CN1197463A

CN1197463A - Dispersions containing polyurethanes with carbonyl groups in the keto function

Info

Publication number: CN1197463A
Application number: CN 96197122
Authority: CN
Inventors: N·科凯尔; M·G·劳; R·厄托; H·拉比格; J－P·迈尔德; E·古宾斯; T·沃斯
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-09-22
Filing date: 1996-09-13
Publication date: 1998-10-28
Also published as: CA2230827A1; AU7281296A; JPH11512475A; WO1997011103A1; EP0851881A1

Abstract

The invention concerns aqueous dispersions containing a polyurethane (A), containing structural units derived from compounds of formula (I), in which the substituents have the following meanings: R<1>, R<2>, R<3> each designate hydrogen, C1-C24 alkyl or C6 - C24 alkenyl; R<4> designates hydrogen; R<5>, R<6> a) together designate C4-C10 alkane-diyl, b) each designate C2-C10 alkyl, C5-C8 cycloalkyl or C7-C20 aralkyl, c) each designate a hydroxyl-terminated poly(C2-C4 alkylene oxide), or d) designate an R<5> or R<6> group with the meaning given in (a) to (c) and the other group designating hydrogen or a group of formula (II), in which X designates C2-C6 alkane-diyl; and R<7> has the same meaning as R<5> or R<6> with the exception that R<7> is not a group of formula II, R<5> and R<6> carrying a total of between 2 and 5 hydroxyl groups bonded to aliphatic carbon atoms; and R<5> and/or R<6> optionally carrying 1 or 2 aromatically bonded hydroxyl groups or 1 nitrile, tertiary amino, carboxylic acid or sulphonic acid group which are optionally present in the form of their salts.

Description

The dispersion that contains the urethane of carbonyl on the ketone

The present invention relates to a kind of water dispersion that contains urethane (A), urethane (A) comprises from the structural unit of the compound deriving of general formula (I)

Wherein, each substituting group has following meanings: R ¹, R ²And R ³Each is hydrogen, C naturally ₁-C ₂₄Alkyl or C ₆-C ₂₄Alkenyl, R ⁴Be hydrogen, R ⁵And R ⁶Be

A) be C jointly ₄-C ₁₀Alkyl group,

B) each C naturally ₂-C ₁₀Alkyl, C ₅-C ₈Cycloalkyl or C ₇-C ₂₀Aralkyl,

C) each hydroxy-end capped naturally poly-(C ₂-C ₄Alkylene oxide),

D) R ⁵Or R ⁶One of as (a) to (c) defined, another group is hydrogen or general formula I I

Group:

Wherein: X is C ₂-C ₆Alkane 2 basis, and R ⁷As R ⁵Or R ⁶Defined, but be not the group of general formula I I, wherein-R ⁵And R ⁶Have 2-5 hydroxyl that is connected on the aliphatic carbons altogether, and-in case of necessity, R ⁵And/or R ⁶Can have 1 or 2 and be connected hydroxyl on the aromatic structure, or have itrile group, tertiary amine groups, carboxyl or a sulfonic group, it exists with the form of its salt in case of necessity.

The water dispersion that contains urethane be known (referring to D.G.Oertel " plastics handbook 7 " the 2nd edition, nineteen eighty-three, Ka Erhansi press, Munich, the dimension also that, 24-25 and 571-574 page or leaf).Also has been known with polyurethane dispersions as the coating composition such as paint or printing-ink.

Later coating is from the performance of its complete processing, economy and requirement, and polyurethane dispersions does not still satisfy a series of requirements that it is proposed at present fully, and this is must satisfy after it.

The use properties of coating will satisfy following requirement usually :-coating material should standing storage and can not make its performance (for example thixotropy) or the performance that produces has any change when using this coating.-coating material should contain minimum solvent, flow agent or other volatile organic components, when coated and dry, reduces emitting of organic compound with convenient coating material.-after coating material was coated on the workpiece, coating material rapid drying subsequently or curing were so that can be used further or process it after very short time.-coating material should show seldom or not show foaming tendency man-hour adding.

For quality coating that obtains by the polyurethane-coated material and surface, should satisfy following composite request :-slick surface and high gloss-water-fast branch, water vapor and such as the chemical substance of diluted alkaline and acid, and organic solvent-resistant and surface

Promoting agent-to such as impact or the stability of the mechanical stress of wearing and tearing-itself is colourless, not such as bubble or fissured defective-at the bottom of the wood based, coating material should make the visible structure of timber manifest more significantly (to expose

Wood grain).

The coating that exploitation has this over-all properties becomes difficult more, because independent performance characteristic can be thought based on different structure propertiess.The prerequisite of wear resistance is the certain rigidity grade, and shock strength requires certain elasticity.And finish plate needs the good leveling property of coating material, and good levelling property means that usually the use volatile organic compounds is as flow agent.

Especially, coating material should be able to be processed with routine techniques in wide as far as possible scope.In order to satisfy the coating of definite quality level with the economical efficiency manufacturing of maximum, need the different technologies of differing complexity, its complexity is relevant with the quality of obtaining coating; In fact, the increase of complicacy and effort often only when its just think during with corresponding quality matches worthwhile.On the other hand, for the coating processor, for the different starting material of each processing technology deposit are complicated in logistics.In these technology, following content particularly important:

The cold-curing technology (coating is at room temperature solidified) of one-component coating systems is least complicated, and should satisfy the fair average quality requirement.

Because two-component coating system requires the processor to mix this system, only be the mixture of limited working life then, therefore this system is relevant with the bigger effort that the processor pays, and the purpose of the cold-curing technology of two-component coating system is to satisfy the higher quality requirement.

Baking technology (usually 100-160 ℃ of curing) is suitable for preparing the coating of peak performance.

Usually, the surface property of printing-ink satisfies the requirement of having explained identical with other coating materials.In addition, it is important making them satisfy further, specific requirement :-high share solid, especially pigment, so that make time of drying the shortest, and-good levelling property, even at the bottom of such as polyethylene and polyacrylic nonpolar group.

The goods of ink printing, especially the requirement that should satisfy of the goods made of non-polar plastic is: the cohesiveness that-printing ink is good to substrate, what especially be subjected to water influences the anti-usual vehicle of time-printing ink, fat, oil, tensio-active agent, aqueous solution, bronsted lowry acids and bases bronsted lowry-good adhesion property.

In some cases, this series of requirements also produces conflicting target, and the printing-ink of prior art can not solve this conflict fully.For example, well-known, the levelling property of printing-ink can improve by adding tensio-active agent, but coated printing ink water tolerance deficiency.Also may improve its wettability by adding solvent, but this can limit the ecological dominance of water-based inks.

EP-B-0 332 326 has described and has been used to apply polyurethane dispersions various substrates, that can be used as the single-component system.In described dispersion system,, comprise the composition of band hydrazine or hydrazone groups in the system in addition except that containing molecular weight greater than 2000 and have the dispersible urethane of water of the carbonyl in ketone or aldehyde functional group; Perhaps this urethane not only has at ketone or the organic carbonyl of aldehyde, also has hydrazine and/or hydrazone groups in addition.For the carbonyl structure unit is incorporated in the urethane, recommend the latter to prepare, as the Michael addition thing of the diamines of the diacetone-acryloamide(DAA) of the Michael addition thing of otan, diacetone-acryloamide(DAA) and diamines or alkanolamine or 2 moles and 2 moles with these monomers.

Yet what be that their produce with the shortcoming of the dispersion of otan preparation is brown film.

