, 4-3-octyl phenol, 4-dodecyl phenol, 2-(3,5-dimethyl heptyl) phenol, 4-(3,5-dimethyl heptyl) phenol, naphthols, dihydroxyphenyl propane, Bisphenol F etc.
Described alkane glycol can enumerate such as ethylene glycol, 1,2-propylene glycol, 1,3-PD, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 1,4-butyleneglycol, neopentyl alcohol, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexylene glycol etc., the alcohol hydroxyl group that alkane diamines can enumerate such as these alkane glycol is replaced to the material etc. of amido.And ethylene oxide and propylene oxide adduct can be random affixture, also can be block affixture.
Described cationic surfactant can enumerate such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, VARISOFT TA100, Timbercote 2000, lauryl benzyl dimethyl ammonium chloride, Timbercote 2000, alkyl bromination pyrrole ingot salt and lauric acid imidazole salts etc.
Described amphoterics can enumerate amido acid type, sulfuric acid ester type and the sulfonic acid type etc. of the betaine type of the metal-salt of such as coco-nut oil fatty acid amido propyl dimethyl acetic acid trimethyl-glycine, lauryl dimethyl Amino acid trimethyl-glycine, 2-alkyl-N-carboxymethyl group-N-hydroxymethylimidazole betaine salt, lauryl hydroxyl sulfo betaine, lauroyl acid amides ethyl hydroxy ethyl carboxymethyl group trimethyl-glycine, hydroxypropyl phosphoric acid etc., the metal-salt of β-lauryl amido propionic acid etc.
The usage quantity of described emulsifying agent has no particular limits, with regard to the physical property of the water tolerance, intensity, extensibility etc. of the film of coating water system polyurethane resins composition gained, for total amount 100 mass parts of described (A) ~ (C) composition, be preferably 1 ~ 30 mass parts, be more preferably 5 ~ 20 mass parts.When being less than 1 mass parts, cannot be improved dispersed effect, during more than 30 mass parts, and the problem that the physical property having described film reduces.
In addition, in water system polyurethane resins composition of the present invention, as required, in order to give polyurethane molecule crosslinked structure, the linking agent that also can use in the general amido formate prepolymer of fusion further.
Described linking agent can enumerate such as melamine, monomethylol melamine, dimethylolmelamine, tri methylol melamine, tetra methylol melamine, pentahydroxy-methylmelamine, hexamethylol melamine, methylated methylol melamine, butylation methylol melamine, melamine resin etc.In the present invention, preferably use the low price melamine of the excellent dispersion to polyurethane suitably selected from them.
When using water system polyurethane resins composition of the present invention as coating etc., suitably can dilute use.Solids content concn during dilution, have no particular limits, just dispersed or for regard to operability when obtained film, molding etc., for total amount 100 mass parts of described (A) ~ (C) composition, be preferably 1 ~ 65 mass parts, be more preferably 5 ~ 50 mass parts.
In addition, in water system polyurethane resins composition of the present invention, the general various additives used can also be added as required.This additive such as pigment; Dyestuff; Membrane producing promoter; Stiffening agent; External crosslinker; Viscosity modifier; Leveling agent; Defoamer; Anti-gelling agent; The photostabilizer of hindered amine etc.; The antioxidant of phenol based compound, phosphorus series compound, chalcogenide compound etc.; The UV light absorber be made up of triazine based compound, benzoic ether based compound, 2-(2-hydroxy phenyl) benzotriazole based compound; Free radical scavenger; Thermotolerance imparting agent; Inorganic or organic filler; Fluidizer; Smooth agent; Static inhibitor; Strengthening agent; Catalyst; Shake change agent; Antiseptic-germicide; Mould inhibitor; Anticorrosive agent; And rust-preventive agent etc.
In addition, when using water system polyurethane resins composition of the present invention in coating or coating agent, also can use and particularly give the silane coupling agent of firm adhesion, colloid silica, tetraalkoxysilane and polycondensate, sequestrant and epoxy compounds to base material.
In described various additive, when water system polyurethane resins composition of the present invention being used in exposure film without or coating, preferably use hindered amine system photostabilizer, UV light absorber and antioxidant.
