CN101497687B - Anti-scratch aqueous polyurethane disperse system with high hygrometric state adhesive force and use thereof - Google Patents
Anti-scratch aqueous polyurethane disperse system with high hygrometric state adhesive force and use thereof Download PDFInfo
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Abstract
The invention discloses an aqueous polyurethane dispersion with scuffing resistance and high wet adhesion and the application thereof. The aqueous polyurethane dispersion is produced from reactive coupling agent, polymer polylol, polyisocyanate, hydrophilic chain extender, neutralizing agent and polyamine. The reactive coupling agent is added in a raw material system, and after being coated on metal, glass, fibre glass, cement substrate material, magnesia, ceramics or stone, the prepared aqueous polyurethane dispersion can remarkably improve the scuffing resistant capability and the adhesive force to the substrate material of the coating, especially the adhesive force to the substrate material under the damp environment, thereby effectively makes up the deficiencies of the prior coating technology.
Description
Technical field
The invention belongs to technical field of coatings, relate to the high aqueous polyurethane dispersion of a kind of anti scuffing and wet adhesion and application thereof.
Background technology
Aqueous polyurethane has the environment-protecting asepsis characteristic with water compositing dispersion medium, has widely application aspect coating, tackiness agent and the seal gum.But the carbamate groups and the hydrophilic ionic group that contain strong polarity in the unmodified aqueous polyurethane molecular structure, water-fast poor with solvent resistance, therefore and can reduce the surface hardness of coating and to the sticking power of base material, in concrete application process, all must carry out modification to aqueous polyurethane.
Contain the difference in functionality group in the coupling agent molecule structure, polymer molecular chain and base material coupling can be got up, can be hydrolyzed and produce crosslinked such as the alkoxy grp of silane coupling agent, improve the aqueous polyurethane solvent resistance.
US Patent No. 6077901-A, world patent WO200059975-A and Chinese patent application CN101020738A adopt the silicone-modified aqueous polyurethane that contains single amido, are used for coating, tackiness agent and seal gum, improve water-fast and solvent resistance; But contain single amido siloxanes to the polyurethane prepolymer end-capped, preparation aqueous polyurethane molecular weight is low, hardness is low, there is the phenomenon of being clamminess dry rear surface, to just can reach certain mechanical strength, water-fast and solvent resistance preferably through long-time crosslinking reaction, adopt the polyamine coupling agent can overcome this shortcoming.
Japanese Patent JP2006104226-A adopts the polyamines organic siloxane modified aqueous polyurethane, siloxane groups is grafted on the aqueous polyurethane chain, be used for adhesive area, physical strength, water tolerance and solvent resistance have been improved, but the siloxane groups mobility is restricted, the raising aqueous polyurethane is limited in one's ability, particularly not good to base material hygrometric state bonding force to the base material bonding.
Patent WO200191923-A adopts polyamines base titanic acid ester modified aqueous polyurethane, improved the cohesive force of aqueous polyurethane to base material, the field that same this patent relates to is tackiness agent and seal gum, do not fail to relate to the paint field that anti scuffing, wet adhesion are had relatively high expectations yet, do not obtain aqueous polyurethane as a coating prerequisite high scratch resistance and wet adhesion.
Chinese patent application CN1554688A adopts polyamines silane coupling agent and the composite modified aqueous polyurethane of inorganic silicate, it is characterized in that relying on the chain extension effect of polyamines silane coupling agent and coupled action to improve aqueous polyurethane physical strength and water tolerance, but this technology is only limited to the polyethers system, more specifically say the polypropylene glycol ether system, because the polyether structure second-order transition temperature is low and wetting ability is strong, therefore sticking power is low especially under prepared aqueous polyurethane particularly soft and the wet environment.
Chinese patent CN1854165A adopts polyamine silane coupling agent such as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane and N-(2-aminoethyl)-3-aminopropyl triethoxysilane modified polyether type aqueous polyurethane, the polyamines organo-silicon coupling agent has improved water tolerance, but polyether segment itself is hydrophilic strong, namely use the modification of polyamines organo-silicon coupling agent, the water tolerance increase rate of aqueous polyurethane is limited; Secondly, the polyether segment second-order transition temperature that this patent adopts is low, and prepared aqueous polyurethane elongation at break is greater than 500%, and the film forming matter particularly soft can only be used as tackiness agent, can not be used as coating.
In a word, existing patent adopts separately monoamine or polyamines organo-silicon coupling agent modified aqueous polyurethane, has following problem: (1) self-vulcanizing is chronic, usually needs more than 7 days; (2) can not improve simultaneously scratch resistance, water tolerance and the wet adhesion of aqueous polyurethane; (3) adopt above-mentioned silane coupler modified aqueous polyurethane because there is performance deficiency, be mainly used in adhesive area, fail for the paint field very high to performance requriements.In paint field, Chinese patent CN1948200A discloses the making of Waterborne color transparent glass paint, mainly adopts water-based organosilicon acrylic resin, water-compatible amino resin and silane coupling agent, but adopts this technology, and coating will could be solidified under 120～150 ℃ of high temperature.
Development along with social progress and science and technology, Application of coatings is also more and more extensive, requirement for coating also is more and more higher, comprise the requirement of water tolerance, solvent resistance, surperficial anti scuffing ability and wet adhesion to coating, the simultaneously shortening of set time also is the major issue that developing application of paints Technology Need solves.Have not yet to see the correlation technique report that above-mentioned over-all properties is improved significantly.