The Michael addition thing that described document is also mentioned in order to following monomer such as diacetone-acryloamide(DAA) and diethanolamine is incorporated into ketone group in the urethane.The single-component system that the monomer of even now can be used as cold-curing really is processed into the coating with satisfactory performance, but they are not suitable as two component system compositions that can produce the coating with premium properties level, can not produce by baking processing to satisfy the coating of being strict with.

In addition, in DE-A-3 837 519, known moisture urethane and the polyhydrazide water dispersion that disperses, is with carbonyl, wherein the carbonyl functional group enters into urethane by use unit or the polyvalent alcohol contain carbonyl in preparation process, contains the unit of carbonyl or affixture that examples of polyhydric alcohols is pyruvic alcohol, hydroxy benzaldehyde, acetoin, bitter almond oil camphor, diepoxides and keto-earboxylic acid and with the esters of keto-carboxylic acid of at least one hydroxyl.Described document has also been introduced these dispersions as coating material or printing-ink.

When there was high request the shelf lives, the dispersion that contains the urethane that is made by the poly-hydroxy carbonyl compound can not be entirely satisfactory.

Up to the present the mechanical property and the solvent resistance that contain the dispersion gained coating of the urethane that makes from above-mentioned monohydroxy carbonyl compound can not be entirely satisfactory.And these dispersions are easy to form coagulum.

EP-A-0 646 609 has also introduced polyurethane dispersions as printing-ink.The described urethane of the document has terminal hydrazine functional group, and can be dispersed in the water owing to having ionic group and polyethylene oxide group.

JP-A-75-98913 has described urethanes, and it is the acid amides (H from alkanolamine and acetate formation ₃CCOCH ₂CON (CH ₂CH ₂OH) ₂Or H ₃CCOCH ₂CONHC (CH ₂CH ₂OH) ₂C ₂H ₅) make, and with the etheric acid complex compound of aluminium or iron as chain propagation agent.

Therefore, an object of the present invention is, provide to have high performance omnipotent water-based coating material, it does not have the deficiencies in the prior art, in the man-hour that adds that this coating is carried out, it is firm, lubricious to require use to use the volatility leveling auxiliary agent just can obtain on a small quantity or not.Especially, coating material should be able to have maximum adaptability in use; The performance level that can reach when in other words, using this coating by different processing technologies should be low unlike prior art.

Further aim of the present invention is, the printing-ink of no prior art weak point is provided, and can be used for making and be printed substrate, particularly nonpolar printing substrate, and printing ink can adhere to securely in these substrates.

We have found that these purposes are achieved by above-mentioned dispersion.

Dispersion contains urethane (A), and urethane (A) comprises from the structural unit of the compound deriving of general formula (I)

R wherein ¹, R ²And R ³Each is hydrogen, C naturally ₁-C ₂₄Alkyl or C ₆-C ₂₄Alkenyl, R ⁴Be hydrogen, R ⁵And R ⁶Usually:

A) be C jointly ₄-C ₁₀Alkane 2 basis, preferably 1,4-butane two bases or 1,5-pentane two bases,

B) each C naturally ₂-C ₁₀Alkyl, C preferably ₂-C ₃-alkyl or C ₅-C ₈Cycloalkyl, preferably cyclopentyl or cyclohexyl or C ₇-C ₂₀Aralkyl, the group of preferably phenyl, or general formula I I:

Wherein: X is C ₂-C ₆Alkane 2 basis, and R ⁷As R ⁵Or R ⁶Defined, but be not the group of general formula I I,

C) each hydroxy-end capped naturally poly-(C ₂-C ₄Alkylene oxide), the group of general formula III preferably,

R wherein ⁸Be hydrogen, methyl and/or ethyl, and n is 1 to 10, wherein-R ⁵And R ⁶Have 2-5 jointly and be connected a hydroxyl on the aliphatic carbons, and-in case of necessity, R ⁵And/or R ⁶Can have 1 or 2 and be connected hydroxyl on the aromatic structure, or have

Itrile group, tertiary amine groups, carboxylic acid group or a sulfonic group, they exist with the form of its salt in case of necessity.

Consider according to above-mentioned required cross-linking density and relevant therewith mechanical property, selected like this by the carbonyl content in the polyurethane structural unit of the compound deriving of general formula (I), be in per 100 gram urethane, have 3 to 140 mmoles usually, be preferably 6 to 100 mmoles, especially be preferably the carbonyl of 10 to 90 mmoles.

The novel water dispersion of the present invention makes usually like this: I. prepares urethane with following substance reaction:

A) with the multifunctional isocyanide ester of 4 to 30 carbon atoms,

B) following polyvalent alcohol:

B1) in total consumption of polyvalent alcohol (b), 10-100% (mole), molecular weight is 500 to 5000 polyvalent alcohol, and

B2) in total consumption of polyvalent alcohol (b), difunctionality and the molecular weight of 0-90% (mole) are the polyvalent alcohol of 62-500g/mol,

C) compound of general formula I and/or have alcoholic hydroxyl and comprise from the condensation product (condenses I) of the structural unit of the compound deriving of general formula I,

D) if desired, in addition, be different from monomer (b) and polyfunctional compound (c), have the reactive group that is selected from alcoholic hydroxyl, primary amino and secondary amino group, and

E) with (a) and (b), (c) and (d) different monomer, have at least one isonitrile acid group group or at least one has the group of reactive behavior to the isonitrile acid group, and have at least one and can make urethane be dispersed in hydrophilic radical or potential hydrophilic radical in the water.II. the urethane that step I is obtained is dispersed in the water.

Suitable monomers (a) is many isocyanide esters general in the polyurethane chemistry.

Especially should be mentioned that diisocyanate X (NCO) ₂, wherein X is C ₄-C ₁₂Aliphatic hydrocarbyl, C ₆-C ₁₅Cyclic aliphatic or aromatic hydrocarbyl or C ₇-C ₁₅The araliphatic alkyl.The example of this diisocyanate is the tetramethylene diisocyanate, the hexa-methylene diisocyanate, ten dimethylene diisocyanates, 1,4-two isonitrile acid group cyclization hexanes, 1-isonitrile acid group closes-3,5,5-trimethylammonium-5-isonitrile acid group closes methylcyclohexane (IPDI), 2,2-two (4-isonitrile acid group cyclization hexyl) propane, the trimethyl cyclohexane diisocyanate, 1,4-two isonitrile acid groups close benzene, 2,4-two isonitrile acid groups close toluene, 2,6-two isonitrile acid groups close toluene, 4,4 '-two isonitrile acid groups close ditan, tetramethyl-xylylene diisocyanate (TMXDI), 2,4 '-two isonitrile acid groups close ditan, to the xylylene diisocyanate, the isomer such as the trans/trans-isomer(ide) of two (4-isonitrile acid group cyclization hexyl) methane, cis/cis-isomeride and cis/trans isomer, with the mixture that constitutes by these compounds.

Mixture as these isocyanic ester, especially two isonitrile acid groups close the mixture that toluene and two isonitrile acid groups close ditan constitutional isomer separately, particularly by 80% (mole) 2,4-two isonitrile acid groups close toluene and 20% (mole) 2, and 6-two isonitrile acid groups close the mixture that toluene constitutes.Such as 2,4-two isonitrile acid groups close toluene and/or 2,6-two isonitrile acid groups close this class aromatics isocyanide ester of toluene and also have special advantage such as the mixture of hexa-methylene diisocyanate or this class aliphatic series of IPDI or cyclic aliphatic isocyanide ester, preferably, aliphatic isocyanide ester is 4: 1 to 1: 4 with the ratio of aromatics isocyanide ester.

Except that isonitrile acid group group freely, the isocyanide ester that is suitable as compound (a) also comprises those that have other isonitrile acid group group of sheltering, as urea diketone (uretdione) or carbodiimide groups.

