CN101151288B - Modified water-based resin composition - Google Patents
Modified water-based resin composition Download PDFInfo
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- CN101151288B CN101151288B CN2006800106917A CN200680010691A CN101151288B CN 101151288 B CN101151288 B CN 101151288B CN 2006800106917 A CN2006800106917 A CN 2006800106917A CN 200680010691 A CN200680010691 A CN 200680010691A CN 101151288 B CN101151288 B CN 101151288B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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Abstract
To provide a polyisocyanate-curable water-based dispersion coating material (such as water-based polyurethane resin composition) which is improved in the dispersibility of the chief material resin in an aqueous medium and prolonged in the pot life by depressing the reaction of water with isocyanate group (which is highly reactive with water) and which can form a coating film exhibiting excellent surface appearance and water resistance equivalent to those of films of conventional solvent-type polyurethane resin coating materials in spite of its being a water-based coating film. A water-based resin composition comprising (A) a water-based acrylic resin or a water-based polyurethane resin obtained by reacting a diisocyanate with a polyol and (B) a polyisocyanate dispersible in the component(A), characterized by containing (C) a low-molecular-weight compound having a carbon-carbon unsaturated bond and a carbonyl group adjacent thereto.
Description
Technical field
The present invention relates to aqueous resin composition, specifically, the serviceable time that relates to, composition compound modified with specific interpolation prolongs, the also improved modified aqueous resin composition of water medium dispersiveness, polyurethane resin composition particularly, with and manufacture method and said composition as the use of coating agents such as coating.
Background technology
Polyurethane resin composition, because its excellent rerum natura, economy etc., with building materials, vehicle with serving as main general and reuse as coating agents such as coating in very many fields, but recently from reply, operation to environmental problem, perhaps in order to realize low price, requiring and generally carrying out avoiding with an organic solvent be, the coating agent of particularly volatile organic solvent system and with the organic solvent water-basedization or change into water medium changes to the coating agent of the polyurethane resin composition of the water system of using water dispersion medium.
In addition, be not limited to polyurethane resin composition,, carrying out the transformation of hydrotropic resin combination with also having same problem in other resin combinations such as polyisocyanates solidified acrylic resin.
In the resin combination of water system (water-based), as basic problem, improve dispersiveness or the solvability of resin host in water medium, the isocyanate group that the reactivity of inhibition and water is very high and the reactivity of water are must be obligato.
In order to tackle such problem, developed very many whole bag of tricks so far, open in patent gazette.
In the aqueous resin composition, in aqueous urethane resin composition, proposed with the composition with the isocyanate group sealing such as polyoxyalkylene diols in order to improve water dispersible in the past, but the reactivity of isocyanate group and water is not inhibited, isocyanate group is consumed early by water, serviceable time as the composition of coating etc. is short, and the hardness of its tunicle, poor water resistance.
Thereafter, disclose with hydrophilic surfactant active or fatty compounds with active hydrogen thereby isocyanate group has been carried out the method (patent documentation 1) that modification improves water dispersible, even isocyanate group improves the stability of water, but the dispersiveness to water is also insufficient, but also (patent documentations 2) such as compositions that has mixed the ionic surfactant in the hydrophilic polyisocyanate of having introduced the compound that contains the nonionic hydrophilic group disclosed, but isocyanate group is to the stability and dispersed insufficient in water of water, and the mixing of ionic emulsifier is to the bad influence of generation of filming.
In addition, as using alcohol with isocyanic ester base section urethane, make as serviceable time of coating and prolong and obtain room temp solidified composition (patent documentation 3), contain carboxylicesters by use, the hydroxyl polyester of sulfonate group, bring the long serviceable time and the composition of rapid-drying properties (patent documentation 4), by using the not end-blocking diisocyanate curing agent that is scattered in imperceptibly in the dispersion liquid, improve the coating (patent documentation 5) that the serviceable time and the man-hour of adding does not produce carbonic acid gas, be combined with polyvalent alcohol and with the polyisocyanates of alkali neutral phosphines by use with specific hydroxyl value, the composition that the reactivity of water dispersible excellence and isocyanate group and water is inhibited (patent documentation 6), use side chain to have the urethane resin of nonionic group, seen in the composition (patent documentation 7) that dispersiveness in the water and serviceable time are improved etc., proposed to adopt the whole bag of tricks to improve the dispersiveness of urethane resin in water medium, suppress the reactivity of isocyanate group and water, improve a large amount of schemes of serviceable time.
But, all these schemes all do not have to improve fully dispersiveness and the serviceable time of aqueous urethane resin composition in water simultaneously, made simultaneously as yet as the dispersiveness in water and the serviceable time of aqueous urethane resin composition major subjects and fully improved, and there are not the decline of the tunicle outward appearance that when lining carbon dioxide generating etc. causes, the aqueous urethane resin composition that intensity, outward appearance and the water tolerance etc. of coating tunicle are also excellent.In the water-borne acrylic resin composition,, also there is same situation from existing patent documentation.