Summary of the invention
The purpose of this invention is to provide a kind of aqueous polyurethane dispersion and application thereof, reactive coupling agent is added in the aqueous polyurethane preparation process and/or afterwards, make aqueous polyurethane molecular backbone chain or side chain with the coupling agent group, unexpectedly improve aqueous polyurethane surface scratch resistance and wet adhesion, overcome the not enough of existing waterborne polyurethane modified technology and as the performance deficiency of the aqueous polyurethane product of application of paints.
Another object of the present invention provides described aqueous polyurethane dispersion as the application of water-borne coatings on metal, glass, glass fibre, cement matrix, magnesium oxide, pottery or stone material material.
Technical scheme of the present invention is as follows:
Provide a kind of anti scuffing and wet adhesion high aqueous polyurethane dispersion, made by following component reaction:
(a) reactive coupling agent;
(b) polyvalent alcohol;
(c) two or more can with the group of-NCO radical reaction and the organism of one or more ions or potential ionic group;
(d) polymer polyatomic alcohol;
(e) polyisocyanates;
(f) neutralizing agent;
(g) water;
(h) polyamine.
The present invention sums up the material system that obtains selective reaction coupling agent adding preparation aqueous polyurethane by lot of experiments can obviously improve aqueous polyurethane scratch resistance and wet adhesion, and the material system of described preparation aqueous polyurethane comprises existing material system.
As preferred scheme, aqueous polyurethane dispersion of the present invention can be made by following component reaction:
(a) reactive coupling agent;
(b) molecular weight 62～400, the polyvalent alcohol of functionality 2～6;
(c) contain two hydroxyls or amido and a carboxyl or sulfonic organism;
(d) molecular-weight average 300～6000, the polymer polyatomic alcohol of functionality 1.5～4;
(e) molecular weight 168～1000, the polyisocyanates of functionality 1.5～4;
(f) neutralizing agent;
(g) water;
(h) molecular weight 60～500, any compound that contains 2 or 2 above primary amine and/or secondary amine group.
More preferred material combination is:
(a) reactive coupling agent;
(b) molecular weight 62～300, the polyvalent alcohol of functionality 2～3;
(c) contain two hydroxyls or amido and a carboxyl or sulfonic organism;
(d) molecular-weight average 700～3000, the miscellany of the polyester polyol of functionality 2～3, polyether glycol or their arbitrary proportions;
(e) molecular weight is 168～800, the polyisocyanates of functionality 2～3;
(f) metal hydroxides, alkaline carbonate, alkali metal hydrocarbonate, ammoniacal liquor and/or tertiary amine;
(g) water;
(h) molecular-weight average is between 60～300, any compound that contains 2 or 2 above primary amine and/or secondary amine group.
The invention provides following material combination, aqueous polyurethane dispersion that can excellent:
(a) a kind of reactive coupling agent or multiple reactive coupling agent composition;
(b) molecular weight 62～300, the polyvalent alcohol of functionality 2～3;
(c) contain two hydroxyls or amido and a carboxyl or sulfonic organism;
(d) molecular-weight average 700～3000, functionality 2～3, contain ring texture the miscellany of polyester polyol, polycarbonate polyol, polyether glycol and their arbitrary proportions;
(e) molecular weight is 168～800, the polyisocyanates of functionality 2～3;
(f) metal hydroxides, alkaline carbonate, alkali metal hydrocarbonate, ammoniacal liquor and/or tertiary amine;
(g) water;
(h) molecular-weight average is between 60～300, any compound that contains 2 or 2 above primary amine and/or secondary amine group.
Wherein calculate with (a)～(h) total mass, the shared massfraction 0.1～15% of component (a), more the preferred mass mark is between 0.3～12%; The shared massfraction of component (b) is 0～10%, and more the preferred mass mark is 0～6%, and the shared massfraction of component (c) is 1～15%, and the preferred mass mark is between 2～12%; (h) preferably between 0～8%, more preferred massfraction is between 0～6% for the shared massfraction of component; Surplus is other components, and the shared massfraction of other each components is with reference to existing routine techniques.
Component among the present invention (a) is reactive coupling agent, and its constitutional features can be used formula (I) expression:
Wherein, a value is 1 or 2, and preferred value is 1; The b value is 1,2 or 3, preferred value 2 or 3; The c value is 0,1 or 2, and preferred value is 0 or 1; The d value is 1,2 or 3; And b+c+d=4; Comprise the group that can react with hydroxyl or carboxyl in the Y group structure, can be preferred but be not limited only to hydroxyl, epoxy group(ing), isocyanate group and amido with the group that hydroxyl or carboxyl react in the Y group structure; M is Si, Ti, Zr or Al atom, preferred Si and Ti atom; X is hydroxyl, contains alkoxyl group or the ester group of 1～4 carbon atom, preferably contains alkoxyl group or the ester group of 1～4 carbon atom; Z is alkyl.
Component (a) preferred silane coupling agent and titanate coupling agent and arbitrary composition thereof, feature be the Y group structure shown in its structural formula contain can with the group of carboxyl or sulfonic group reaction, include but are not limited to hydroxyl, epoxy group(ing), isocyanate group and amido.