If desired, only also may use simultaneously with the isocyanide ester of an isonitrile acid group group, in monomeric integral molar quantity, its common consumption is no more than 10% (mole).Single isocyanide ester generally has other functional group, and as thiazolinyl or carbonyl, and for introduction in the urethane functional group, it makes, and polymkeric substance may disperse, the similar reaction of crosslinked or other urethane.The monomer that is suitable for this purpose is as pseudoallyl-α, those of α-Er Jiajibianji isocyanide ester (TMI).

The urethane that has the suitable degree of branching and suitable degree of crosslinking for preparation, may use for example trifunctional or four functionalized isocyanide esters, trifunctional or four functionalized isocyanide esters are reflected at together dual functional isocyanide ester by reaction and obtain, in the reaction, some isonitrile acid group group is wherein derived and is formed allophanic acid foundation group, biuret group or isocyanide urea foundation group.The example of commodity compound is the isocyanide urea ester or the biuret of hexa-methylene diisocyanate.

The example of the more multi-functional many isocyanide esters of other suitable bands is the many isocyanide esters that contain urethane groups, it is on the one hand based on 2,4-two isonitrile acid groups close toluene and/or 2,6-two isonitrile acid groups close toluene, isophorone diisocyanate or tetramethylene diisocyanate, on the other hand based on the polyol such as the low molecular mass of TriMethylolPropane(TMP).

For good film-forming properties and elasticity, the suitable polyvalent alcohol of ideal (b) is the high-molecular weight polyvalent alcohol, dibasic alcohol (b1) preferably, and the molecular weight that is had is about 500-5000g/mol, preferably, is about 1000-3000g/mol.

Polyvalent alcohol (b1) is polyester polyol especially, for example from " Ullmanns encyclopedia of chemical technology " the 4th edition, and the 19th volume, known in the 62-65 page or leaf, preferably by dibasic alcohol and di-carboxylic acid are reacted these that obtain.For the preparation polyester polyol, except that the free polycarboxylic acid, also may use they acid anhydrides or with the ester of lower alcohol or their mixture.Polycarboxylic acid can be aliphatic, cyclic aliphatic, araliphatic, aromatics or the heterocyclic carboxylic acid, and can be carboxylic acid undersaturated and/or that replaced by halogen for example.These examples for compounds are the lipid acid of suberic acid, nonane diacid, phthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride, tetrahydronaphthalic anhydride, hexahydro phthalic anhydride, tetrachloro Tetra hydro Phthalic anhydride, nadic anhydride, Pyroglutaric acid, toxilic acid, maleic anhydride, fumaric acid and dimerization.Preferred dicarboxylic acid is that general formula is HOOC-(CH ₂) _yThe dicarboxylic acid of-COOH, wherein y is 1 to 20,2 to 20 even number preferably, the example of above-mentioned dicarboxylic acid is succsinic acid, hexanodioic acid, dodecane dicarboxylic acid, sebacic acid.

Examples of polyhydric alcohols is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, such as 1, two (methylol) hexanaphthene of 4-two (methylol) hexanaphthene, 2-methyl isophthalic acid, ammediol, methyl pentanediol, glycol ether, Triethylene glycol, tetraethylene-glycol, polyoxyethylene glycol, dipropylene glycol, polypropylene glycol, contract dibutylene glycol and polytetramethylene glycol.Preferably neopentyl glycol and general formula are HO-(CH ₂) _xThe alcohol of-OH, wherein x is 1 to 20,2 to 20 even number preferably, the example is an ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol and 1,12-dodecyl glycol.

Many carbonic ethers dibasic alcohol also is suitable, and it can be by for example making the low-molecular-weight alcohol reaction of carbonyl chloride and synthetic ingredient excessive, that be mentioned as polyester polyol.

Suitable compound also comprises the polyester diol based on lactone, and they are the homopolymer or the multipolymer of lactone, preferably the terminal hydroxy group adduct of lactone and suitable difunctionality raw molecule.Suitable lactone is HO-(CH from general formula preferably ₂) _z-COOH, wherein z is those of compound deriving of 1-20, the example of lactone is 6-caprolactone, β-Bing Chunsuanneizhi, gamma-butyrolactone and/or methyl-6-caprolactone and their mixture.The example of proper raw material composition is the low-molecular-weight dibasic alcohol of referred synthetic ingredient as polyester polyol.The polymkeric substance of corresponding 6-caprolactone is especially preferred.Rudimentary polyester diol or polyether Glycols also can be used as the raw material of ε polymkeric substance.Except that lactone polymer, also may use polycondensation product corresponding corresponding to lactone, stoichiometric hydroxycarboxylic acid.

Polyesterols also can from a small amount of simple function-and/or polyfunctional monomer make.

Other suitable monomers (b1) is a polyether Glycols.They especially can pass through for example at BF ₃Existence under, oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF), Styrene oxide 98min. or Epicholorohydrin and itself polymerization are obtained; Perhaps with these compounds individually or mix ground or continuously with the material composition that contains reactive hydrogen such as alcohol or amine for example water, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-two (4-hydroxy diphenyl) propane or aniline carry out addition reaction.Especially preferred be molecular weight in the 240-5000 scope, the polytetrahydrofuran in the 500-4500 scope particularly.

What be suitable as monomer (b1) equally is poly-hydroxyl alkene, preferably with the poly-hydroxyl alkene of two terminal hydroxy group, and α-w-dihydroxy polybutadiene, α-w-dihydroxyl polymethacrylate or α-w-dihydroxyl polyacrylic ester for example.These compounds are from for example learning the EP-A-0 622 378.

Other suitable polyol is polyacetal, polysiloxane and Synolac.

Polyol also can use by the mixed of any needs.

If employed polyol (b) not only comprises polyol (b1), comprise that also molecular weight is about 62-500g/mol, be preferably the low-molecular-weight dibasic alcohol (b2) of 62-200g/mol, the consistency and elasticity modulus of urethane can obtain increasing.

Especially be mentioned the synthetic ingredient of the short chain paraffinic hydrocarbons dibasic alcohol that is used to prepare polyester polyol as the compound of monomer (b2), preferably neopentyl glycol and with the non-branching dibasic alcohol of 2,4,6,8,10 or 12 carbon.

In the total amount of polyol (b), the preferable amount of polyol (b1) is 10-100% (mole), and the preferable amount of monomer (b2) is 0-90% (mole).The ratio of polyol (b1) and monomer (b2) preferably 0.2: 1 to 5: 1, especially preferred is 0.5: 1 to 2: 1.

The compound that is particularly suitable for composition (c) is these compounds of general formula (I), and they carry out addition reaction by the alkanolamine with the diketone of general formula (IV) and logical formula V and obtain.

In the amine of the diketone of general formula (IV) and logical formula V, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶And R ⁷Respectively as defined in the general formula (I).

Preferably use wherein R ¹, R ²And R ³Be the diketone of hydrogen, or R wherein ¹And R ²In one be hydrogen, another and R ³Be linear, saturated and hexadecyl non-replacement.

Especially preferred amine is to have two mono amino polyvalent alcohols that are connected the hydroxyl on the aliphatic carbons, 1-amino-2 for example, ammediol, 2-amino-1, ammediol, 2-amino-2-methyl-1, ammediol, 2-amino-2-ethyl-1, ammediol, 2-amino-1-phenyl-1, ammediol, diethanolamine, diisopropanolamine (DIPA), 3-(2-hydroxyethylamino) propyl alcohol and N-(3-hydroxypropyl)-3-hydroxyl-2,2-dimethyl-1-aminopropane.