Patent documentation 1: the spy opens flat 7-113005 communique (summary)
Patent documentation 2: the spy opens flat 9-71720 communique (summary)
Patent documentation 3: the spy opens flat 7-109327 communique (summary)
Patent documentation 4: the spy opens flat 9-157585 communique (summary, claims the 1st)
Patent documentation 5: the spy opens flat 10-140084 communique (summary)
Patent documentation 6: the spy opens flat 10-306255 communique (summary)
Patent documentation 7: the spy opens 2003-64149 communique (summary)
Summary of the invention
The problem that invention will solve
Described in paragraph 0002～0005, in the general cured with isocyanates aqueous resin compositions such as aqueous urethane resin composition that mainly use as the urethane resin coating agent of water system, improve the dispersiveness of resin host in water medium, and the reaction of very high isocyanate group of the reactivity of inhibition and water and water thereby to prolong the serviceable time be important problem always, therefore the present invention's problem that will solve is to address this problem as far as possible, and to obtain unlike existing organic solvent in the coating tunicle of water-based be the tunicle outward appearance of the excellence of urethane resin coating agent difference, hardness and water tolerance etc.
Be used to solve the method for problem
The present inventor is in order to solve above-mentioned problem, at aqueous urethane resin composition, aspects such as water-borne acrylic resin composition, in order to improve the dispersiveness of resin host in water medium, from the viewpoint different with previous methods, host and the dispersing method of solidifying agent or the use of dispersing auxiliary etc. for composition, in addition, in order to suppress the reactivity of isocyanate group and water, for the method for modifying of isocyanate group or be used for the use etc. of the additive of modification, seek new method and carry out investigating and trial property experiment continuously many-sidedly, in its process, newly created the present invention with the basis that is characterized as aspect following two: thus discovery can suppress the properties-correcting agent as additive that the reactivity of isocyanate group and water prolongs the serviceable time of aqueous resin composition, and the effect by this properties-correcting agent, the dispersiveness of aqueous resin composition in aqueous medium improved.
Among the present invention, because the chemical action of specific property-modifying additive, thereby the reactivity that can suppress isocyanate group and water fully prolongs the serviceable time of aqueous resin composition, in addition, effect by this properties-correcting agent, can also make the dispersed fully raising of aqueous resin composition in aqueous medium, the viscosity of resin combination is reduced, operation as the coating agent also improves, and can to obtain to have unlike existing organic solvent be the tunicle of tunicle outward appearance, hardness and water tolerance etc. of the excellence of urethane resin coating agent difference.
The additive that is used for its modification in the aqueous urethane resin composition etc. be specific aqueous resin composition use have unsaturated link(age) between carbon and in abutting connection with the low-molecular weight compound of carbonyl.
So-called specific aqueous urethane resin composition, be to contain (A) composition and (B) resin combination of composition, described (A) composition is to make the reaction of diisocyanate cpd and diatomic alcohol compounds (polyol compound) and the waterborne polyurethane resin that obtains, described (B) composition is the polyisocyanate compound that can be scattered in (A) composition, specifically, be to contain (A) composition and (B) coating composition of composition, described (A) composition is to make polyester polyol or polyether glycol and the reaction of aliphatic diisocyanate compound and the aqueous polyurethane prepolymer host that obtains, described (B) composition is a solidifying agent, be to be scattered in the tripolymer of the diisocyanate cpd in (A) composition or to add adult, have unsaturated link(age) between carbon and be to add unsaturated dicarboxylic acid diester in this coating composition etc. to as (C) composition in abutting connection with the low-molecular weight compound of carbonyl.
In addition, among the present invention the polyisocyanates of (B) composition and (C) composition have unsaturated link(age) between carbon and in abutting connection with the combination of the low-molecular weight compound of carbonyl, be not limited to aqueous urethane resin composition, the solidifying agent that also can be used as the such aqueous resin composition of water-borne acrylic resin uses, same action effect in acquisition and the aqueous urethane resin composition.
Below, in aqueous resin composition, mainly aqueous urethane resin composition is described.
More particularly, as preferred scheme, (B) solidifying agent of composition is the allophanate solidifying agent of the several hexamethylene diisocyanates more than 4 of functional group, (C) property-modifying additive of composition is a dialkyl maleate, this coating composition mainly is a coating composition, it itself is the two-pack type coating composition, the i.e. waterborne polyurethane resin of (A) composition and (B) the binary composition material as the polyisocyanates of solidifying agent of composition, when using binary is mixed as coating, in advance the additive of (C) composition is added to (A) composition or (B) in the composition, perhaps add during the mixing of composition at (A) composition with (B).
In addition, representational manufacture method as aqueous resin composition of the present invention, be to make the solidifying agent of (B) composition and (C) low-molecular weight compound of composition and dispersing auxiliary as required are scattered in the water medium and form water dispersion, with the combination of the resin host of (A) composition, thereby form their composition.
Even the careful prior art (each patent documentation) of record in the paragraph 0003～0005 or the prior art of isocyanate-based water-borne acrylic resin composition of checking, also at all can not find the formation of the present invention and the feature of paragraph 0009～0010 general description, in specific aqueous urethane resin composition of the present invention or water-borne acrylic resin composition, add the formation of the properties-correcting agent that uses, and adopt it can fully prolong the serviceable time of aqueous resin composition, can also fully improve the dispersiveness in aqueous medium, can obtain unlike existing organic solvent is the action effect of tunicle of the excellence of urethane resin coating agent difference, as aqueous resin composition is novel, and is significance.