Concrete, component of the present invention (a) reactive coupling agent is according to the different choice of the group of the selectivity value of a, b, c, d and X, Y, Z representative, and (a) component can include but are not limited to following compound:
A=1, b=3, c=0, d=1, Y are hydroxyethyl, and X is methoxyl group, and M is the Si atom, i.e. hydroxyethyl Trimethoxy silane (D-1);
A=1, b=3, c=0, d=1, Y are 3,4-epoxy hexamethylene-ethyl, and X is trimethoxy, and M is the Si atom, i.e. (3,4-epoxycyclohexyl) ethyl trimethoxy silane (D-2);
A=1, b=3, c=0, d=1, Y are 3,4-epoxy hexamethylene-ethyl, and X is oxyethyl group, and M is the Si atom, i.e. (3,4-epoxycyclohexyl) ethyl triethoxysilane (D-3);
A=1, b=3, c=0, d=1, Y are the glycidyl ether propyl group, and X is methoxyl group, and M is the Si atom, i.e. glycidoxypropyltrimethoxysilane alkane (D-4);
A=1, b=3, c=0, d=1, Y are the glycidyl ether propyl group, and X is oxyethyl group, and M is the Si atom, i.e. glycidyl ether propyl-triethoxysilicane (D-5);
A=1, b=2, c=1, d=1, Y are the glycidyl ether propyl group, and X is methoxyl group, and Z is methyl, and M is the Si atom, i.e. glycidyl ether propyl group methyl dimethoxysilane (D-6);
A=1, b=3, c=0, d=1, Y are the glycidyl ether propyl group, and X is propoxy-, and M is the Si atom, i.e. glycidyl ether propyl group tripropoxy silane (D-7);
A=1, b=3, c=0, d=1, Y are the glycidyl ether propyl group, and X is isopropoxy, and M is the Si atom, i.e. glycidyl ether propyl group three isopropoxy silane (D-8);
A=1, b=3, c=0, d=1, Y are the glycidyl ether propyl group, and X is isopropoxy, and M is the Si atom, i.e. glycidyl ether propyl group three butoxy silanes (D-9);
A=1, b=3, c=0, d=1, Y are the isocyanate group propyl group, and X is methoxyl group, and M is the Si atom, i.e. isocyanate group propyl trimethoxy silicane (D-10);
A=1, b=3, c=0, d=1, Y are the isocyanate group propyl group, and X is oxyethyl group, and M is the Si atom, i.e. isocyanate group propyl-triethoxysilicane (D-11);
A=1, b=3, c=0, d=1, Y are aminocarbonyl propyl, and X is methoxyl group, and M is the Si atom, i.e. aminocarbonyl propyl Trimethoxy silane (D-12);
A=1, b=3, c=0, d=1, Y are aminocarbonyl propyl, and X is oxyethyl group, and M is the Si atom, i.e. aminocarbonyl propyl triethoxyl silane (D-13);
A=1, b=3, c=0, d=1, Y are N-phenyl aminocarbonyl propyl, and X is methoxyl group, and M is the Si atom, i.e. N-phenyl amido propyl trimethoxy silicane (D-14);
A=1, b=3, c=0, d=1, Y are N-(2-aminoethyl)-3-aminopropyl, and X is methoxyl group, and M is the Si atom, i.e. N-(2-aminoethyl)-3-aminopropyl trimethoxysilane (D-15);
A=1, b=3, c=0, d=1, Y are N-(2-aminoethyl)-3-aminopropyl, and X is oxyethyl group, and M is the Si atom, i.e. N-(2-aminoethyl)-3-aminopropyl triethoxysilane (D-16);
A=1, b=3, c=0, d=1, Y are N-(6-ammonia hexyl)-3-aminopropyl, and X is oxyethyl group, and M is the Si atom, i.e. N-(6-ammonia hexyl)-3-aminopropyl triethoxysilane (D-17);
A=1, b=3, c=0, d=1, Y are N-(2-aminoethyl)-11-ammonia undecyl, and X is methoxyl group, and M is the Si atom, i.e. N-(2-aminoethyl)-11-ammonia undecyl Trimethoxy silane (D-18);
A=1, b=3, c=0, d=1, Y are aminoethyl-aminomethyl-styroyl, and X is methoxyl group, and M is the Si atom, i.e. aminoethyl-aminomethyl-styroyl-Trimethoxy silane (D-19);
A=1, b=3, c=0, d=1, Y are N-3-[amino (polyoxytrimethylene base)]-aminopropyl, X is methoxyl group, M is the Si atom, i.e. N-3-[amino (polyoxytrimethylene base)]-aminopropyl trimethoxysilane (D-20);
A=1, b=3, c=0, d=1, Y are N-(6-ammonia hexyl)-aminomethyl, and X is oxyethyl group, and M is the Si atom, i.e. N-(6-ammonia hexyl)-aminomethyl triethoxyl silane (D-21);
A=1, b=3, c=0, d=1, Y are N-(2-aminoethyl)-3-aminopropyl, X is-OD that M is the Si atom, i.e. N-(2-aminoethyl)-3-aminopropyl silanetriol (D-22);
A=1, b=2, c=1, d=1, Y are N-(2-aminoethyl)-3-aminopropyl, and X is methoxyl group, and Z is methyl, and M is the Si atom, i.e. N-(2-aminoethyl)-3-aminopropyl-methyl-dimethoxy silane (D-23);
A=1, b=1, c=2, d=1, Y are N-(2-aminoethyl)-3-ammonia isobutyl-, and X is methoxyl group, and Z is methyl, and M is the Si atom, i.e. N-(2-aminoethyl)-3-ammonia isobutyl--dimethyl-methoxy silane (D-24);
A=1, b=3, c=0, d=1, Y are diethylenetriamine base propyl group, and X is methoxyl group, and M is the Si atom, i.e. (3-Trimethoxy silane base propyl group)-diethylenetriamine (D-25);
A=2, b=3, c=0, d=1, Y are N-propyl group-aminoethyl-aminopropyl, and X is methoxyl group, and M is the Si atom, i.e. two [(3-Trimethoxy silane base) propyl group]-quadrols (D-26);
A=1, b=1, c=0, d=3, Y are 2-quadrol base oxethyl, and X is isopropoxy, and M is the Ti atom, and namely (2-quadrol base oxethyl)-titanium (IV) is (D-27) for isopropoxy-three;
A=1, b=1, c=0, d=3, Y are 2-quadrol base oxethyl, and X is isopropoxy, and M is the Zr atom, and namely (2-quadrol base oxethyl)-zirconium (IV) is (D-28) for isopropoxy-three.