Have more than two mono amino polyvalent alcohols that are connected the hydroxyl on the aliphatic series and also be fit to, for example three (methylol) methylamine, 2-[three (methylol) methylamino-] ethane sulfonic acid, 3-[three (methylol) methylamino-] propane sulfonic acid, N-[three (methylol) methyl] Padil, three (3-hydroxypropyl) methylamine, glycosamine and N-(2-hydroxyethyl) glycosamine; Or the diamino dibasic alcohol also is fit to, N for example, the reaction product of oxyethane, propylene oxide and/or the butylene oxide ring of N '-two (2-hydroxyethyl) ethylene diamine, two uncle's formula polyether diamines of every mole and 2 moles, select the reaction conditions of polyether diamine and alkylene oxide like this, so that obtain having the N of two secondary formula amino, N '-two (hydroxyl oxygen substituted alkyl amine) derivative with high selectivity.The example of polyether diamine is 4,7-dioxadecane-1,10-diamines, 4, the 11-two oxa-tetradecanes-1,14-diamines, molecular weight are the poly-[oxidation (methyl isophthalic acid of α-(2-aminomethyl ethyl)-ω-(the 2-aminomethyl oxyethyl group) of 200-3000,2-two ethyl groups)] and molecular weight be α-(3-aminopropyl)-ω-(the 3-ammonia propoxy-) poly-[oxidation (1,4-butane two bases)] of 300-3000.

Also can use and only have a mono amino polyvalent alcohol that is connected the hydroxyl on the aliphatic carbons, thanomin for example, the N-Mono Methyl Ethanol Amine, the N-ehtylethanolamine, the N-butylethanolamine, N-cyclohexyl ethyl alcohol amine, N-tertiary butyl thanomin, leucine alcohol (leucinol), Isoleucine alcohol, valine alcohol, proline(Pro) alcohol, Qiang Yijibenan, 2-(methylol)-piperidines, 3-(methylol)-piperidines, 2-(2-hydroxyethyl)-piperidines, 2-amino-2-phenylethyl alcohol, 2-amino-1-phenylethyl alcohol, ephedrine, to hydroxyephedrine, norephedrine, suprarenin, norepinephrine, Serine, isoserine, Phenserine, 1,2-phenylbenzene-2-monoethanolamine, 3-amino-1-propyl alcohol, 2-amino-1-propyl alcohol, 2-amino-2-methyl-1-propanol, Yi Bingchunan, N-ethyl Yi Bingchunan, 2-amino-3-phenyl propanol, 4-amino-1-butanols, 2-amino-1-butanols, the 2-aminoisobutanol, neopentyl alcohol amine, 2-amino-1-amylalcohol, 5-amino-1-amylalcohol, the amino amylalcohol of 2-ethyl-2-butyl-5-, 6-amino-1-hexanol, 2-amino-1-hexanol, 2-(2-amino ethoxy) ethanol, 3-(aminomethyl)-3,5, the 5-cyclonol, the 2-aminobenzyl alcohol, the 3-aminobenzyl alcohol, 2-amino-5-xylyl alcohol, 2-amino-3-xylyl alcohol, 3-amino-2-methyl benzylalcohol, 3-amino-4-xylyl alcohol, 3-aminomethyl benzylalcohol, 1-aminoethyl-4-hydroxy-benzyl alcohol, 2-(4-aminophenyl) ethanol, 2-(2-aminophenyl) ethanol, 1-(3-aminophenyl) ethanol, Serine [sic], homoserine, Threonine, thanomin acetate, 4-amino-3-hydroxybutyric acid, N-(2-hydroxyethyl) glycinonitrile, 4-(2-hydroxyethyl) piperazine and 1-amino-4-(2-hydroxyethyl) piperazine, 2-itrile group ethanol; Or use diamino unit alcohol, and as N-(2-aminoethyl) thanomin, 1-[2-(2-hydroxyl-oxethyl) ethyl] piperazine and 1,3-diamino-2-propyl alcohol.

Preferably use from the compound of the general formula (I) of mono amino monohydroxy-alcohol or the preparation of polyamino monohydroxy-alcohol, consumption in all monomers (c), the consumption of mono amino monohydroxy-alcohol or polyamino monohydroxy-alcohol is no more than 50% (mole), especially preferably is no more than 20% (mole).

With a small amount of use contain single-or the effect of these monomers (c) of polyamino monohydroxy-alcohol be the viscosity of for example controlling in the urethane building-up process.

Preferred general formula I adduct is R wherein ¹, R ²And R ³Be the diketone of hydrogen and those adducts of compound (Ia).

The compound of general formula (I) can be used for example DE11 42 859 or GB715, and 896 modes of describing with preparation acetoacetyl sulfonamide derivatives are prepared.

The compound that is suitable for composition (c) can also be the condensation product (condenses I) that contains from the structural unit of the compound deriving of general formula (I), for example molecular weight is the polyester polyol that contains carbonyl of 300-5000, and for example obtains by following material is carried out polycondensation:

X) compound of general formula (I) wherein is connected on the aliphatic carbons and by substituent R ⁵And R ⁶, as

Fruit is suitable, with R ⁷The total hydroxy of carrying together be 2 (Compound I a), and

Y) if desired, molecular weight is dibasic alcohol (binary 62-500g/mol, except that Compound I a

Alcohol y)

Z) and dicarboxylic acid,

The mol ratio of compound (Ia) and dibasic alcohol (y) sum and dicarboxylic acid is 2: 1 to 1.05: 1.

Preferred dibasic alcohol (y) and preferred dicarboxylic acid (z) are these compounds that also are used for synthesizing polyester dibasic alcohol (b1).

Be preparation condenses (I), also may be preferably use simple function-and/or more than two functional alcohol or carboxylic acids with less amount.The preparation method of this condenses (I) is from for example US5, learns in 321,118.

The monomer (d) that is different from composition (b) and dibasic alcohol (c) generally is used for crosslinked or chainpropagation.Usually, they are three-or higher functional non-aromatic alcohol, with 2 or more primary-and/or the amine of secondary amino group and not only have one or more alcoholic extract hydroxyl groups, and have one or more primary-and/or the compound of secondary amino group.

Be used to produce the ternary of the suitable degree of crosslinking or the degree of branching and the example of Geng Gao functional alcohol is TriMethylolPropane(TMP), glycerol and sucrose.

Other alcohol that is considered is monohydroxy-alcohol, this monohydroxy-alcohol hydroxyl-removal also have outward other can with the group of isocyanide ester reaction, for example one or more primary aminos and/or secondary amino group; An example is a monoethanolamine.

When water exists chainpropagation takes place or when crosslinked down, the especially available polyamine that has two or more primary aminos and/or secondary amino group because with alcohol or water ratio, the reaction of amine and isocyanide ester is faster usually.When requiring it is that this point is normally essential when being used for the water dispersion of crosslinked polyurethane or high molecular urethane.In these cases, preparation contains that back to back step is that it is dispersed in the water fast behind the prepolymer that the isonitrile acid group closes, and can carry out crosslinked or chainpropagation by interpolation with the compound of the amino of isocyanide ester reaction with two or more then.

The amine that is suitable for above-mentioned purpose is polyfunctional amine normally, and its molecular weight preferably in the scope of 60-300g/mol, and contains at least two primary aminos, two secondary amino groups or a primary amino and a secondary amino group in the 32-500g/mol scope.Example is a diamine, as diaminoethanes, diaminopropanes, diaminobutane, diamino hexane, piperazine, 2,5-lupetazin, amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophorone diamine, IPDA), 4,4 '-diamino-dicyclohexyl methane, 1,4-diamino-cyclohexane, N-aminoethyl ethanolamine, hydrazine or hydrazine hydrate; Or tertiary amine, as diethylenetriamine or 1,8-diamino-4-aminomethyl octane.