For the present invention who creates and have notable feature as mentioned above, the record clearly if look down its integral body, the present invention is made of following invention unit's group, invention with [1] is invented as basic, and its following invention is that invention is specialized and even embodimentization (integral body is organized in invention be generically and collectively referred to as " the present invention ") substantially.
Aqueous resin composition, it is characterized in that: be to contain (A) composition and (B) resin combination of composition, described (A) composition is a water-dispersed resin host, described (B) composition for can be scattered in polyisocyanate compound in (A) composition, add have unsaturated link(age) between carbon and in abutting connection with the low-molecular weight compound of carbonyl as (C) composition.
The aqueous resin composition of above-mentioned [1], it is characterized in that: contain (A) composition and (B) composition, described (A) composition is water-borne acrylic resin host or makes polyvalent alcohol and aqueous polyurethane prepolymer host that diisocyanate cpd reaction obtains, described (B) composition is a solidifying agent, be can be scattered in (A) composition diisocyanate cpd tripolymer or add adult, (C) composition is a number-average molecular weight less than 500 low-molecular weight compound; (B)/(A) composition quality ratio is 0.01～0.50, adds (C) composition 0.01～30 mass parts with respect to (B) composition 100 mass parts; Resin combination is a coating composition.
The aqueous urethane resin composition of above-mentioned [2] is characterized in that: (B) solidifying agent of composition is the allophanate solidifying agent of the several hexamethylene diisocyanates more than 4 of functional group, and (C) composition is the unsaturated dicarboxylic acid diester.
The aqueous urethane resin composition of above-mentioned [3] is characterized in that: the unsaturated dicarboxylic acid diester is a dialkyl maleate.
Each aqueous urethane resin composition of above-mentioned [2]～[4], it is characterized in that: coating composition is a coating composition.
The aqueous urethane resin composition of above-mentioned [5], it is characterized in that: aqueous urethane resin composition is the two-pack type coating composition, be the waterborne polyurethane resin of (A) composition and (B) the binary composition material as the polyisocyanates of solidifying agent of composition, when using binary is mixed as coating, add the additive of (C) composition to (A) composition in advance or (B) in the composition, perhaps add during the mixing of composition at (A) composition with (B).
The manufacture method of the aqueous resin composition of above-mentioned [1] or [2], it is characterized in that: make the solidifying agent of (B) composition and (C) low-molecular weight compound of composition and dispersing auxiliary as required be scattered in the water medium and form water dispersion, form and (A) composition of the water-dispersed resin host of composition.
The invention effect
Among the present invention, can fully prolong the serviceable time of cured with isocyanates aqueous resin composition, but also can fully obtain the dispersiveness of aqueous resin composition in aqueous medium, make resin combination become even thus, in addition, the viscosity of resin combination is minimized, and also be improved as the operation of coating agent, and to access unlike existing organic solvent is the tunicle with excellent tunicle outward appearance, hardness and water tolerance etc. of urethane resin coating agent difference.
Embodiment
For the present invention, as the means that are used to solve problem, the front is illustrated according to basic comprising of the present invention, below mainly for aqueous urethane resin composition, aforesaid of the present invention group working of an invention mode is specifically described in detail.
1. aqueous resin composition
(1) basic comprising of composition
Aqueous resin composition of the present invention is to contain (A) composition and (B) composition basically, with water is the resin combination of medium, described (A) composition is water-borne acrylic resin or makes diisocyanate cpd and polyol compound reaction and the waterborne polyurethane resin (prepolymer) that obtains, described (B) composition is the polyisocyanate compound that can be scattered in (A) composition (its water dispersion), adds (C) composition that describes in detail in the paragraph 0027～0030 to it.
In the said composition, composition quality ratio (B)/(A) is preferably 0.01～0.50.Than this scope after a little while, cross-linking set is very few, can not obtain good rerum natura.In the time of too much, the remarkable tackify of said composition, appearance of film variation.In addition, the serviceable time shortens, and is therefore not preferred.
(2) diisocyanate cpd
As the vulcabond composition that uses among the present invention, use the organic diisocyanate compound, wherein use common raw-material organic diisocyanate compound as urethane resin, and not specially provided for., compare because of the ultraviolet ray xanthochromia for fear of the coating tunicle, more preferably aliphatics or alicyclic diisocyanate (should illustrate, below in stay in succinct narration) with the particular instantiation of the irrelevant compound of the essence of invention with aromatic diisocyanate.
Specifically, as aliphatic diisocyanate, can enumerate tetramethylene diisocyanate, hexamethylene diisocyanate, lysinediisocyanate, 2-methyl-pentane-1,5-vulcabond, 3-methyl-pentane-1,5-vulcabond, 2,2,4-trimethylammonium-hexane-1,6-vulcabond etc.In addition, as alicyclic diisocyanate, can enumerate cyclohexylidene vulcabond, dicyclohexyl methane diisocyanate, isophorone diisocyanate, hydrogenation of benzene dimethylene diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation Three methyl Benzene dimethylene diisocyanate etc.
These vulcabond can a kind will mix more than 2 kinds separately or as required and use.