Component (b) is mainly regulated the prepolymer molecular size range as chainextender, can be the aliphatic diol of carbonatoms between 2～22, alicyclic diol, the glycol or glycol condenses and their miscellany that contain aromatic nucleus, preferred glycol is aliphatics or the alicyclic diol between the carbonatoms 2～12, ethylene glycol for example, 1, ammediol, 1, the 2-propylene glycol, 1, the 4-butyleneglycol, 1,3 butylene glycol, 1,5-PD, neopentyl glycol, the 2-methyl isophthalic acid, ammediol, 1, the 6-hexylene glycol, Isosorbide-5-Nitrae-dihydroxyl hexanaphthene, 1,3-dihydroxyl hexanaphthene, 1,4-hydroxymethyl-cyclohexane or 1,2-ring pentanediol etc.; The condenses of alcohol can be selected glycol ether, Triethylene glycol or dipropylene glycol etc.; Functionality is that 3 alcohol can be selected glycerol or TriMethylolPropane(TMP).
The selective basis of component (c) is: contain two or more can with group and one or more ions or the potential ionic group of-NCO radical reaction, the for example affixture of dimethylol propionic acid, dimethylolpropionic acid, tartrate, trivalent alcohol and acid anhydrides affixture, (methyl) vinylformic acid and polyamine, N-(2-aminoethyl)-2-aminoethane sulfonic acid, preferred dimethylol propionic acid, dimethylolpropionic acid or N-(2-aminoethyl)-2-aminoethane sulfonic acid.
Wherein component (d) polymer polyatomic alcohol is the polymer polyatomic alcohol that contains ester bond or ehter bond, can be polyester polyol, polycarbonate polyol, polyether glycol or their arbitrary proportion multipolymer or blend.Wherein contain massfraction 2～80% ring texturees on the more excellent polyester polyol molecular chain, it is characterized in that any one ring texture carbonatoms is 3～12, described ring texture is aromatic series ring-type structure and/or aliphatics ring texture, and ring texture is that single ring and/or many rings link to each other, and more preferably contains the ring texture of 5～8 carbon atoms.The applicant has comparatively detailed discussion in application number is 200810028099.0 patent application.
Wherein polyester polyol can be by the preparation of normal polyester synthetic method, and the preparation method can be with reference to prior art, for example elaboration of kind ancestral's benevolence in the third editions in 2003 of " polymer chemistry ".Suitable polyester polyol can prepare by the normal polyester synthesis technique with the pure and mild acid of functionality 2～6, and preferred functionality is 2 pure and mild acid and acid anhydrides preparation.Described functionality is that 2 alcohol comprises aliphatic diol, alicyclic diol, the glycol that contain aromatic nucleus and/or the glycol condenses of carbonatoms between 2～22, preferred glycol is aliphatics and the alicyclic diol between the carbonatoms 2～12, ethylene glycol, 1 for example, ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 2-methyl isophthalic acid, ammediol, 1,6-hexylene glycol, 1,4-dihydroxyl hexanaphthene, 1,3-dihydroxyl hexanaphthene, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane or 1,2-ring pentanediol etc.; The preferred glycol ether of glycol condenses, Triethylene glycol or dipropylene glycol etc.; Two (hydroxyethyl) ethers of the preferred Resorcinol of glycol, two (2-hydroxyethyl) ethers of quinhydrones or the Resorcinol bis-hydroxypropyl ether etc. that contain aromatic nucleus.Functionality is that 3 alcohol can be selected glycerol or TriMethylolPropane(TMP).Described functionality is that 2 acid comprises aliphatic diacid, alicyclic diacid, aromatic diacid or the hydrogenated aromatic diacid etc. of carbonatoms between 2～22, preferred carbonatoms is at 4～12 diprotic acid, for example oxalic acid, propanedioic acid, Succinic Acid, hexanodioic acid, nonane diacid, SA, 1,2-cyclohexane diacid, 1,4-cyclohexane diacid, tetrahydrochysene phthalic acid, terephthalic acid, phthalic acid or m-phthalic acid etc., preferred acid anhydrides comprises Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride or trimellitic anhydride etc.Also can adopt as the case may be acid anhydride mixture.
Adopt above-mentioned polyvalent alcohol and polyprotonic acid the preparation polyester polyol can for but be not limited only to following several:
The I polyester polyol is by terephthalic acid, SA, propylene glycol and 1,4 cyclohexane dimethanol preparation, functionality 2.0, molecular weight 1000～2000;
II gathers (hexanodioic acid-butanediol ester) glycol, molecular weight 1000～2000;
III gathers (phthalic acid-propylene glycol-glycol ether ester) glycol, molecular weight 700～1500;
The IV polyester polyol is by Tetra hydro Phthalic anhydride, hexanodioic acid, propylene glycol and TriMethylolPropane(TMP) preparation, functionality 2.2, molecular weight 1500;
The V polyester polyol is by m-phthalic acid, hexanodioic acid, propylene glycol and neopentyl glycol preparation, functionality 2.0, molecular weight 1000～2000;
The acid esters ring-opening polymerization is also included within the scope of the invention through the polycaprolactone polyol of glycol end-blocking in oneself.