Described hindered amine system photostabilizer can enumerate such as 2, 2, 6, 6-tetramethyl--4-piperidyl stearate, 1, 2, 2, 6, 6-pentamethyl--4-piperidyl stearate, 2, 2, 6, 6-tetramethyl--4-piperidyl benzoic ether, two (2, 2, 6, 6-tetramethyl--4-piperidyl) decylate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) decylate, two (1-octyloxy-2, 2, 6, 6-tetramethyl--4-piperidyl) decylate, 1, 2, 2, 6, 6-pentamethyl--4-piperidyl methyl methyl acrylate, 2, 2, 6, 6-tetramethyl--4-piperidyl methyl methyl acrylate, four (2, 2, 6, 6-tetramethyl--4-piperidyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, four (1, 2, 2, 6, 6-pentamethyl--4-piperidyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, two (2, 2, 6, 6-tetramethyl--4-piperidyl) two (dodecyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) two (dodecyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl)-2-butyl-2-(3, 5-bis--3-butyl-4-hydroxyphenylmethyl) malonic ester, 1-(2-hydroxyethyl)-2, 2, 6, 6-tetramethyl--4-piperidine alcohols/ethyl succinate bunching thing, 1, 6-two (2, 2, 6, 6-tetramethyl--4-piperidyl amido) hexane/ethylene dibromide bunching thing, 1, 6-two (2, 2, 6, 6-tetramethyl--4-piperidyl amido) the chloro-6-morpholinyl of hexane/2.4-bis--s-triazine bunching thing, 1, 6-two (2, 2, 6, 6-tetramethyl--4-piperidyl amido) hexane/2, 4-bis-chloro-6-3-octyl group amido-s-triazine bunching thing, 1, 5, 8, 12-tetra-[2, two (N-butyl-the N-(2 of 4-, 2, 6, 6-tetramethyl--4-piperidyl) amido)-s-triazine-6-base]-1, 5, 8, 12-teteaazacyclododecane, 1, 5, 8, 12-tetra-[2, two (N-butyl-the N-(1 of 4-, 2, 2, 6, 6-pentamethyl--4-piperidyl) amido)-s-triazine-6-base]-1, 5, 8, 12-teteaazacyclododecane, 1, 6, 11-tri-[2, two (N-butyl-the N-(2 of 4-, 2, 6, 6-tetramethyl--4-piperidyl) amido)-s-triazine-6-base amido] undecane, 1, 6, 11-tri-[2, two (N-butyl-the N-(1 of 4-, 2, 2, 6, 6-pentamethyl--4-piperidyl) amido)-s-triazine-6-base amido] undecane, 3, 9-two [1, 1-dimethyl-2-[three (2, 2, 6, 6-tetramethyl--4-piperidyl oxidation carbonyl oxygen base) butyl carbonyl oxygen base] ethyl]-2, 4, 8, 10-tetra-oxa-spiral [5, 5] undecane, 3, 9-two [1, 1-dimethyl-2-[three (1, 2, 2, 6, 6-pentamethyl--4-piperidyl oxidation carbonyl oxygen base) butyl carbonyl oxygen base] ethyl]-2, 4, 8, 10-tetra-oxa-spiral [5, 5] undecane etc.
Described UV light absorber can enumerate such as 2,4-dihydroxy benaophenonel, ESCALOL 567,2-hydroxyl-4-octyloxybenzophenone, 5, the 2-hydroxy benzophenone ketone of 5 '-methylene-bis (ESCALOL 567) etc., 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-5-3-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, 5-bis--3-butyl phenyl)-5-chlorination benzotriazole, 2-(2-hydroxyl-3-3-butyl-5-aminomethyl phenyl)-5-chlorination benzotriazole, 2-(2-hydroxyl-3, 5-bis-cumenyl phenyl) benzotriazole, 2, 2 '-methylene-bis (4-3-octyl group-6-benzotriazole base phenol), the macrogol ester of 2-(2-hydroxyl-3-3-butyl-5-carboxyl phenyl) benzotriazole, 2-[2-hydroxyl-3-(2-acryloyl-oxyethyl)-5-aminomethyl phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-5-3-butyl phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-5-3-octyl phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-5-3-butyl phenyl]-5-chlorination benzotriazole, 2-[2-hydroxyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-3-butyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-3-amyl group-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-3-butyl-5-(3-methacryloxypropyl) phenyl]-5-chlorination benzotriazole], 2-[2-hydroxyl-4-(2-methacryloxymethyl) phenyl] benzotriazole, 2-[2-hydroxyl-4-(3-methacryloxy-2-hydroxypropyl) phenyl] benzotriazole, 2-(2-hydroxy phenyl) benzotriazole category of 2-[2-hydroxyl-4-(3-methacryloxypropyl) phenyl] benzotriazole etc., 2-(2-hydroxyl-4-p-methoxy-phenyl)-4, 6-phenylbenzene-1, 3, 5-triazine, 2-(2-hydroxyl-4-cyclohexyl phenyl)-4, 6-phenylbenzene-1, 3, 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-hydroxyl [2-hydroxyl-4-(3-C12 ~ C13 mixed oxyalkyl-2-hydroxy propyloxy group) phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-acryloyloxyethoxy) phenyl]-4, two (the 4-aminomethyl phenyl)-1 of 6-, 3, 5-triazine, 2-(2, 4-dihydroxyl-3-allyl phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2, 4, 6-tri-(2-hydroxy-3-methyl-4-Hexyloxy-phenyl)-1, 3, the 2-(2-hydroxy phenyl)-4 of 5-triazine etc., 6-diallyl-1, 3, 5-triazines, phenyl salicylic acid esters, resorcinol monobenzoate, 2, 4-bis-3-butyl phenyl-3, 5-bis-3-butyl-4-HBA ester, octyl group (3, 5-bis-3-butyl-4-hydroxyl) benzoic ether, dodecyl (3, 5-bis-3-butyl-4-hydroxyl) benzoic ether, tetradecyl (3, 5-bis--3-butyl-4-hydroxyl) benzoic ether, hexadecyl (3, 5-bis--3-butyl-4-hydroxyl) benzoic ether, octadecyl (3, 5-bis--3-butyl-4-hydroxyl) benzoic ether, Shan Yu base (3, 5-bis--3-butyl-4-hydroxyl) benzoates of benzoic ether etc., the replacement oxanilide class of 2-ethyl-2 '-oxyethyl group oxanilide, 2-oxyethyl group-4 '-dodecyl oxanilide etc., the cyanoacrylate of ethyl-alpha-cyano-β, β-diphenylacrylate ester, methyl-2-cyano group-3-methyl-3-(p-p-methoxy-phenyl) acrylate etc., the salt of various metal-salts or metallo-chelate, particularly nickel or chromium or inner complex class etc.