Amine also can use with protected form, for example with the form of corresponding ketoimine (seeing for example CA-1129 128), ketazine (referring to for example US-A4,269,748) or amine salt (seeing US-A4,292,226).In addition, at for example US-A4, such ， oxazolidine used in 192,937 constitutes the polyamines of sheltering, and this polyamines can be used in the chainpropagation of prepolymer for the novel urethane of preparation.When using this polyamines of sheltering, they mix with prepolymer under anhydrous situation usually, form thereafter with water-dispersion mutually or with portion water disperse phase bonded mixture, obtain release to cause suitable polyamine by hydrolysis.

Urethane does not preferably contain polyamine, or in composition (b), (c) and total amount (d), contains 1-10% (mole), especially preferably contains the polyamine (as monomer (d)) of few 2 amino that react with isocyanide ester of bringing to of 4-8% (mole).

And, also can use more a spot ofly, promptly in composition (b) and amount (d), preferably the monohydroxy-alcohol less than 10% (mole) is used for chain termination.Its effect promptly mainly is that the urethane that has free redical polymerization C=C is worked usually similar in appearance to the effect of single isocyanide ester.

And, also can use more a spot of, promptly in composition (b) and amount (d), preferably the unit alcohol less than 10% (mole) is used for chain termination.Its effect promptly mainly is to make the urethane of the C=C that has free redical polymerization carry out functionalization usually similar in appearance to the effect of single isocyanide ester.

For making urethane in water, have dispersibility, they not only comprise composition (a)-(d) usually, also comprise the monomer (e) that is different from composition (a)-(d), monomer (e) has at least one isonitrile acid group base or at least one isonitrile acid group closes reactive group, has the group that at least one hydrophilic radical maybe can change into hydrophilic radical in addition.Hereinafter, term " hydrophilic radical or potential hydrophilic radical " abbreviates " (potential) hydrophilic radical " as.(potential) hydrophilic radical is slower than functional group that monomer is with that is used for the synthetic polymer main chain and isocyanide ester significant reaction ground with the isocyanide ester reaction.

In the total amount of composition (a)-(e), the components in proportions that has (potential) hydrophilic radical normally like this, promptly in all monomeric weight of (a)-(e), the molar weight of (potential) hydrophilic radical is 30-1000mmol/kg, preferably 50-500mmol/kg and especially preferably 80-400mmol/kg.

(potential) hydrophilic radical can contain non-ionic type or (potential) ionic hydrophilic group group preferably.

Suitable non-ionic hydrophilic group especially has preferably 5-100, especially preferably the polyglycol ether of 10-80 oxyethane repeating unit.In all monomeric weight of (a)-(e), the unitary content of polyethylene oxide is 0-10% (weight) normally, preferably 0-6% (weight).

The preferred monomers that contains non-ionic hydrophilic group is the reaction product of polyoxyethylene glycol and diisocyanate, and this diisocyanate has the polyethylene group of end group etherificate.The preparation method of this diisocyanate and they is described in US3, in 905,929 and 3,920,598.

Ionic hydrophilic group group is the anionic group especially, as sulfonate radical, carboxylate radical and the phosphate radical of alkali metal salts or ammonium salt form with them; Can be cation group also, as ammonium, especially protonated tertiary amino group or quaternary ammonium group.

Potential ionic hydrophilic group group especially changes into the group that above-mentioned ionic hydrophilic group is rolled into a ball by simple neutralization, hydrolysis or quaternization, so example is carboxyl, uncle's amino or anhydride group.

(potential) ionic comonomer (e) for example is described in detail in " Ullmanns encyclopedia of chemical technology ", and the 4th edition, the 19th volume is among 311-313 page or leaf and the DE-A-1495745.

As (potential) cationic monomer (e), the monomer of the particularly tertiary-amino-containing group that is even more important in force, for example three (hydroxyalkyl) amine, N, N '-two (hydroxyalkyl) alkylamine, N-(hydroxyalkyl) dialkylamine, three (aminoalkyl) amine, N, N '-two (aminoalkyl) alkylamine and N-aminoalkyl dialkylamine, wherein alkyl and alkane 2 basis are C independently of one another ₂-C ₆Segment.What other took in is the polyethers that has tertiary N atom and preferred two terminal hydroxy group, this polyethers can by for example in essence the mode of known alkoxylated amines obtain, this amine has two hydrogen atoms on the nitrogen-atoms that is connected ammonia, and the example is methylamine, aniline or N, N '-dimethylhydrazine.The molecular weight of this polyethers is 500-6000g/mol normally.

These tertiary amines or change into ammonium salt with acid-respons, preferred acid is strong inorganic acid or the strong organic acid such as phosphoric acid, sulfuric acid or haloid acid; Perhaps change into ammonium salt, quaternizing agent such as C with the reaction of suitable quaternizing agent ₁-C ₆Alkyl halide, for example their bromide or muriate.

The suitable monomer that contains (potential) anionic group be general aliphatic series-, cyclic aliphatic-, araliphatic-or aromatic carboxylic acid and sulfonic acid, these carboxylic acids and sulfonic acid have at least one alcoholic extract hydroxyl group or at least one primary-or secondary amino group.Dihydroxyalkyl carboxylic acid preferably, especially with the dihydroxyl alkyl carboxylic acid of 3 to 10 carbon atoms, they particularly are described in US-A3, in 412,054.Especially preferred is the compound of following general formula:

R wherein ^aAnd R ^bEach is C naturally ₁-C ₄The alkane 2 basis unit, R ^cBe C ₁-C ₄Alkyl unit; Or dimethylol propionic acid (DMPA) especially.

Appropriate dihydroxyl sulfonic acid and dihydroxyl phosphonic acids are as 2, and 3-dihydroxypropane phosphonic acids also is fit to.

Learn that from DE-A39 11 827 molecular weight is 500-10,000g/mol and the dihydroxy compound that has at least two carboxylate group also are suitable.They pass through with dihydroxy compound and such as 1,2,4, and the tetracarboxylic dianhydride of 5-pyromellitic acid dianhydride or cyclopentane tetracarboxylic acid dianhydride reaction is carried out polyaddition reaction with 2: 1 to 1.05: 1 mol ratios and obtained.Especially suitable dihydroxy compound is above-mentioned monomer as chain propagation agent (b2), also can be polyvalent alcohol (b1).

The proper monomer (e) that contains the amino of responding property of isocyanide ester is the aminocarboxylic acid that is described among the DE-A2034 479, as Methionin, β-An Jibingsuan and aliphatic di-primary formula diamines and α, the affixture of beta-unsaturated carboxylic acid such as N-(2-aminoethyl)-2-ethylamine carboxylic acid and corresponding N-aminoalkyl aminoalkyl carboxylic acid, two alkyl groups wherein have 2 to 6 carbon atoms.

Have the monomeric occasion of potential ionic group in use, they can be before the isocyanide ester polyaddition reaction, during or preferably after change into ionic species because these ionic comonomers are difficult to be dissolved in the reaction mixture usually.Especially preferably, carboxylate group exists with the form of their salt, and with alkalimetal ion or ammonium ion as its counter ion.

In the polyurethane chemistry field, it is normally known how to regulate the molecular weight of urethane by the arithmetical av of reactive functionality in the monomeric ratio selecting to react to each other and the per molecule.

Usually, selection component (a) and (b), (c), (d) and (e) and their mole numbers separately, i.e. ratio A between A, the B: B like this

A) mole number of isonitrile acid group group and

B) can be from 0.5: 1 to 2: 1 with the hydroxyl of isocyanide ester reaction and the mole number sum of functional group in the addition reaction, preferably from 0.8: 1 to 1.5: 1, especially preferably 0.9: 1 to 1.2: 1, and more especially preferably as far as possible near 1: 1.