The polycarbonate diol of carbonic diester, phosgene or cyclic carbonate and ethylene glycol, butyleneglycol, hexylene glycol and dihydroxyphenyl propane or the preparation of their mixture reaction is also included within the scope of the invention.
Suitable polyether glycol comprises the ring-opening polymerization polymer of Styrene oxide 98min., oxyethane, propylene oxide, tetrahydrofuran (THF) and their mixture ring-opening polymerization polymer and graft copolymer, preferred molecular weight between 1000～2000 and functionality be 2 polyoxypropyleneglycol (PPG) and PTMG (PTMEG).
Component (e) is the polyisocyanate compound of functionality between 1.5～4, preferred functionality is 2～3 polyisocyanates, particularly, functionality is that 2 isocyanic ester can be selected isophorone diisocyanate, hexamethylene diisocyanate, the decamethylene vulcabond, 1,12-12 carbon vulcabond, 2-methyl-pentane vulcabond, dicyclohexyl methane diisocyanate, 1, the 4-cyclohexyl diisocyanate, the cyclohexanedimethyleterephthalate vulcabond, trimethylammonium-1, the 6-hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, how vulcabond, PPDI, xylylene diisocyanate, the dimethyl diphenyl vulcabond, norborneol vulcabond or tetramethyl-mphenylenedimethylim-vulcabond.The isocyanic ester of preferred 2 functionality is isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate or diphenylmethanediisocyanate, and the composition of their any kinds and ratio; The dimer that also comprises above-mentioned polyisocyanates.
Functionality is that 3 polyisocyanates can be the tripolymer of vulcabond or the affixture of trivalent alcohol and vulcabond.
Among the present invention, neutralizing agent (f) component of preparation aqueous polyurethane dispersion be can with the alkali of carboxylic acid or sulfonic acid reaction, comprise tertiary amine, ammoniacal liquor, alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate, preferred tertiary amine, triethylamine for example, N, the N-diethylethanolamine, trolamine, tri-isopropyl amine, tri-isopropanolamine, Tributylamine, two (dimethylaminoethyl) ether, N, the N-dimethylcyclohexylamine, N-methyl bicyclic hexylamine, N-cocoa morpholine, lupetazin, N, the N-dimethyl benzylamine, N, N-dimethyl (hexadecyl) amine, N-methylmorpholine, N-ethylmorpholine, N methyl piperazine, N-crassitude or N-picoline.In addition, these neutralizing agents mix with arbitrary proportion and also are fit to the present invention.
(h) component is that functionality is primary amine and/or the secondary amine compound more than 2 or 2, functionality is that 2 amine can be quadrol, propylene diamine, butanediamine, hexanediamine, isophorone diamine, piperazine, N, N '-two-(2-aminoethyl) piperazine, hydrazine and adipic dihydrazide; Functionality can be selected the adduct of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethyene diamine, trimeric cyanamide and polyamine and epoxy greater than 2 amine.Preferred quadrol, isophorone diamine, diethylenetriamine and triethylene tetramine and their arbitrary composition do to expand even agent.
The present invention provides the application of described aqueous polyurethane dispersion simultaneously, can be used as water-borne coatings, is specially adapted to metal, glass, glass fibre, cement matrix, magnesium oxide, pottery or stone material.The present invention adds the performance that reactive coupling agent has significantly been improved aqueous polyurethane in the process of preparation aqueous polyurethane, in application, can in aqueous polyurethane dispersion, again add a certain amount of reactive coupling agent, further improve anti scuffing and the wet adhesion performance of aqueous polyurethane, the add-on of reactive coupling agent can be conventional with reference to determining according to art technology.
The invention has the beneficial effects as follows:
According to technical scheme of the present invention, the selective reaction coupling agent adds material system, reactive coupling agent and aqueous polyurethane reaction, improved wet adhesion and the anti scuffing ability of aqueous polyurethane on metal, glass, glass fibre, cement matrix, magnesium oxide, pottery or stone material, can clearly understand through experiment results, aqueous polyurethane dispersion solid content of the present invention is between 10～60%, and emulsion particle diameter is between 30～300nm, and stability in storage was above 6 months.
The present invention sums up by lot of experiments and obtains being used in combination of reactive coupling agent, can more significantly improve the above-mentioned performance of aqueous polyurethane.Being used in combination of described reactive coupling agent comprises being used in combination of multiple reactive coupling agent, also comprise reactive coupling agent being used in combination in the preparation process of aqueous polyurethane, use procedure, be to add reactive coupling agent in the preparation process, be equipped with again reactive coupling agent during use, so that the above-mentioned performance of aqueous polyurethane dispersion further guaranteed and strengthen, effectively remedied the deficiency of existing coating technology.
Embodiment
Further describe the present invention below in conjunction with specific embodiment.The applicant sums up through a large amount of experimental studies and draws the beneficial effect that the selective reaction coupling agent adds the material system of preparation aqueous polyurethane, existing conventional preparation system is not given unnecessary details in an embodiment one by one, the mixing use and simple the substituting that comprise this area routine techniques, material are not given unnecessary details in an embodiment yet, embodiment selects typical case's preference, but does not therefore limit scope of the present invention.