(3) polyol compound
As the polyhydroxy reactant that uses among the present invention (dibasic alcohol and trivalent alcohol etc.), mainly use polyester polyol or polyether glycol, also can use polycarbonate polyol, acrylic polyol and polyolefin polyhydric alcohol etc.Wherein use common raw-material polyvalent alcohol as urethane resin, and not specially provided for.
Typically, can enumerate polypropylene glycol (PPG), polytetramethylene ether diol (PTG), polytetramethylene glycol (PTMG) etc.
More specifically, as polyester polyol, can use by phthalic acid, m-phthalic acid, terephthalic acid, naphthalic acid, succsinic acid, propanedioic acid, hexanodioic acid, 1,4-cyclohexyl dioctyl phthalate, toxilic acid, fumaric acid, other diprotic acid etc. and ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 3,3-dihydroxymethyl heptane, glycol ether, dipropylene glycol, neopentyl glycol, hexanaphthene-1, the 4-glycol, other glycol, or glycerine, TriMethylolPropane(TMP), the polyester polyol that the polycondensation of polyalcohols such as tetramethylolmethane obtains.
In addition, also can use cyclic esters such as 6-caprolactone, the part of glycol changed into polyesteramide polyvalent alcohol of amines such as hexamethylene-diamine, isophorone diamine etc.
As polyether glycol, can use by with above-mentioned di-alcohols, polyalcohols, perhaps they are with amines such as quadrol, propylene diamine, tolylene diamine, mphenylenediamine, ditan diamines, with epoxy alkane such as oxyethane, propylene oxide, alkyl or aryl glycidyl ethers such as methyl glycidyl ether, phenylglycidyl ether, addition polymerization such as cyclic ethers such as tetrahydrofuran (THF) and the polyether glycol that obtains.
As polycarbonate polyol, the polycarbonate polyol that can use the reaction by aforesaid di-alcohols, polyalcohols and carbonic acid ethylidene ester, diethyl carbonate, diphenyl carbonate etc. in the paragraph 0022 to obtain.
(4) water-borne acrylic resin and urethane resin
Water-borne acrylic resin among the present invention, have can with polyisocyanate curing agent reactive activity hydrogen base, and polymer chain is ionized or possess hydrophilic property group and by Water-borne modification.
Urethane resin of the present invention, make by the urethane reaction of the various diatomic alcohol compounds (or polyol compound) described in various diisocyanate cpds described in the paragraph 0020 and the paragraph 0021～0024, have the so hydrophilic main chain of polyoxyethylene glycol, perhaps polymer chain is ionized or possess hydrophilic property group and by Water-borne modification.For example, during urethane reaction, also can organize in molecular backbone chain and go into 2, ends such as 2-dimethylol propionic acid have the lipid acid of two hydroxyls, improve water dispersible.
Use the resinifying catalyzer (urethane catalyzer) of curing catalysts (polymerizing catalyst) as required as urethane reaction, use dibutyl tin laurate, the metal series catalysts that zinc naphthenate is such, or triethylamine, tripropyl amine, Tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethyl benzylamine, N, N, N ', N '-tetramethyl-hexamethylene-diamine, two-(2-dimethyl aminoethyl) ether, triethylenediamine, 1, the 2-methylimidazole, dimethylethanolamine, N, N-dimethyl-so common the curing catalysts such as amines catalyst of N-hexanol amine, can improve speed of response, reduce temperature of reaction.
(5) polyisocyanate compound
In aqueous resin composition of the present invention, as (B) composition, use can be scattered in the polyisocyanate compound in (A) composition, as (A) composition solidified curing agent component as host is played a role.
As making water-base resin solidified solidifying agent, liquid as dual-fluid system (composition of two-pack type) uses in the present invention, use comes from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), the NCO base in 1 molecule be more than 3 tripolymer, add adult.As preferred example, be the allophanate solidifying agent of the several hexamethylene diisocyanates more than 4 of functional group.
As the tripolymer of these vulcabond, add adult, can utilize various modification bodies such as urethane-modified body, urea modification body, allophanate-modified body, biuret modified body, urea diketone (ウ レ ト ジ オ Application) modification body, isocyanurate-modified body.
2. has unsaturated link(age) between carbon and in abutting connection with the low-molecular weight compound of carbonyl
(1) as the composition of composition
As (C) composition in the aqueous resin composition of the present invention, use to have unsaturated link(age) between carbon and in abutting connection with the low-molecular weight compound of carbonyl.
It is composition as the additive of the modification that is used for aqueous urethane resin composition etc., be because the chemical action of this property-modifying additive, thereby the reactivity that suppresses isocyanate group and water fully prolongs the serviceable time of aqueous urethane resin composition, and because the effect of this properties-correcting agent also makes the dispersed fully integrants at the centers of the present invention of raising in aqueous medium such as aqueous urethane resin composition.
With respect to (B) composition 100 mass parts, add 0.01～30 mass parts (C) composition.If not enough lower limit, the modified effect deficiency, if surpass the upper limit, the gloss of filming that obtains, rerum natura reduce, drying property is variation also, and is therefore not preferred.
(2) for compound
Has unsaturated link(age) between carbon and in abutting connection with the low-molecular weight compound of carbonyl, preferred number average molecular weight is less than 500 low-molecular weight compound, mainly be α, beta-unsaturated carbonyl compound, α, the beta-unsaturated carboxylic acid compounds, be unsaturated aldehyde, beta-unsaturated ketone, or unsaturated carboxylic acid, ester, acid anhydrides or the acid amides of unsaturated carboxylic acid, halogenide, and their various substitutive derivatives etc.