Described antioxidant can enumerate such as phosphorus system, phenol system or sulphur system antioxidant.
Phosphorous antioxidant can enumerate such as triphenyl, three (2,4-bis-3-butyl phenyl) phosphoric acid ester, three (2,5-bis--3-butyl phenyl) phosphoric acid ester, three (nonyl phenyl) phosphoric acid ester, three (dinonylphenyl) phosphoric acid ester, three is (single, two mixing nonyl phenyl) phosphoric acid ester, phenylbenzene acid phosphoric acid ester, 2,2 '-methylene-bis (4,6-bis--3-butyl phenyl) octyl phosphate, phenylbenzene decylphosphonic acid ester, phenylbenzene octyl phosphate, two (nonyl phenyl) pentaerythritol diphosphate, phenyl diiso decyl phosphoric acid ester, Tributyl phosphate ester, three (2-ethylhexyl) phosphoric acid ester, tridecyl phosphate esters, three Tryfac 5573s, dibutyl acid phosphoric acid ester, dilauryl acid phosphoric acid ester, three lauryl phosphorous sulphide acid esters, two (neopentyl alcohol) Isosorbide-5-Nitrae-cyclohexanedimethyl bisphosphate, two (2,4-bis--3-butyl phenyl) pentaerythritol diphosphate, two (2,5-bis--3-butyl phenyl) pentaerythritol diphosphate, two (2,6-bis--3-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate, two (2,4-bis-cumenyl phenyl) pentaerythritol diphosphate, distearyl pentaerythritol diphosphate, four (C12-C15 mixed alkyl)-4,4 '-diisopropylidene diphenyl phosphoester, two [2,2 '-methylene-bis (4,6-diamyl phenyl)] isopropylidene diphenyl phosphoester, four-tridecyl 4, two (the 2-3-butyl-5-methylphenol) bisphosphate of 4 '-butylidene, six (tridecyl) 1,1,3-tri-(2-methyl-5-3-butyl-4-hydroxy phenyl) butane triguaiacyl phosphate, four (2,4-bis--3-butyl phenyl) biphenyl bisphosphate, three (2-[[2,4,7,9-tetra--3-butyl dibenzo [d, f] [1,3,2] dioxa phosphorus (phosphepin)-6-base) oxidation] ethyl] amine, 9,10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound, three (2-[(2,4,8,10-tetra--3-butyl dibenzo [d, f] [1,3,2] dioxa phosphorus-6-base) is oxidized] ethyl) amine, 2-(1,1-dimethyl ethyl)-6-methyl-4-[3-[[2,4,8,10-trans (1,1-dimethyl ethyl) dibenzo [d, f] [1,3,2] dioxa phosphorus-6-base] oxidation] propyl group] phenol-2-butyl-2-ethyl glycol 2,4,6-tri--3-butylphenol phosplate etc.