Embodiment 1 aqueous polyurethane dispersion 1
With 100.0g polyester polyol II (molecular weight 1000), 8.0g dimethylol propionic acid and 18.0gN-methyl-2-pyrrolidone Hybrid Heating to 70 ℃, stir until dimethylol propionic acid all dissolves; Add the 21.0g tolylene diisocyanate, 70 ℃ of reaction 30min add the 30.2g hexamethylene diisocyanate again, are warmed up to 100 ℃ of reactions, until-NCO content reaches 6.4%, cools to 60 ℃, adds in the 6.0g triethylamine and prepolymer; Add 156.0g water, vigorous stirring dispersed polyurethane prepolymer slowly adds 7.9g quadrol and 1.74g D-15 coupling agent mixed solution simultaneously, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 50%.
Embodiment 2 aqueous polyurethane dispersion 2
With 80.0g polyester polyol I (molecular weight 2000), 20.0gPTMEG (molecular weight 1000), 7.7g dimethylol propionic acid and 16.5gN-methyl-2-pyrrolidone Hybrid Heating to 80 ℃, stir until dimethylol propionic acid all dissolves; Add the 10.5g diphenylmethanediisocyanate, 70 ℃ of reaction 30min, and then add the 37.3g isoflurane chalcone diisocyanate are warmed up to 100 ℃ of reactions, until-NCO base content reaches 5.0%, cools to 60 ℃, adds in the 8.2g tri-isopropyl amine and prepolymer; Then add 410.0g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds 2.3g quadrol and 17.1g D-17 coupling agent mixed solution, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 30%.
Embodiment 3 aqueous polyurethane dispersion 3
With 100.0g polyester polyol V (molecular weight 1000), 13.4g dimethylol propionic acid and 36.4gN-methyl-2-pyrrolidone Hybrid Heating to 70 ℃, stir until dimethylol propionic acid all dissolves; Add 5.0g hexamethylene diisocyanate, 14.0g hexamethylene diisocyanate tripolymer and 65.0g isophorone diisocyanate, be warmed up to 100 ℃ of reactions, until-NCO content reaches 5.8%, cools to 60 ℃, adds in the 10.1g triethylamine and prepolymer; Add 785g water, vigorous stirring dispersed polyurethane prepolymer stirs until demonstration-NCO group absorption peak no longer in the FTIR spectrum again.Get the aqueous polyurethane dispersion of solid content 20%.
Embodiment 4 aqueous polyurethane dispersion 4
With 80.0g polycaprolactone polyol (molecular weight 1000), 20.0g PPG (molecular weight 1000), 9.3g N-(2-aminoethyl)-2-aminoethane sulfonic acid, 11.2g D-13 coupling agent and 20.7gN, N-N,N-DIMETHYLACETAMIDE Hybrid Heating to 70 ℃ stirs until N-(2-aminoethyl)-2-aminoethane sulfonic acid all dissolves.Then add 66.6g isophorone diisocyanate and 10.1g hexamethylene diisocyanate tripolymer, be warmed up to 100 ℃ of reactions, until-NCO content reaches 5.7%, cools to 60 ℃, adds in the 5.6g triethylamine and prepolymer.Then add 1190.0g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds the 10.9g triethylene tetramine, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 15%.
Embodiment 5 aqueous polyurethane dispersion 5
With 97.0g polyester polyol IV (molecular weight 2000), 3.0g 1,2-PD, 8.3g dimethylolpropionic acid and 18.5g N,N-dimethylacetamide Hybrid Heating to 70 ℃, stir until dimethylolpropionic acid all dissolves; Add 58.5g isophorone diisocyanate and 10.0g D-11 isocyanate group propyl-triethoxysilicane, be warmed up to 100 ℃ of reactions, until-NCO content reaches 5.1%, cools to 60 ℃, adds in the 5.7g triethylamine and prepolymer; Add 266.0g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds the 6.7g cyclohexanediamine, adds rear restir 30min again, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 40%.
Embodiment 6 aqueous polyurethane dispersion 6
With 100.0g polyester polyol III (molecular weight 1000), 12.1g affixture and the 19.0g N by 1mol TriMethylolPropane(TMP) and 1mol butyryl oxide reaction generation, N-N,N-DIMETHYLACETAMIDE Hybrid Heating to 70 ℃ stirs until TriMethylolPropane(TMP) and butyryl oxide affixture all dissolve.Add the 21.0g tolylene diisocyanate, 70 ℃ of reaction 30min, and then add the 40.0g isophorone diisocyanate are warmed up to 100 ℃ of reactions, until-NCO content reaches 6.3%, cools to 60 ℃, adds in the 5.2g triethylamine and prepolymer.Then add 420.0g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds 4.1g hydrazine and 5.8g D-26 coupling agent mixed solution, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 30%.
Embodiment 7 aqueous polyurethane dispersion 7
With 100.0g polyester polyol V (molecular weight 700), 9.7g dimethylol propionic acid and 33.0gN, N-N,N-DIMETHYLACETAMIDE Hybrid Heating to 70 ℃ stirs until dimethylol propionic acid all dissolves.Add 31.8g hexamethylene diisocyanate and 57.1g isophorone diisocyanate, be warmed up to 100 ℃ of reactions, until-NCO content reaches 7.8%, cools to 60 ℃, adds in the 7.3g triethylamine and prepolymer.Then add 487.6g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds 8.9g quadrol and 8.3g D-27 coupling agent mixed solution, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 30%.