If the compound that illustration is concrete can use multiple compounds such as toxilic acid, maleic acid ester, fumaric acid, fumarate, vinylformic acid, acrylate, methacrylic acid, methacrylic ester, methylene-succinic acid, itaconic ester and propenal, Methylacrylaldehyde, Ba Dousuan, benzoquinones, isophorone.Moreover ester wherein uses mainly as diester.
Wherein, be representational compound as the dialkyl maleate of unsaturated dicarboxylic acid diester, optimal compound is ethyl maleate, dibutyl maleinate and the dioctyl maleate that embodiment described later confirmed.
(3) effect of compound
Thereby have unsaturated link(age) between carbon and bring the reactivity that suppresses isocyanate group and water fully to prolong the serviceable time of aqueous urethane resin composition etc. in abutting connection with the low molecular compound of carbonyl, and because the effect of this properties-correcting agent, also make the reason of the dispersed action effect that fully improve of aqueous urethane resin composition in aqueous medium still indeterminate, but infer it is relevant with so-called Michael reaction.
Promptly, for having unsaturated link(age) between carbon and in abutting connection with unsaturated link(age) between the carbon of the low-molecular weight compound of carbonyl, the amino isocyanic ester of the basic cpd that exists as the reaction origin because of organic diisocyanate in the composition and water plays a role, carry out Michael addition, and then the secondary amino group of addition reaction resultant and organic diisocyanate reaction, generation has saturated bond between carbon and in abutting connection with carbonyl and the organic diisocyanate that replaces urea groups, infers the response delay or the prevention that make isocyanate group and water thus.In addition, have unsaturated link(age) between carbon and when the low-molecular weight compound of carbonyl has the such hydrophobic group of long alkyl, push away and examine hydrophobic group and hinder water molecules, thereby suppress the reactivity of isocyanate group and water near isocyanate group.
3. other auxiliary agents
(1) chain extension agent
In composition of the present invention, can use the chain extension agent in the common polyaddition reaction as required.
As chain extension agent, use common low molecular compound with 2 above active hydrogen bases, particularly, make spent glycol, propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, neopentyl glycol, diethanolamine, trolamine etc.
(2) additive
Various additives as composition, in order further to improve rerum natura, and, can use fire retardant, softening agent, antioxidant, UV light absorber, dyestuff, pigment, weighting agent, internal mold release, supporting material, matting agent, electroconductibility imparting agent, charged control agent, static inhibitor, lubricant, other processing aids in order to add various rerum naturas etc.
4. as the form of composition
Aqueous urethane resin composition of the present invention, as mentioned above by as host (A) composition and (B) dual-fluid system that constitutes of the solidifying agent of composition, as the form of using, be as binary composition materials such as the two-pack type coating composition of coating agent or two-pack type adhesive composites, during as uses such as coating, binary is mixed, utilize the multifunctional NCO compound of solidifying agent that it is solidified three-dimensionally.
Normally, the implication of coating composition may not be beyond all doubt, among the present invention, is not in advance with whole composition blended compositions, but as the composition with binary composition material form.
5. the manufacture method of aqueous resin composition
Aqueous resin composition of the present invention, solidifying agent that can be by making (B) composition and (C) low-molecular weight compound of composition and dispersing auxiliary as required are scattered in and form water dispersion in the water medium, form and (A) composition of the resin host of composition, thereby make.
Particularly, form (1) water-dispersion water-base resin liquid and (2) make the solidifying agent of (B) composition and (C) low-molecular weight compound of composition be scattered in the composition of the two-pack type of the dispersion liquid that water medium forms.When using, binary is mixed as coating agents such as coating.
Moreover (C) additive of composition preferably, adds (A) composition to or (B) in the composition in advance, perhaps adds during the mixing of composition at (A) composition with (B).
Embodiment
Following discloses embodiment and compare example specifies in more detail to the present invention, makes formation of the present invention more clear, confirms the reasonableness of each important document of formation of the present invention.
[synthesis example of waterborne polyurethane resin]
Polyvalent alcohol A (the polytetramethylene glycol: Mn=2000f=2) 161.7g, 2 of in the reactor of the capacity 3000ml that agitator, thermometer, nitrogen sealed tube and water cooler are installed, packing into, 2-dimethylol propionic acid (DMPA) 10.5g, dipropylene glycol dme (DMDPG) 63.8g, heating made its dissolving in 10 minutes under 90 ℃.Be cooled to pack into after 60 ℃ isocyanic ester A (the Virahol modified urea carbamate compound of HDI: NCO=19.1%) 102.9g, under 80 ℃, make its reaction 2 hours, obtain containing the terminal pre-polymer solution of isocyanate group of carboxyl.The isocyanate content of this pre-polymer solution is 3.40%, and the carboxylic acid import volume in the prepolymer is 0.75mmol/g.