Phenol system antioxidant can enumerate such as 2,6-bis--3-butyl-p-cresols, 2,6-phenylbenzene-4-octade-cyloxyphenol, stearyl (3,5-bis--3-butyl-4-hydroxy phenyl) propionic ester, distearyl (3,5-bis--3-butyl-4-hydroxyphenylmethyl) phosphoric acid ester, tridecyl 3,5-bis--3-butyl-4-hydroxyphenylmethyl sulfuration acetic ester, sulfuration divinyl two [(3,5-bis--3-butyl-4-hydroxy phenyl) propionic ester], 4,4 '-sulfuration two (6-3-butyl-m-cresols), 2-octyl group sulfuration-4,6-bis-(3,5-bis--3-butyl-4-hydroxyphenoxy)-s-triazine, 2,2 '-methylene-bis (4-methyl-6-3-butylphenol), two [two (4-hydroxyl-3-3-butyl phenyl) butyric acid of 3,3-] glycol ester, 4,4 '-butylidene two (2,6-bis--3-butylphenol), 4,4 '-butylidene two (6-3-butyl-3-methylphenol), 2,2 '-ethylenebis (4,6-bis--3-butylphenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-3-butyl phenyl) butane, two [2-3-butyl-6-(2-hydroxyl-3-3-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tri-(2,6-dimethyl-3-hydroxyl-4-3-butyl benzyl) isocyanic ester, 1,3,5-tri-(3,5-bis-3-butyl-4-hydroxyphenylmethyl) isocyanic ester, 1,3,5-tri-(3,5-bis-3-butyl-4-hydroxyphenylmethyl)-2,4,6-Three methyl Benzenes, 1,3,5-tri-[(3,5-bis--3-butyl-4-hydroxy phenyl) Among] isocyanic ester, four [methylene radical-3-(3 ', 5 '-two-3 butyl-4 '-hydroxy phenyl) propionic ester] methane, 2-3-butyl-4-methyl-6-(2-acryloxy-3-3-butyl-5-methylbenzyl) phenol, two [2-(3-3-butyl-4-hydroxy-5-methyl base hydroxy cinnamate acyl-oxygen base)-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxa-spiral [5.5] undecanes of 3,9-, triethylene glycol two [β-(3-3-butyl-4-hydroxy-5-methyl base phenyl) propionic ester], tocopherol etc.
Sulphur system antioxidant can enumerate such as sulfuration dipropionic acid two the 8th lunar month ester, the cool ester of Er Rou Beans, myristin, stearate, SUNSOFT Q-182S etc. the β-alkylmercaptopropionates class of polyvalent alcohol of dialkyl group sulfuration dipropionate class and tetramethylolmethane four (β-dodecy propionic ester) etc.
Each usage quantity of described hindered amine system photostabilizer, UV light absorber and antioxidant, for total amount 100 mass parts of described (A) ~ (C) composition, be preferably 0.001 ~ 10 mass parts, be particularly preferably 0.01 ~ 5 mass parts.When being less than 0.001 mass parts, sufficient additive effect cannot be obtained, and if be greater than 10 mass parts time, bad impact can be had on dispersed or coating physical property.
Add the method for these hindered amine system photostabilizers, UV light absorber, antioxidant, can be the method be added in polyvalent alcohol, the method be added in prepolymer, the method be added on when water-dispersion in aqueous phase, when any method in the method for adding after water-dispersion, but the method being preferably added on the method in polyvalent alcohol and being added in prepolymer with regard to easy operation.
The purposes of water system polyurethane resins composition of the present invention can enumerate the sticking agent, molding etc. of such as coating, sticking agent, surface modifier, organic and/or inorganic powder.
Specifically, the inorganic series structure material coating such as the sticking agent of such as glass fibre collecting agent, heat sensitive paper coating agent, ink jetting paper coating agent, printing-ink, steel plate coating agent, agricultural film coating agent, glass, slabstone, concrete, carpenter's coating, fibre finish, sponge, protection pad, gloves, condom etc. can be enumerated.In these, be preferably used as the coating material of coating, timber, paper, fiber, glass, electronic material part and steel plate, particularly preferably for being used as the coating of surface treated steel plate.
When using water system polyurethane resins composition of the present invention as coating, such as, method by the suitable selection of brush coating, cylinder coating, spraying coating, photogravure coating, the coating of reversible roller coat cloth, cutter, rod coating, heavy curtain roller coat cloth, dip coated, rod coating, scraper for coating etc. is coated on base material.
Below, by embodiment, the present invention will be described in more detail, but the present invention not limited by these.
Embodiment
Embodiment 1
1 as long-chain alkane diol compound (a) in polyvalent alcohol (A) is added in reaction flask, 12-octadecandiol 6.0g (0.0209 mole), as other (A) composition by 1, polyester polyol (number average molecular weight 1750) 65.7g (0.0375 mole) of 6-hexylene glycol and hexanodioic acid and different terephthalic acid (mass ratio of hexanodioic acid/different terephthalic acid is 50/50) gained, as the dicyclohexyl methyl hydride-4 of isocyanic ester (B), 4 '-vulcabond (being recited as hydrogenation MDI below) 42.5g (0.1620 mole), as the dimethylol propionic acid 5.74g (0.0428 mole) of the polyvalent alcohol (C) of importing anionic property base.
The ratio of (a) composition in the total amount of (A) now ~ (C) composition is 5 quality %, and the ratio of (C) composition is the equivalence ratio of 4.8 quality %, NCO/OH is 1.6.
In addition, add the METHYLPYRROLIDONE 25.7g of solvent, carry out reaction 2 ~ 3 hours in stream of nitrogen gas, at 100 ~ 110 DEG C, confirm that the containing ratio of NCO is less than 3.4%.Then, add the triethylamine 4.33g (0.0428 mole) as anionic property base neutralizing agent (D), make neutralization ratio become 1.0, obtained solids content is the amido formate prepolymer of 80 quality %.