Embodiment 8 aqueous polyurethane dispersion 8
With 100.0g polyester polyol VI (molecular weight 1500), 18.6g dimethylol propionic acid and 18.0g N,N-dimethylacetamide Hybrid Heating to 70 ℃, stir until dimethylol propionic acid all dissolves.Add the 100.0g isophorone diisocyanate, be warmed up to 100 ℃ of reactions, until-NCO content reaches 7.5%, cools to 60 ℃, adds in the 14.9g triethylamine and prepolymer.Then add 496.6g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds 25.2g isophorone diamine and 18.4g D-28 coupling agent mixed solution, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 35%.
Embodiment 9 contrast experiments
(1) preparation Comparative Examples aqueous polyurethane dispersion
Comparative Examples 1
With 100.0g polymer polyatomic alcohol I (molecular weight 2000), 7.3g dimethylol propionic acid and 16.3g N,N-dimethylacetamide, be heated to 70 ℃, stir until dimethylol propionic acid all dissolves; Add the 38.8g isophorone diisocyanate, be heated to 100 ℃ of reactions, until-NCO content reaches 3.5%, cools to 60 ℃, adds in the 5.5g triethylamine and prepolymer.Then add 217.0g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds the 4.2g quadrol, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 40%.
Comparative Examples 2
With 100.0g PTMG (molecular weight 1000), 8.9g dimethylol propionic acid and 20.0gN-methyl-2-pyrrolidone Hybrid Heating to 70 ℃, stir until dimethylol propionic acid all dissolves.Then add the 25g diphenylmethanediisocyanate, 70 ℃ of reaction 30min, and then add the 44.4g isophorone diisocyanate are warmed up to 100 ℃ of reactions, until-NCO content reaches 5.6%, cools to 60 ℃, adds in the 6.7g triethylamine and prepolymer.Then add 271.3g water, vigorous stirring dispersed polyurethane prepolymer simultaneously slowly adds the 9.2g diethylenetriamine, adds rear restir 30min, until demonstration-NCO group absorption peak no longer in the FTIR spectrum.Get the aqueous polyurethane dispersion of solid content 40%.
(2) aqueous polyurethane dispersion sample preparation of the present invention
Get embodiment 1～8 described aqueous polyurethane dispersion 200.0g, add certain EFKA-3580 wetting agent, clariant black wash and reactive coupling agent, stir evenly mixed, stand-by.The concrete prescription such as table 1:
Table 1
| Sample | Aqueous polyurethane dispersion | Reactive coupling agent | Black wash (g) | EFKA-3580 |
| A | 1 | D-58.80g | 10.0 | 0.2 |
| B | 2 | D-25.60g | 10.0 | 0.2 |
| C | 3 | D-44.96g | 10.0 | 0.2 |
| D | 4 | D-61.96g | 10.0 | 0.2 |
| E | 5 | D-37.80g | 10.0 | 0.2 |
| F | 6 | - | 10.0 | 0.2 |
| G | 7 | D-56.24g | 10.0 | 0.2 |
| H | 8 | D-811.12g | 10.0 | 0.2 |
| Comparative Examples 1 | - | 10.0 | 0.2 | |
| Comparative Examples 2 | - | 10.0 | 0.2 |
(3) performance test
Prepare coating at tinplate, glass, ceramic tile and marble respectively according to GB/T 1727-92, natural drying at room temperature was tested after 2 days.
(1) coating sticking power test under dry environment
Adopt the cross-hatching testing coating at timber, tinplate and sticking power on glass according to GB/T 9286-1998.With cutter 5 * 5 lattice on coating is drawn, tear after drawing the adhesion evenly of lattice place with Pressuresensitive Tape, the damaged situation of observation grid, determination methods is divided into the 0-5 level, and 0 grade is that the cut edge is fully level and smooth, and none comes off; 1 grade for to have a little coating shedding at the otch infall, can not be obviously greater than 5% but the cross cut area is influenced; 2 grades for the otch infall and or along notching edge coating shedding is arranged, affected cross cut area is obviously greater than 5%, but can not obviously beat in 15%; 3 grades partly or entirely come off with large fragment along the cut edge for coating, and/or partly or entirely peel off on the grid different sites, and affected cross cut area is obviously greater than 15%, but can not be obviously greater than 35%; 4 grades for coating large fragment peels off along the cut edge, and/or to come off partly or entirely appear in some grids, affected cross cut area is obviously greater than 35%, but can not be obviously greater than 65%; 5 grades for the degree of peeling off above 4 grades.Test result sees Table 2:
Table 2
| Sample | Tinplate | Glass | Ceramic tile | Marble |
| A | 1 | 0 | 1 | 1 |
| B | 1 | 0 | 0 | 1 |
| C | 1 | 0 | 0 | 1 |
| D | 1 | 1 | 1 | 1 |
| E | 1 | 0 | 0 | 1 |
| F | 1 | 0 | 0 | 1 |
| G | 1 | 1 | 0 | 1 |
| H | 1 | 0 | 0 | 1 |
| Comparative Examples 1 | 3 | 2 | 3 | 2 |
| Comparative Examples 2 | 3 | 2 | 2 | 2 |
(2) water tolerance and wet adhesion test
To be coated with cated tinplate, glass, ceramic tile and marble and soak in water 24 hours, and take out and to blot coatingsurface moisture with blotter, the observation coating color changes and bubble whether, and adopts cross-hatching test sticking power according to GB/T 9286-1998 immediately.The results are shown in Table 3 and table 4.