Then, the triethylamine of packing into (TEA) 7.9g with in the carboxyl and after, water 497.8g and the diethyl triamine of packing into while stirring (DETA) 5.4g carries out the chain reaction that increases that emulsification in 12 hours and water and amine causes under 30 ℃.Fill when utilizing FT-IR to confirm not have isocyanate group to exist, obtain aqueous polyurethane emulsion PU-1.The solids component of PU-1 is 2.5%, and pH is that 9.5,25 ℃ viscosity is 40mPas.
[manufacturing of aqueous urethane resin composition]
Cooperate polyisocyanates A (the methoxy poly (ethylene glycol) modification body of the 3-methyl pentanediol modified urea carbamate compound of HDI: NCO=16.4%) in the waterborne polyurethane resin of in above-mentioned synthesis example, making as solidifying agent, table 1,2 described property-modifying additives are disperseed, form aqueous urethane resin composition.
[serviceable time as aqueous coating agent is measured]
(1) (B)+(C) the NCO survival rate % of the water dispersion of composition
Survival rate with the NCO base of (B)+(C) composition in water medium is estimated as the isocyanate group of the serviceable time of coating agent and reactive inhibition degree of water the regulation aqueous urethane resin composition with the outward appearance of the composition liquid that adopts visual observation.
The total 12g of the additive (2.4g) of the polyisocyanates A (9.6g) of solidifying agent and table 1 is mixed with water 42g, after stirring second with 2000rpm/30 under 25 ℃, in the 100ml bottle container, be placed in 25 ℃ of thermostatic baths.In the sampling of the elapsed time shown in the table 1, carry out the titration of NCO base, measure the % of remaining NCO base.The titration of NCO base is following to be carried out: add after quantitative dibutylamine reacts, with the amino amount of the remaining dibutylamine of salt acidometric titration.In addition, in the outward appearance of observation group's compound liquid of described elapsed time of table 1.With their table 1 that the results are shown in.
Can keep the survival rate value near the NCO survival rate (100%) of theoretical value more for a long time, in addition, outward appearance does not change, and does not produce foaming, the generation of insoluble branch, and the serviceable time of coating agent is long more.
(2) (A)+(B)+(C) the NCO survival rate % of the water dispersion of composition
Will as the waterborne polyurethane resin liquid of (A) composition and make the solidifying agent of (B) composition and (C) low-molecular weight compound of composition be scattered in water medium and the biliquid of the dispersion liquid that obtains mixes, with the survival rate of the NCO base in the biliquid blend compositions regulation aqueous urethane resin composition is estimated as the isocyanate group of the serviceable time of coating agent and reactive inhibition degree of water.
The polyisocyanates A (9.6g) of solidifying agent and the total 12g of the additive (2.4g) shown in the table 2 are mixed with host 60g, after stirring second with 2000rpm/30 under 25 ℃, in the 100ml bottle container, be placed in 25 ℃ of thermostatic baths.Through certain hour the time, take a sample, carry out the titration of NCO base, measure the % of remaining NCO base.The titration of NCO base is following to be carried out: add after quantitative dibutylamine reacts, with the amino amount of the remaining dibutylamine of salt acidometric titration.In addition, also estimate the water tolerance of tunicle.With their table 2 that the results are shown in.
Can keep the survival rate value near the NCO survival rate (100%) of theoretical value more for a long time, the serviceable time of coating agent is long more.
[viscosity of biliquid blend compositions]
25 ℃ viscosity number with the biliquid blend compositions is estimated the dispersiveness of aqueous urethane resin composition in water medium of the water dispersion of (A)+(B)+(C) composition.Take a sample during certain elapsed time, carry out viscosimetric analysis, it be the results are shown in table 2.
It is low more to measure viscosity number, and the visbreaking effect is big more, and dispersiveness is high more, as the operation of coating agent, good more by film properties.
Table 1
| Embodiment 1 DBM | Embodiment 2 DOM | Comparative example 1 DEDEG | Comparative example 2 DOA | |
| After just having stirred | Oyster white | Oyster white | Translucent | Oyster white |
| After 2 hours | 100 | 86.4 | 92.2 | 100 |
| 2.5 after hour | Foaming |
| After 3 hours | 0 produces insoluble composition | |||
| After 4 hours | 100 | 80.7 | 92.8 | |
| 4.5 after hour | Foaming | |||
| After 5 hours | 100 | 19.3 | 0 produces insoluble composition | |
| 5.5 after hour | 0 produces insoluble composition | |||
| After 6 hours | 80.9 | |||
| 6.5 after hour | Foaming | |||
| 7.5 after hour | 0 produces insoluble composition | |||
| Reach the time of NCO=0% | 7～7.5 hours | 5～5.5 hours | 2.5～3 hours | 4.5～5 hours |
(explanation of mark in the table 1)
DBM: dibutyl maleinate DOM: dioctyl maleate DEDEG: diethyl carbitol DOA: Octyl adipate
Table 2
| Composition C | Composition B/C=80/20 viscosity NCO content (mPas25 ℃) (%) | Composition A/ (B+C)=100/20 dispersive composition gelation time film after 4 hours (hour) water tolerance | |||
| Comparative example | Do not have | 2700 | 16.4 | 3 | × |
| DEDEG | 200 | 13.1 | 3.5 | × | |
| DMDPC | 250 | 13.1 | 3.5 | × | |
| DOA | 250 | 13.1 | 4～4.5 | × | |
| PC | 450 | 13.1 | 4～4.5 | × | |
| Embodiment | DEM | 500 | 13.1 | 5～5.5 | ○ |
| DBM | 700 | 13.1 | 6 | ○ | |
| DOM | 800 | 13.1 | 7 | ○ |
(water tolerance test of record in the table 2)
After the application, carry out dip test in 50 ℃, 3 hours water, the test back is adopted visual and finger touches to observe and films, have or not albefaction according to filming and be clamminess, in table 2 with " zero: good, △: good substantially; *: filming produces albefaction and is clamminess no water tolerance " put down in writing evaluation result.