Add in water 110g defoamer (ADEKA (stock) system, B1016) 0.1g and in order to make the neutralization ratio of described amido formate prepolymer become 0.2 triethylamine 1.18g (0.0117 mole) and in the aqueous solution carrying out stirring and obtain, add described amido formate prepolymer 109g, at 20 ~ 40 DEG C, carry out stirring disperseed for 15 minutes.By the dispersion liquid of the amido formate prepolymer of gained, water lengthening reaction is carried out 12 hours at 30 ~ 40 DEG C, and then confirm until the time that NCO base disappears carries out water lengthening reaction to be measured by IR (infrared spectrophotometry luminance meter) at 50 ~ 55 DEG C, take obtained solids content as the water system polyurethane resins composition of 40%.
Embodiment 2
1 as long-chain alkane diol compound (a) in polyvalent alcohol (A) is added in reaction flask, 12-octadecandiol 12.0g (0.0593 mole), as other (A) composition by 1, polycarbonate diol (number average molecular weight 2000) 49.0g (0.0245 mole) of 6-hexylene glycol and hexanodioic acid, as different Buddhist ketone vulcabond (the being recited as IPDI below) 51.9g (0.234 mole) of isocyanic ester (B) and as the dimethylol propionic acid 7.17g (0.0535 mole) of polyvalent alcohol (C) importing anionic property base.
The ratio of (a) composition in the total amount of (A) now ~ (C) composition is 10 quality %, and the ratio of (C) composition is the equivalence ratio of 6.0 quality %, NCO/OH is 1.7.
In addition, add the METHYLPYRROLIDONE 24.6g as solvent, carry out reaction 2 ~ 3 hours in stream of nitrogen gas, at 100 ~ 110 DEG C, confirm that NCO% is less than 5.4%.Then, add the triethylamine 5.41g (0.0535 mole) as anionic property base neutralizing agent (D), make neutralization ratio become 1.0, obtained solids content is the amido formate prepolymer of 80 quality %.
Defoamer (ADEKA (stock) system, B1016) 0.1g is added in water 110g, and in order to make to become with the neutralization ratio of described amido formate prepolymer 0.2 and add triethylamine 1.47g (0.0145 mole).And then, in the aqueous solution stirring gained, add described amido formate prepolymer 108g, at 20 ~ 40 DEG C, carry out stirring disperseed for 15 minutes.By the dispersion liquid of the amido formate prepolymer of gained, water lengthening reaction is carried out 12 hours at 30 ~ 40 DEG C, and then confirm to carry out water lengthening reaction in the time till the disappearance of NCO base at 40 ~ 45 DEG C, being measured by IR (infrared spectrophotometry luminance meter), take obtained solids content as the water system polyurethane resins composition of 40%.
Embodiment 3
1, the 12-octadecandiol 2.4g (0.0084 mole) as long-chain alkane diol compound (a) in polyvalent alcohol (A), polytetramethylene ether diol (number average molecular weight 2000) 81.4g (0.0407 mole) as other (A) composition is added, as the hydrogenation MDI31.9g (0.1216 mole) of isocyanic ester (B) and as the dimethylol propionic acid 4.30g (0.0321 mole) of polyvalent alcohol (C) importing anionic property base in reaction flask.
The ratio of (a) composition in the total amount of (A) now ~ (C) composition is 2 quality %, and the ratio of (C) composition is the equivalence ratio of 3.6 quality %, NCO/OH is 1.5.
In addition, add the METHYLPYRROLIDONE 26.8g as solvent, reaction is carried out 2 ~ 3 hours in stream of nitrogen gas, at 100 ~ 110 DEG C, confirm that NCO% becomes after below 2.3%, the triethylamine 3.24g (0.0320 mole) added as anionic property base neutralizing agent (D) makes neutralization ratio become 1.0, take obtained solids content as the amido formate prepolymer of 80 quality %.
In water 110g, add defoamer (ADEKA (stock) system, B1016) 0.1g, and make the neutralization ratio of described amido formate prepolymer become the triethylamine 0.88g (0.0087 mole) of 0.2.Then, in the aqueous solution carrying out stirring gained, add described amido formate prepolymer 109g, at 20 ~ 40 DEG C, carry out stirring disperseed for 15 minutes.By the dispersion liquid of the amido formate prepolymer of gained, water lengthening reaction is carried out 12 hours at 30 ~ 40 DEG C, and then confirm until the time that NCO base disappears carries out water lengthening reaction to be measured by IR (infrared spectrophotometry luminance meter) at 60 ~ 65 DEG C, take obtained solids content as the water system polyurethane resins composition of 40%.
Comparative example 1
Except the polyester polyol 77.7g (0.0444 mole) being used as the embodiment 1 of (A) composition to use and the hydrogenation MDI36.6g (0.140 mole) as (B) composition, and do not use outside (a) composition, by the method identical with embodiment 1, make (A) ~ (C) composition reacts.Confirm that NCO% is less than 2.9%.Then, the triethylamine 4.33g (0.0428 mole) added as anionic property base neutralizing agent (D) makes neutralization ratio become 1.0, take obtained solids content as the amido formate prepolymer of 80 quality %.