Except that composition (a) and (b), (c), (d) with (e), only can use with the monomer of a reactive group, in the total amount of composition (a)-(e), its consumption reaches 15% (mol) usually, preferably reaches 8% (mol).

The polyaddition reaction of composition (a)-(e) usually under normal atmosphere or autogenous pressure, at from 20 to 180 ℃, preferably carry out under from 50 to 150 ℃ the temperature.

The reaction times that needs can be from several minutes to several hours.In the polyurethane chemistry field, how various parameters such as temperature, monomer concentration and monomer reaction performance influence the reaction times is known.

By using general catalyzer such as dibutyltin dilaurate, stannous octoate (II) and diazabicylo [2.2.2] octane, can quicken the reaction of diisocyanate.

Suitable polymerizing reactor comprises stirred vessel, if when especially using solvent for the heat radiation that provides low viscosity to become reconciled.

Reaction during for solvent-free the existence, under the situation in normally high viscosity and normally short reaction times, it is especially suitable using extrusion machine, especially self-cleaning type multiscrew extrusion machine.

Usually with a kind of preparation dispersion in the following technology:

According to acetone process, under atmospheric pressure boiling point is lower than in 100 ℃ the mixable solvent of water, preparation anionic polyurethane from composition (a)-(e).Adding the water of q.s, is the dispersion of its external phase to form water.

The hybrid technique of prepolymer is different from the acetone process part and is, the initial product that makes is not (potential) anionic polyurethane of complete reaction, but the prepolymer of band isonitrile acid group group.In this case, selection component (a)-(d), so that the ratio that makes A defined above: B is greater than from 1.0 to 3, preferably from 1.05 to 1.5.At first, prepolymer is dispersed in the water, then, perhaps by with isonitrile acid group group with have more than 2 can with the amine reaction of the amino of isocyanide ester reaction, carry out crosslinkedly, perhaps can carry out chainpropagation with the amine of the amino of isocyanide ester reaction with having 2.If do not add amine, also chainpropagation can take place.In this case, isonitrile acid group group is hydrolyzed into amino, and the isonitrile acid group radical reaction that keeps in amino and the prepolymer makes chainpropagation.

In a kind of especially preferred work-around solution of acetone process and prepolymer hybrid technique, prepolymer prepares with 2 steps, the 1st step, part in composition (c) and in case of necessity (b2) and the composition (a) is reacted at first mutually, goes up all isocyanide ester groups up to composition (a) and in fact all reacts.By measuring N CO value, promptly measure the quantity of remaining NCO group, know the progress of this reaction.In next step, but the residual component interreaction forming prepolymer, and this step can do and can not do, add to by (a), (c) and, if use, (b2) in the reaction mixture of Xing Chenging, make to react and proceed.

Having used solvent to prepare the occasion of urethane, by for example underpressure distillation most solvent is removed from dispersion usually.Solvent in the dispersion does not especially preferably have solvent preferably less than 10% (weight) in dispersion.

The solids content of dispersion is generally 10-75% (weight), is preferably 20-65% (weight), viscosity be 10-500mPas (at 20 ℃, 250s ^-1Velocity of shear the time measure).

Usually, in fact novel water dispersion does not contain polyvalent metal ion.

According to the method for describing in two pieces of documents above-mentioned, for example can add the hydrophobicity auxiliary agent that is difficult to be dispersed in the finished product dispersion in urethane or in the prepolymer, even can before dispersion, add, described hydrophobicity auxiliary agent for example is phenol condensation resins or Resins, epoxy and other polymkeric substance as mentioning in DE-A-39 03 538,43 09 079 and 40 24 567 of the derivative of aldehyde and phenol and/or phenol, and they are used for polyurethane dispersions as adhesive accelerant.The example of suitable hydrophobicity auxiliary agent has detailed description in DE-A-39 03 538,40 24 567 and 43 09 079.

In a work-around solution of the present invention, with having the two keys of C=C but do not have isonitrile acid group group or monomer group, free redical polymerization (monomer f) of responding property of isonitrile acid group group is carried out modification to novel polyurethane dispersions.These monomers comprise the monomer of especially using usually in emulsion polymerization.

The example of suitable monomers (f) is (methyl) vinylformic acid C ₁-C ₆Alkyl ester and dodecylacrylate and butyleneglycol dicarboxylic ester; Or contain compound such as methyl vinyl ketone, (methyl) propenal, crotonic aldehyde, diacetone-acryloamide(DAA) or diacetone (methyl) acrylate of carbonyl.

Other monomeric example is the vinyl ester that contains the carboxylic acid of 20 carbon atoms at the most, for example vinyl laurate, stearic acid vinyl ester, vinyl-acetic ester and propionate; Reach the vinyl aromatic compounds of 20 carbon atoms, as vinylbenzene and Vinyl toluene; Vinyl unsaturated nitrile such as vinyl cyanide and methacrylonitrile; Vinyl unsaturated amides such as acrylamide and Methacrylamide; Vinyl halide such as vinylchlorid and vinylidene chloride; And with the C of 1 or the two keys of 2 C=C ₂-C ₈Aliphatic hydrocrbon such as divinyl and ethene.

Monomer (f) can disperse before or comprise the water dispersion dispersion interpolation before of urethane (A) in the building-up process of urethane (A), at urethane (A), and can use ordinary method, by in the mixture of polyurethane dispersions and monomer (f), adding radical initiator to carry out radical polymerization.Also can be used as charging is metered in the polyurethane dispersions that comprises initiator.

If the polymer graft that requirement will form from monomer (f) is to urethane, when synthesis of polyurethane, the monomer of the two keys of C=C that contain free redical polymerization is used in suggestion.

For cross-linked polyurethane (A), in water dispersion, usually add the linking agent (B) that contains sense substituent, these sense substituents carry out addition or condensation reaction with structural unit from the compound deriving of general formula (I).The example of this linking agent (B) is the compound with at least one aldehyde radical or at least two sense substituents, the isocyanide ester base that described sense substituent is selected from primary amino, secondary amino group, diazanyl, hydrazide group, amino oxygen base, isocyanide ester base, N-methylol and shelters.

The example of suitable polyamine is non-polymeric amine, as 1,2-quadrol, diethylenetriamine, Triethylenetetramine (TETA), 1,2-diaminopropanes, 1,2-diaminobutane, 1,6-hexanediamine, 1,12-dodecyl diamines, cyclohexanediamine, piperazine, 2-lupetazin, isophorone diamine, phenylenediamine, tolylene diamine, dimethylphenylene diamine, 4,4 '-diaminodiphenyl-methane, the Meng alkane diamines and m-xylene diamine.Active aminocompound also can be a polymkeric substance, for example contains amino acrylic resin, vibrin or urethane resin, contains amino polyoxytrimethylene (Jeffamines) or polymine.

These amine also can use with the form of sheltering, and promptly use with their aldimine or the form of ketoimine.These amine of sheltering are known, and for example be described in K.J.Kim and R.C.William in " water base high body solids content system processing nd Annual Meeting collection; New Orleans; 57; (1995) " and B.Vogt-Birnbrich in " the 21st organic coating international conference collection of thesis; Athens, 55, (1995) " and among EP-A-552 469 and the EP-A-584 818.Preferably use the amine of sheltering by such as the aromatic aldehyde of phenyl aldehyde.

The example of suitable polyhydrazide is the dicarboxyl acid dihydrazide, as what describe in the 12nd page of the 1st row at the 11st page of the 52nd row of for example EP-A-442 652.These polyhydrazides preferably make from dicarboxylic acid, and these dicarboxylic acid also form the basis of the polyester glycol that can be used as composition (b1).And, also can use corresponding polyhydrazone derivative, these as obtaining from acetone or butanone.