(explanation of mark in the table 2)
DEM: ethyl maleate DMDPG: dipropylene glycol dme PC: propylene carbonate
[result's of embodiment and comparative example investigation]
By contrasting each above embodiment and each comparative example as can be known, in aqueous urethane resin composition of the present invention, by add as properties-correcting agent have unsaturated link(age) between carbon or in abutting connection with the low-molecular weight compound of carbonyl, and do not have unsaturated link(age) between carbon or contrast in abutting connection with the comparative example of the conventional example of the compound of carbonyl as utilizing, serviceable time is able to abundant prolongation, dispersiveness in water medium is also good, operation as the coating agent, become good by film properties, and as the coating agent, under moistening atmosphere, do not have to produce the albefaction of filming and be clamminess the water tolerance excellence of tunicle.
Specifically; embodiment 1 at table 1; in 2; in the waterborne compositions of composition B and C; back from firm stirring to the NCO base survival rate that shows more than 4 hours near theoretical value (100%); the waterborne compositions foaming; produce insoluble composition and become can not use be 5 hours after; but in comparative example 1; only just can't show NCO base survival rate after just having stirred near theoretical value by 2 hours; the waterborne compositions foaming; produce insoluble composition and become can not use be 2.5 hours after; DOA is than the hydrophobicity height of the DEDEG of comparative example 1 in the comparative example 2; protect isocyanic ester not react slightly with water; compare with comparative example 1; the survival rate height of NCO, but its survival rate is than embodiment 1; 2 is poor, confirmed the brilliance of the serviceable time prolongation effect of composition C in the waterborne compositions of the present invention.
In addition as can be known, the composition C of all embodiment in the aqueous resin composition of table 2 compares with each composition of comparative example, and gelation time is prolonged significantly, and the water tolerance of filming is also good.By the data of viscosity as can be known, compare with the conventional example of added ingredients C not, the visbreaking effect is big, and is dispersed high, as the operation of coating agent, become good by film properties.
Investigated by above data results, the reasonableness of constitutive requirements of the present invention and having a mind to property are confirmed, and the present invention compared with prior art we can say that it is clear and definite having significant superiority.
Utilize the field on the industry
According to the present invention, can fully prolong the up time of cured with isocyanates aqueous resin composition, but also can fully obtain the dispersiveness of aqueous resin composition in aqueous medium, make thus resin combination become even, in addition, the viscosity of resin combination is minimized, operation as the smears also is improved, and to access unlike existing organic solvent be the excellent tunicle outward appearance of having of polyurethane resin smears difference, the tunicle of hardness and resistance to water etc., therefore industrially, as the water-base resin smears, particularly useful in paint field, utilize the possibility height.
Claims (6)
1. aqueous resin composition, it is characterized in that: be to contain (A) composition and (B) resin combination of composition, described (A) composition is a water-borne acrylic resin host, or the aqueous polyurethane prepolymer host that polyvalent alcohol and diisocyanate cpd reaction are obtained, described (B) composition is a solidifying agent, it is the adult that adds that can be scattered in beyond the tripolymer of the diisocyanate cpd in (A) composition or the tripolymer, added have unsaturated link(age) between carbon and in abutting connection with the low-molecular weight compound of carbonyl as (C) composition, (C) composition is a number-average molecular weight less than 500 low-molecular weight compound; (B)/(A) composition quality ratio is 0.01～0.50, adds (C) composition 0.01～30 mass parts with respect to (B) composition 100 mass parts.
2. the described aqueous resin composition of claim 1, it is characterized in that: (B) solidifying agent of composition is the allophanate solidifying agent of the several hexamethylene diisocyanates more than 4 of functional group, and (C) composition is the unsaturated dicarboxylic acid diester.
3. the described aqueous resin composition of claim 2, it is characterized in that: the unsaturated dicarboxylic acid diester is a dialkyl maleate.
4. claim 2 or 3 described aqueous resin compositions, it is characterized in that: aqueous resin composition is a coating composition.
5. the described aqueous resin composition of claim 4, it is characterized in that: aqueous resin composition is the two-pack type coating composition, be the waterborne polyurethane resin of (A) composition and (B) the binary composition material as the polyisocyanates of solidifying agent of composition, when using binary is mixed as coating, add the additive of (C) composition to (A) composition in advance or (B) in the composition, perhaps add during the mixing of composition at (A) composition with (B).