In the total amount of (A) during charging ~ (C) composition, the ratio of (C) composition is the equivalence ratio of 4.8 quality %, NCO/OH is 1.6.
By the method identical with embodiment 1, the amido formate prepolymer of gained being carried out water-dispersion and water lengthening reaction, take obtained solids content as the water system polyurethane resins composition of 40%.
Comparative example 2
Except being used as 1 of (a) composition, 12-octadecandiol 30.0g (0.105 mole), the polyester polyol 18.0g (0.0103 mole) used as the embodiment 1 of other (A) compositions and as (B) composition hydrogenation MDI66.2g (0.252 mole) outward, by the method identical with embodiment 1, make (A) ~ (C) composition reacts.Confirm that the containing ratio % of NCO is after less than 5.3%, the triethylamine 4.33g (0.0428 mole) added as anionic property base neutralizing agent (D) makes neutralization ratio become 1.0, take obtained solids content as the amido formate prepolymer of 80 quality %.
The ratio adding (a) composition in the total amount of fashionable (A) ~ (C) composition is 25 quality %, and the ratio of (C) composition is the equivalence ratio of 4.8 quality %, NCO/OH is 1.6.
Use the amido formate prepolymer of gained, by the method identical with embodiment 1, during tentative manufacture water system polyurethane resins composition, the moisture scattered error of amido formate prepolymer, cannot obtain the water system polyurethane resins composition of favorable dispersity.
Comparative example 3
The polyester polyol 77.1g (0.0441 mole) used except the embodiment 1 as (A) composition used except (a) composition and as (B) composition hydrogenation MDI31.1g (0.119 mole) outward, by the method identical with embodiment 1, make (A) ~ (C) composition reacts.Confirm that the containing ratio % of NCO is after less than 0.6%, the triethylamine 4.33g (0.0428 mole) added as anionic property base neutralizing agent (D) makes neutralization ratio become 1.0, take obtained solids content as the amido formate prepolymer of 80 quality %.
In the total amount of (A) during charging ~ (C) composition, the ratio of (a) composition is 5 quality %, and the ratio of (C) composition is the equivalence ratio of 4.8 quality %, NCO/OH is 1.1.
By the amido formate prepolymer of gained by the method identical with embodiment 1, during tentative manufacture water system polyurethane resins composition, amido formate prepolymer cannot be scattered in water, cannot obtain water system polyurethane resins composition.
Comparative example 4
The polyester polyol 53.8g (0.0307 mole) used except the embodiment 1 as (A) composition used except (a) composition and as (B) composition hydrogenation MDI54.5g (0.208 mole) outward, by the method identical with embodiment 1, make (A) ~ (C) composition reacts.Confirm that the containing ratio % of NCO is after less than 6.3%, the triethylamine 4.33g (0.0428 mole) added as anionic property base neutralizing agent (D) makes neutralization ratio become 1.0, take obtained solids content as the amido formate prepolymer of 80 quality %.
In the total amount of (A) during charging ~ (C) composition, the ratio of (a) composition is 5 quality %, and the ratio of (C) composition is the equivalence ratio of 4.8 quality %, NCO/OH is 2.2.
Use the amido formate prepolymer of gained, by the method identical with embodiment 1, during tentative manufacture water system polyurethane resins composition, when amido formate prepolymer carries out water-dispersion, supervene carbonic acid gas and cause remarkable foaming, water system polyurethane resins composition cannot be obtained.
Comparative example 5
Except use 1, the polyester polyol 58.9g (0.0337 mole) that 8-ethohexadiol 6.0g (0.041 mole) replaces (a) long-chain alkane diol compound, use as the embodiment 1 of other (A) composition and as (B) composition hydrogenation MDI49.3g (0.188 mole) outward, by the method identical with embodiment 1, make (A) ~ (C) composition reacts.What confirm NCO is after less than 4.0% containing rate %, and the triethylamine 4.33g (0.0428 mole) added as anionic property base neutralizing agent (D) makes neutralization ratio be 1.0, take obtained solids content as the amido formate prepolymer of 80 quality %.
In the total amount of (A) during charging ~ (C) composition, 1,8-ethohexadiol be 5 quality %, the ratio of (C) composition is the equivalence ratio of 4.8 quality %, NCO/OH is 1.6.
Use the amido formate prepolymer of gained, by the method identical with embodiment 1, carry out water-dispersion and water lengthening reaction, obtained solids content is the water system polyurethane resins composition of 40%.
Comparative example 6
After carrying out water-dispersion with the identical amido formate prepolymer that described embodiment 1 uses under the same terms, the quadrol 3.57g (0.119 mole) of usage chain elongation agent gives polymer and quantizes, and obtained water system polyurethane resins composition.