More suitable polyhydrazide with the water dissolvable that has improved for example is described among the EP-A-629657.

Suitable crosslinking agent (B) is by changing the poly-isocyanide ester that amination has crosslinked action more.These compounds for example are described among the DE-A-41 21 946.

The linking agent (also can use with their form of salt) that contains the amino oxygen base is learnt from for example EP-A-516 074 and EP-A-42 19 384.

Another kind of selectable crosslinking method is to add single-or polyfunctional aldehyde in novel dispersion, if desired, also can protect aldehyde.

The example of suitable single aldehyde is that general formula is X-R ⁹The compound of-CHO, wherein R ⁹Be C ₁-C ₆Alkane 2 basis, X is hydrogen or alkyl.Preferred aldehyde is formaldehyde, acetaldehyde and phenyl aldehyde.

Suitable multifunctional aldehyde is that low-molecular-weight compound, especially general formula are OCH-(CH ₂) _nThe aliphatic aldehyde of-CHO, wherein n is from 0 to 8, from 0 to 4 integer preferably is as oxalic dialdehyde or glutaraldehyde.

The oligopolymer of the aldehyde of the undersaturated free redical polymerization of vinyl, polymkeric substance and multipolymer also can be used as crosslinked composition.Suitable examples is propenal, Methylacrylaldehyde, formyl radical vinylbenzene and (methyl) vinylformic acid methylol furfuryl group ester.If can not fully dissolve, when dispersion was used as binding agent, so crosslinked composition can be dispersed in the aqueous phase of dispersion and participate in film forming.Preferably this weight-average molecular weight is 1000-500,000 the crosslinked composition of oligomeric or polymeric.

The derivative that has the aldehyde radical of protection is considered to the quite reactive of its reactivity and free aldehyde radical itself.Suitable example is acetal, mercaptal and mereaptol, dioxolane and dithiolane.Preferably aldehyde radical and C ₁-C ₄Alkanol or and C ₂-C ₃Alkanediol the reaction acetal and the dioxolane group that form.

The example of unsaturated monomer that has the aldehyde functional group of protection is diethoxy propyl diester, acryl or the methacryloyl propoxy--1 of vinylformic acid and methacrylic acid, the 3-dioxolane.

Other suitable aldehyde derivatives is from aromatics that replace or non-replacement or heteroaromatic aldehyde and single-or aldimine compound of obtaining of multifunctional primary amine reaction.These compounds are the parts in the general knowledge, and are described in EP552 469 A3 and US-A-5, in 451,653.

Process Michael receptor also can take place crosslinked, and such suitable combination thing is generally known, and is described among the DE-A-42 37 492.

Finish in the presence of the crosslinked suitable Lewis base of in as DE-A-42 37 492, describing usually that the process Michael reaction is carried out or the catalyzer of brnsted base.

Composition (A) and consumption (B) are preferably selected like this, and promptly the mol ratio of the sense substituent of carboxyl from the structural unit of the compound deriving of general formula I and compound (B) is from 0.1: 1 to 10: 1, preferably from 1.5: 1 to 0.5: 1.

Other suitable crosslinking agent (B) is an aminoresin, carbamide condensation product for example, and as at D.H.Solomon, organic membrane polymer chemistry, 235 pages, John Wiley﹠amp; Sons, NewYork describes in 1967.They preferably molecular weight be preferably the carbamide condensation resins of 250-1000, especially preferred is their part or all of etherfied derivative.The etherificate degree based on maximum possible, preferably is at least 45%.Carbamide condensation product C ₁-C ₄The monohydroxy-alcohol etherificate, as with methyl alcohol, ethanol, propyl alcohol or preferably use butanols, and/or the monoether etherificate of the dibasic alcohol of 2 to 7 carbon atoms is arranged with synteny.

Yet the carbamide condensation product also can part be replaced by other crosslinked aminoresin, as (Houben-Weyl) in for example " organic chemistry method ", and the 14/2nd volume, second section, the 4th edition, Georg Thieme press, the Stuttgart is described in 1963,319 pages.

Another kind of selectable crosslinking method is to use many isocyanide esters.Especially suitable isocyanide ester compound is an isocyanide ester (referring to DE-A-42 16 536) conventional, well-known and the commercially available highly filled isocyanide ester that gets, hydrophilization and/or protection.

Suitable isocyanide ester is that those are listed in the monomer (a) that is used for synthesis of polyurethane.In these monomers (a), especially preferred is the multifunctional isocyanide ester that has more than 2 isonitrile acid group groups.

The suitable protectant example that is used for isocyanide ester is pure and mild oxime, as acetoxime or methyl ethyl ketoxime.

Other possible linking agent (B) is the polymer resin that has the isonitrile acid group group of oxime protection, as DE-A-42 37 030, DE-A-33 45 448, WO93/01245 and US-A-5, describes in 358,997.

What be present in urethane (A) and many isocyanide esters in the novel water dispersion crosslinkedly takes place in the presence of such as the basic catalyst of alkyl amine usually.

Except that unprotected isocyanide ester and aldimine, novel dispersion is mixed with linking agent in any needs before processing usually.Equally also may even before urethane (A) is distributed in the water, linking agent be joined in the urethane (A).

But novel dispersion can comprise other water emulsification or the dispersible resin of water in addition, as polymkeric substance, urethane, polyester, epoxy-or Synolac; And commercially available accessory ingredient of in common use and additive, as whipping agent, defoamer, emulsifying agent, thickening material, flow agent and thixotropic agent with such as the tinting material of dyestuff and pigment.

If the linking agent in the novel dispersion (B) is the compound that contains following groups; said group is aldehyde radical, primary-or the isonitrile acid group group of secondary amino group, hydrazine, amino oxygen base, hydrazides or ketoxime protection; or aminoresin; then dispersion constitutes the system be called the single-component system, because process in the time of any needs that they can be after preparation.

Add the compound have unprotected isonitrile acid group group and be called as two component systems as the novel dispersion of linking agent (B); because corresponding mixture must be processed (about 8 hours) in limited time durations, make mixing process finish by the user of dispersion usually.

Zhi Bei coating composition adopts the general technology of coatings industry to be coated on the base article usually in this way, promptly for example by roller coat, spraying, extension be coated with, inclining is coated with and technologies such as dip-coating.

Coating material drying subsequently and curing can be passed through cold-curing (promptly under 0-80 ℃, being preferably room temperature), perhaps finish by baking (promptly usually at 80-280 ℃).

The linking agent that is particularly suitable for cold-curing is to contain aldehyde radical, aldimine, primary-or the linking agent of secondary amino group, hydrazine, aminooxy or hydrazide group.

By inference, cause that in these systems crosslinked addition polymerization or polycondensation only just take place after most of water has evaporated.Therefore coating composition constitutes a kind of single-component system that comprises binding agent and linking agent.

Cold-curing also can contain the linking agent of isonitrile acid group group (B) freely in the presence of finish.Under this processing situation, novel dispersion should be carried out mix afterwards less than 8 hours time with linking agent in the coating of goods.

When containing (mixing) aromatic aldimines group, used linking agent (B) also can carry out cold-curing.In this case, in several weeks, do not wait in one hour according to not coexisting of composition the storage time of novel dispersion.

Must toast the situation of processing for coating, particularly suitable linking agent is above-mentioned aminoresin, through protection or unprotected many isocyanide esters and michael acceptor.