6. the manufacture method of the described aqueous resin composition of claim 1, it is characterized in that: make the solidifying agent of (B) composition and (C) low-molecular weight compound of composition and dispersing auxiliary as required be scattered in the water medium and form water dispersion, form and (A) composition of the water-dispersed resin host of composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP094151/2005 | 2005-03-29 | ||
| JP2005094151 | 2005-03-29 | ||
| PCT/JP2006/306187 WO2006104111A1 (en) | 2005-03-29 | 2006-03-27 | Modified water-based resin composition |
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| CN101151288A CN101151288A (en) | 2008-03-26 |
| CN101151288B true CN101151288B (en) | 2011-06-08 |
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| WO (1) | WO2006104111A1 (en) |
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| CN105131801A (en) * | 2015-09-23 | 2015-12-09 | 上海贻赛新材料科技有限公司 | Water-based polyurethane coating material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120201963A1 (en) | 2010-10-08 | 2012-08-09 | Ecolab Usa Inc. | Polyurethane floor finishes with hybrid performance |
| CN102020759B (en) * | 2010-10-27 | 2012-09-05 | 中国科学院长春应用化学研究所 | Preparation method of waterborne resin and water-based paint composition |
| CN102408826B (en) * | 2011-06-30 | 2013-04-24 | 昆山市万胜化工有限公司 | American type water-based coating finish paint and preparation method thereof |
| JP2013151645A (en) * | 2011-12-27 | 2013-08-08 | Sumika Bayer Urethane Kk | Aqueous urethane resin composition |
| CN102898615A (en) * | 2012-09-11 | 2013-01-30 | 青岛文创科技有限公司 | Method for modification of waterborne polyurethane by using epoxy resin |
| CN102936330A (en) * | 2012-11-19 | 2013-02-20 | 李莲 | Production process for water dispersible polyisocyanate cross-linking agents containing phosphate-radical functional groups |
| CN103030774A (en) * | 2012-12-07 | 2013-04-10 | 青岛文创科技有限公司 | Preparation method of organic silicon modified cationic waterborne polyurethane |
| US10883026B2 (en) * | 2017-12-21 | 2021-01-05 | Covestro Deutschland Ag | Adhesive based on a special polyurethaneurea with adjustable bonding force, and production and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401686A (en) * | 2002-09-04 | 2003-03-12 | 清华大学 | Process for preparing quick response pH-sensitive polyurethane film |
| CN1430657A (en) * | 2000-05-19 | 2003-07-16 | 阿克佐诺贝尔股份有限公司 | Aqueous cross-likable binder composition and coating, lacquer or sealing composition comprising such binder composition |
| CN1440988A (en) * | 2002-05-31 | 2003-09-10 | 段友芦 | Aquious carbaminate-olefine hybrid polymer dispersing liquid and its prepn and use |
| CN1524116A (en) * | 2001-09-28 | 2004-08-25 | ����ϣ��ʽ���� | Self-reactive/curable water-based solid adhesive and method of bonding with the self-reactive/curable water-based solid adhesive |
| CN1670052A (en) * | 2005-03-16 | 2005-09-21 | 上海市建筑科学研究院有限公司 | Water-base polyurethane / acrylate composite elastic resin and method for synthesizing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3484784B2 (en) * | 1994-11-08 | 2004-01-06 | 三菱瓦斯化学株式会社 | Polyurea resin |
| JP2000063514A (en) * | 1998-08-17 | 2000-02-29 | Toyo Ink Mfg Co Ltd | Water-based resin composition |
| DE10237193A1 (en) * | 2002-08-14 | 2004-02-26 | Bayer Ag | Polyurethane-Polyacrylathybride as a coating agent |
-
2006
- 2006-03-27 CN CN2006800106917A patent/CN101151288B/en not_active Expired - Fee Related
- 2006-03-27 WO PCT/JP2006/306187 patent/WO2006104111A1/en active Application Filing
- 2006-03-27 JP JP2007510502A patent/JPWO2006104111A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1430657A (en) * | 2000-05-19 | 2003-07-16 | 阿克佐诺贝尔股份有限公司 | Aqueous cross-likable binder composition and coating, lacquer or sealing composition comprising such binder composition |
| CN1524116A (en) * | 2001-09-28 | 2004-08-25 | ����ϣ��ʽ���� | Self-reactive/curable water-based solid adhesive and method of bonding with the self-reactive/curable water-based solid adhesive |
| CN1440988A (en) * | 2002-05-31 | 2003-09-10 | 段友芦 | Aquious carbaminate-olefine hybrid polymer dispersing liquid and its prepn and use |
| CN1401686A (en) * | 2002-09-04 | 2003-03-12 | 清华大学 | Process for preparing quick response pH-sensitive polyurethane film |
| CN1670052A (en) * | 2005-03-16 | 2005-09-21 | 上海市建筑科学研究院有限公司 | Water-base polyurethane / acrylate composite elastic resin and method for synthesizing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131801A (en) * | 2015-09-23 | 2015-12-09 | 上海贻赛新材料科技有限公司 | Water-based polyurethane coating material and preparation method thereof |
| CN105131801B (en) * | 2015-09-23 | 2018-03-30 | 上海贻赛新材料科技有限公司 | A kind of aqueous polyurethane coating and preparation method thereof |
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| Publication number | Publication date |
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| JPWO2006104111A1 (en) | 2008-09-11 |
| WO2006104111A1 (en) | 2006-10-05 |
| CN101151288A (en) | 2008-03-26 |
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