Comparative example 7
Except relative to described (A), and total amount 100 mass parts of (C) composition (B), emulsifying agent (ADEKA (stock) system that described comparative example 6 is used of 10 mass parts is added in water, ProductName Adeka Pluronic F-108): the ethylene oxide adduct of polypropylene glycol, molecular-weight average 15500, ethylene oxide content 80 quality %) and carry out outside water-dispersion, the equivalence ratio of NCO/OH, the setting such as neutralization ratio and solids content is identical with comparative example 6, with the manufacturing condition identical with comparative example 6, obtained water system polyurethane resins composition.
< Performance Evaluation >
As described below, the water tolerance of the paint stability of the water system polyurethane resins composition of described embodiment 1 ~ 3 and comparative example 1,5 ~ 7 gained, film, acid resistance, alkali resistance and adhesion are assessed.
These results are as shown in table 1.
Paint stability
With respect to water system polyurethane resins composition 100 mass parts of described embodiment and comparative example gained, CYMEL325 (Japanese Cytec Industries Inc., methylated melamines resin, solids content 80%) 15 mass parts are made to carry out mix and blend, add dimethylethanolamine again, pH value is adjusted to 8.5, obtained experimental liquid.The experimental liquid measuring gained places the viscosity of front and back on the 10th at 40 DEG C, by the stability of the viscosity assessment coating after rising.
Zero: there is no viscosity rising situation, have good stability
△: observe viscosity rising situation
×: observe significant viscosity rising situation
Test body makes
Use electrogalvanizing steel plate as base material, and use pH value to be the grease-removing agent of 11 ~ 13, at 60 DEG C, carry out skimming treatment 5 minutes.On the electrogalvanizing steel plate through skimming treatment, the water system polyurethane resins composition by described embodiment 1 ~ 5 and comparative example 1 ~ 4 gained of coating thickness 1 μm.Heat drying 4 second under the environment of 300 DEG C, to make the plate temperature of steel plate become 75 DEG C, and obtained test body.
Water tolerance test
About the test body of gained, 65 DEG C, under the relative humidity of 95%, carry out the water-fast patch test of 24 hours, the painting membrane stage after being tested by visual assessment with following benchmark.
5: film does not have abnormal conditions
4: the emersion situation of film is less than 5% of gross area
3: the emersion situation of film is 6 ~ 20% of gross area
2: the emersion situation of film is more than 21% of gross area
1: film is peeled off completely
Acid resisting test
By the H of test body in 1 quality %
2sO
4dipping 24 hours in the aqueous solution (25 DEG C), and the painting membrane stage after being flooded by visual assessment with following benchmark.
5: film does not have abnormal conditions
4: the emersion situation of film is less than 5% of gross area
3: the emersion situation of film is 6 ~ 20% of gross area
2: the emersion situation of film is more than 21% of gross area
1: film is peeled off completely
Alkaline resistance test
Use described test body to flood 1 hour in the NaOH aqueous solution (25 DEG C) of 1 quality %, pass through visual assessment with following benchmark.
5: film does not have abnormal conditions
4: the emersion situation of film is less than 5% of gross area
3: the emersion situation of film is 6 ~ 20% of gross area
2: the emersion situation of film is more than 21% of gross area
1: film is peeled off completely
Adhesion
On untreated electrogalvanizing steel plate, after the water system polyurethane resins composition of coating 1 μm of thickness, under the environment of 300 DEG C, heat drying makes the temperature of steel plate be 150 DEG C for 15 seconds, obtained test body.
By JIS K5600-5-6 (staggered breaks method), peel off situation with the film of following this test film of benchmarking exercise.
5: film does not have abnormal conditions
4: film has slightly emersion situation (area of less than 5%)
3: film seldom has the emersion situation area of less than 20% (more than 5%)
2: film has a lot of emersion situation (area more than 20%)
1: film is peeled off completely
[table 1]
* 1:C18:1,12-octadecandiol
* 2:C12:1,12-dodecanediol
* 3: blended amount: relative to the quality % for the total amount of (A), (B) and (C) composition
* 4: quadrol
* 5:Adeka Pluronic F-108: the mass fraction of the emulsifying agent for total amount 100 mass parts of (A), (B) and (C) composition
From the result of described embodiment and comparative example, confirm only water system polyurethane composition of the present invention, the result that paint stability, water tolerance, resistance to chemical reagents and adhesion are all good can be obtained.
Industrial applicibility
Water system polyurethane resins composition of the present invention, owing to being water system, not only can not damage and good work environment, the film of the resistance to chemical reagents with excellent paint stability, water tolerance, acid resistance and alkali resistance etc. can be formed, by coating on the surface of timber, paper, fiber, glass, electronic material part and steel plate etc., be suitable for manufacturing water tolerance, the material of resistance to chemical reagents excellence or molding.