Table 3
Table 4
(3) scratch resistance experiment
Row dry with nail on the good coating of drying, cut do not occur and be designated as 1, cut is obvious and dark, is designated as 5.Experimental result sees Table 5:
Table 5:
| Sample | Tinplate | Glass | Ceramic tile | Marble |
| A | 2 | 2 | 2 | 2 |
| B | 2 | 2 | 2 | 2 |
| C | 2 | 1 | 1 | 1 |
| D | 3 | 3 | 3 | 3 |
| E | 2 | 2 | 2 | 2 |
| F | 3 | 2 | 2 | 3 |
| G | 2 | 2 | 2 | 2 |
| H | 1 | 1 | 1 | 1 |
| Comparative Examples 1 | 5 | 5 | 5 | 5 |
| Comparative Examples 2 | 5 | 5 | 5 | 5 |
Can find out from above test result, sample A, B, D, E, G and H are through the composition modified aqueous polyurethane of reactive coupling agent, sample C and F use separately the reactive coupling agent modified aqueous polyurethane, sample A～H obviously improves tinplate, glass, ceramic tile and marmorean scratch resistance and sticking power, particularly through after the long-time immersion of water, has good water tolerance and higher sticking power at tinplate, glass, ceramic tile and marble.Comparative Examples 1 adopts the aqueous polyurethane of the polyester polyol I preparation that contains ring texture, Comparative Examples 2 adopts the aqueous polyurethane of PTMG preparation, Comparative Examples 1 and 2 aqueous polyurethane all do not add any reactive coupling agent in preparation process and after the preparation, after being coated on tinplate, glass, ceramic tile and the marble, scratch resistance is not good, through behind the water soaking, and the coating whiting, it is floating to come off, and water tolerance and wet adhesion are poor especially.
Claims (3)
1. an anti scuffing and the high aqueous polyurethane dispersion of wet adhesion is characterized in that being made by following component reaction:
(a) a kind of reactive coupling agent or multiple reactive coupling agent composition;
(b) molecular weight 62～300, the polyvalent alcohol of functionality 2～3;
(c) contain two hydroxyls or amido and a carboxyl or sulfonic organism;
(d) molecular-weight average 700～3000, and functionality 2～3 contains the miscellany of polyester polyol, polycarbonate polyol, polyether glycol and their arbitrary proportions of ring texture;
(e) molecular weight 168～800, the polyisocyanates of functionality 2～3;
(f) metal hydroxides, alkaline carbonate, alkali metal hydrocarbonate, ammoniacal liquor and/or tertiary amine;
(g) water;
(h) molecular weight 60～300, any compound that contains 2 or 2 above primary amine and/or secondary amine group;
Calculate with component (a)～(h) total mass, the shared massfraction of component (a) is 0.1～15%, the shared massfraction of component (b) is 0～10%, and the shared massfraction of component (c) is 1～15%, and the shared massfraction of component (h) is 0～8%;
Component (a) adds in the process of preparation aqueous polyurethane dispersion and adds in the aqueous polyurethane dispersion when using, and component (a) is to have a kind of reactive coupling agent of structure shown in the formula (I) or the composition of multiple reactive coupling agent:
Wherein, a value is 1 or 2; The b value is 1,2 or 3; The c value is 0,1 or 2; The d value is 1,2 or 3;
And b+c+d=4;
Comprise the group that can react with hydroxyl or carboxyl in the Y group structure; M is Si, Ti or Zr atom; X is hydroxyl, contain alkoxyl group or the ester group of 1～4 carbon atom; Z is alkyl;
Containing the ring texture carbonatoms that the polyester polyol of ring texture comprises in the component (d) is 3～12, described ring texture is aromatic series ring-type structure and/or aliphatics ring texture, and ring texture is that single ring and/or many rings link to each other, and ring texture accounts for polyester polyol massfraction 2～80%;
The aqueous polyurethane dispersion that described anti scuffing and wet adhesion are high is applicable to the water-borne coatings as metal, glass, glass fibre, cement matrix, magnesium oxide, pottery or stone material.
2. the high aqueous polyurethane dispersion of described anti scuffing and wet adhesion according to claim 1 is characterized in that a value is 1 in the formula (I); The b value is 2 or 3; The c value is 0 or 1; The d value is 1,2 or 3;
And b+c+d=4;
Comprise hydroxyl, epoxy group(ing), isocyanate group or amido in the described Y group structure; M is Si or Ti atom; X is alkoxyl group or the ester group that contains 1～4 carbon atom; Z is alkyl.
3. the high aqueous polyurethane dispersion of described anti scuffing and wet adhesion according to claim 1, it is characterized in that calculating with component (a)～(h) total mass, the shared massfraction of component (a) is 0.3～12%, the shared massfraction of component (b) is 0～6%, the shared massfraction of component (c) is 2～12%, and the shared massfraction of component (h) is 0～6%.
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Denomination of invention: Anti-scratch aqueous polyurethane disperse system with high hygrometric state adhesive force and use thereof Effective date of registration: 20170505 Granted publication date: 20131030 Pledgee: Guangzhou Caold financing Company limited by guarantee Pledgor: Haijv High Polymer Materials Technology (Guangzhou) Co., Ltd. Registration number: 2017440000020 |
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Address after: 510000 4 / F, building A5, No. 11, Kaiyuan Avenue, Science City, Guangzhou high tech Industrial Development Zone, Guangdong Province Patentee after: Sea Polymer Polymer Material Science and Technology (Guangzhou) Co., Ltd. Address before: 510730, Guangdong, Guangzhou economic and Technological Development Zone Road 12 building, building five, East Patentee before: Sea Polymer Polymer Material Science and Technology (Guangzhou) Co., Ltd. |