Claims (6)
1. a water system polyurethane resins composition, it is by by polyvalent alcohol (A), isocyanic ester (B), and the polyvalent alcohol (C) containing carboxyl or sulfonic importing anionic property base reacts the terminal isocyanate group amido formate prepolymer of gained, be scattered in water with anionic property base neutralizing agent (D), give the water system polyurethane resins composition that water extends, it is characterized in that, described (A) composition with long-chain alkane diol compound (a) of carbonatoms 10 ~ 32 for neccessary composition, and the blended amount of described (a) composition is (A), and 1 ~ 20 quality % of the total amount of (C) composition (B), the equivalence ratio (NCO/OH) of whole hydroxyls (OH) of the isocyanate group (NCO) of described (B) composition and described (A) composition and described (C) composition is 1.3 ~ 1.8.
2. water system polyurethane resins composition as claimed in claim 1, it is characterized in that, described (a) compound is the long-chain alkane diol compound of carbonatoms 12 ~ 18.
3. water system polyurethane resins composition as claimed in claim 1 or 2, it is characterized in that, the blended amount of the polyvalent alcohol (C) of described importing anionic property base is 0.1 ~ 30 quality % of total amount of described (A), (B) and (C) composition.
4. a coating, is characterized in that, containing water system polyurethane resins composition as claimed any one in claims 1 to 3.
5. application product, is characterized in that, board-like material is coated with coating as claimed in claim 4 and forms.
6. application product as claimed in claim 5, it is characterized in that, described board-like material is surface treated steel plate.
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| JP2010250813A JP5643613B2 (en) | 2010-11-09 | 2010-11-09 | Water-based polyurethane resin composition, paint and coated article using the composition |
| JP2010-250813 | 2010-11-09 | ||
| PCT/JP2011/006186 WO2012063450A1 (en) | 2010-11-09 | 2011-11-07 | Water-based polyurethane resin composition, coating material using said composition, and coated article |
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| KR101990796B1 (en) * | 2013-09-24 | 2019-06-19 | 에스케이이노베이션 주식회사 | Composition of solvent-based gravure ink using polyalkylene carbonate and manufacturing method for thereof |
| CN107614616B (en) * | 2015-05-25 | 2021-05-18 | Dic株式会社 | Aqueous polyurethane resin composition and article |
| TW201906887A (en) * | 2017-06-29 | 2019-02-16 | 日商迪愛生股份有限公司 | Aurethane resin composition, steel sheet surface treatment agent and steel sheet having the same |
| WO2019124011A1 (en) * | 2017-12-22 | 2019-06-27 | 三菱ケミカル株式会社 | Resin composition, coating composition and coated article |
| CN109554090A (en) * | 2018-11-12 | 2019-04-02 | 安徽科创美涂料科技股份有限公司 | A kind of aqueous functional polyurethane coating of anion and preparation method thereof |
| CN113163884A (en) * | 2018-12-07 | 2021-07-23 | Dic株式会社 | Gloves |
| EP3901366A4 (en) * | 2018-12-18 | 2022-03-02 | DIC Corporation | Urethane resin composition, film and synthetic leather |
| CN111607057A (en) * | 2020-06-03 | 2020-09-01 | 东莞市神乐高分子科技有限公司 | Water-based transparent polyurethane, water-based UV (ultraviolet) curing gloss oil, water-based UV curing printing ink and preparation method thereof |
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| CN101265318A (en) * | 2008-05-15 | 2008-09-17 | 海聚高分子材料科技（广州）有限公司 | High-performance water-based polyurethane dispersoid and application thereof |
| WO2009107325A1 (en) * | 2008-02-27 | 2009-09-03 | 株式会社Adeka | Aqueous polyurethane resin composition and article coated with the same |
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| JP2000007909A (en) * | 1998-06-19 | 2000-01-11 | Sekisui Chem Co Ltd | Urethane based aqueous composition |
| JP4104229B2 (en) * | 1998-11-06 | 2008-06-18 | 株式会社Ａｄｅｋａ | Water-based polyurethane resin composition |
| US20130022746A9 (en) * | 2007-12-10 | 2013-01-24 | Harry Joseph Spinelli | Aqueous inkjet inks with ionically stabilized dispersions and polyurethane ink additives |
| US9410010B2 (en) * | 2007-12-10 | 2016-08-09 | E I Du Pont De Nemours And Company | Urea-terminated polyurethane dispersants |
| WO2009076386A1 (en) * | 2007-12-10 | 2009-06-18 | E. I. Du Pont De Nemours And Company | Aqueous inkjet inks with ionically stabilized dispersions and polyurethane ink additives |
| US20100093927A1 (en) * | 2007-12-10 | 2010-04-15 | Roberts C Chad | Polyurethanes with Nonionic Hydrophilic Terminating Groups and Aqueous Dispersions Thereof |
| JP5511537B2 (en) * | 2010-06-18 | 2014-06-04 | 株式会社Ａｄｅｋａ | Water-based polyurethane resin composition and paint using the composition |
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| WO2009107325A1 (en) * | 2008-02-27 | 2009-09-03 | 株式会社Adeka | Aqueous polyurethane resin composition and article coated with the same |
| CN101265318A (en) * | 2008-05-15 | 2008-09-17 | 海聚高分子材料科技（广州）有限公司 | High-performance water-based polyurethane dispersoid and application thereof |
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