Even when not having linking agent to exist, urethane crosslinks to a certain degree takes place also really under baking condition.Especially true when crosslinking reaction takes place in the presence of Lewis base or brnsted base, described Lewis base or brnsted base are described among the DE-A-4237492, for example are tertiary amine, and example is 1,8-phenodiazine two heterocycles [5.4.0] 11 carbon-7-alkene (DBU).

Novel coating composition is particularly suitable for applying timber, metal, plastics, paper, leather and textiles; Be used to prepare molding and printing-ink; And as tackiness agent.

The feature of novel dispersion is, can with in addition the dispersion that contains relatively small amount or do not contain flow agent be processed into high-quality coatingsurface.

In addition, novel dispersion both can be used as the single-component system and also can be used as two component systems, and the also available baking technology of both available cold-curing technology is processed.For the operator who adopts two or more methods in above-mentioned four kinds of different processing methods altogether is useful, because for different complete processings, only needs to store a spot of polyurethane dispersions.

And the water dispersion that contains urethane (A) is applicable to the making printing-ink highlightedly.

These printing-inks preferably contain following ingredients:

(I) binding agent that mainly constitutes of 15-30% (weight) by urethane (A) and linking agent (B)

(II) pigment of 7-15% (weight)

(III) alcohol that is suitable as solvent of 2-5% (weight)

(IV) universal additive of 4.5-10% (weight)

(V) water of 45-70% (weight).

Preferred what use is according to the above ratio polyhydrazide as linking agent (B), has made more detailed description above.

Universal additive is usually a used auxiliary agent in printing-ink, i.e. for example wax, defoamer, dispersion agent, wetting agent and microorganism killing agent.

In addition, in the printing-ink used composition (ii) to (v) be those compositions that use in these printing ink usually, these printing ink are for example from Ullmann " industrial chemistry encyclopaedia ", the 5th edition, the A22 volume; 1993VCH publishing company; Known in the 143-155 page or leaf.

These printing-inks especially are suitable for the printed polymeric film, and as polyethylene or polypropylene screen, the surface tension of polymeric film is from 30 to 50, is preferably from 35 to 40, especially is preferably from 37 to 39mN/m (using water gaging down at 23 ℃).Print (referring to loc.cit.145 and 146 pages) with general technology.

Having above-mentioned capillary polymeric film is by the commercially available film that gets of corona treatment.

When combining with the substrate of being introduced, these printing-inks have showed good profit warm nature.Mechanical stress and solvent that film ability after the printing is common.

Abbreviation and trade(brand)name:

ADDH: adipic dihydrazide

Basonat ^PLR8878: hand over by the emulsible isocyanide ester of water that BASF AG provides

The connection agent

Basophob ^WE: the polyethylene wax dispersion that provides by BASF AG

Basoplast ^20 enriched materials: the stearic acid diketene that provides by BASF AG

BD-1,4: by BASF AG provide 1, the 4-butyleneglycol

The adduct of BHAA:1 mole diethanolamine and 1 mole of diketene

DAAM: diacetone-acryloamide(DAA)

DBU:1,8-phenodiazine two heterocycles [5.4.0] 11 carbon-7-alkene

DETA: by the N-(2-aminoethyl)-1 that BASF AG provides, 2-ethane diamine

DMEA: the 2-dimethylaminoethanol that provides by BASF AG

DMPA: the dimethylol propionic acid that provides by Angus Chemie

SC: the solids content % (weight) that the distillation back is measured

IPDI: the Vestanat IPDI/ isophorone diisocyanate that provides by Huls

Luhydran ^A848S: the automatically cross-linked polymerization of water-based that provides by BASF AG

The thing dispersion

MEK: methylethylketone

MW: molecular weight

Neutral.1: be used for urethane ionic group neutral neutralizing agent

Neutral.2: as Neutral.1

The NMP:N-methyl-2-pyrrolidone

Theoretical cross-linking density (the unit: mmol/kg of the BHAA reaction of NCD:ADDH and fusion

Solid)

PD-1,3:1, ammediol

Pluriol ^P600: the polypropylene glycol that provides by BASF AG

P-THF2000: the polytetrahydrofuran 2000 that provides by BASF AG

PUD: polyurethane dispersions

TEA: triethylamine

TMP: TriMethylolPropane(TMP)

Th.: theoretic

Theoretical cross-linking density (the unit: mmol/kg of VCD:DETA and isonitrile acid group radical reaction

Solid)

Wacoblau ^9A918018: starch by the blue pigments that BASF K+E company provides.

Embodiment

The synthetic embodiment of the compound of general formula I

Compound I a

At 25 ℃, in 1 hour, 168.14g diketene (2mol) is added in the initial feed of 231.3g (2.22mol) diethanolamine, 1000ml tetrahydrofuran (THF) and 25g pyridine.Add ion-exchanger (Lewatit 100G1, strong acid type) and filtration, excessive diethanolamine is separated with pyridine.In the clear solution of the degassing, add the 2.7g triphenylphosphine, subsequently solvent is removed in rotatory evaporator.Isolate 341.09g light yellow liquid (theoretical value 90.14%).Analytical data ( ¹³C-and ¹H-NMR) show that purity is greater than 95%.Do not find any starting compound in the product, but have triphenylphosphine oxidation thing.

Compounds ib

At 25 ℃, in 90 minutes, 599.4g diketene (7.129mol) is added in the initial feed of 749.5g (7.129mol) diethanolamine and 1250ml tetrahydrofuran (THF).By distillation tetrahydrofuran (THF) is removed subsequently.Isolating weight is the heavy-gravity light yellow oil of 1354.4g (theoretical value is 1348.9g). ¹³C-and ¹The H-NMR spectrum has been determined the structure of product, and shows that purity is at least 95%.Do not find any raw material.

Compound I c

With the process that compounds ib is described, 261g (3.105mol) dienone and 326.4g (3.104mol) diethanolamine are reacted in 1000ml acetone, different is, is reflected under 15 ℃ and finishes, dienone added in 15 minutes.After removing acetone, separate obtaining 596.9g (theoretical value 587.4g) low viscosity light orange look oil.The NMR spectrum has been determined the structure of product.Do not find any raw material.

Compound I d

At 15 ℃, in 2 hours, 565.4g diketene (6.726mol) is added in the initial feed of 707.2g (6.726mol) diethanolamine and 848.4g methylethylketone.Subsequently, this solution is warmed up to 40 ℃, add solution and the 0.5ml dibutyltin dilaurate of the isophorone diisocyanate of 996.79g (4.484mol) as 50% concentration in dimethylbenzene, this mixture is 85 ℃ of down reactions 4 hours, and (signal of isocyanide ester is at about 2270cm for the density loss by the infrared spectroscopy monitor isocyanide ester ^-1).

Compound I e

With the process that compounds ib is described, 1614g (19.2mol) dienone and 2018.6g (19.2mol) diethanolamine are reacted in the THF of 2422ml.In this example, the initial feed of THF and diethanolamine is cooled to 0 ℃, and the interpolation of dienone is finished in 2 hours 30 minutes.Subsequently, most of solvent is removed by underpressure distillation.Separating the product that is still contained residual solvent is that viscosity is the light yellow oil of 2400mPa.s.

The synthetic embodiment that has the polyurethane dispersions of carbonyl

Compound I I

The first step, amination Pluriol P600: 150ml/ hour Pluriol P600 is reacted in 1.2 liters tubular reactor with 450ml/ hour ammonia continuously, contain in the reactor by 50%NiO, 20%CuO and 30%ZrO ₂The 500ml catalyzer of forming.Temperature of reaction in the reactor is 20-215 ℃, and pressure is 200 crust, and the consumption of hydrogen is 50 l/ hours.Under at the pressure of 1-3 millibar, up to 100 ℃ liquidus temperature high volatile volatile composition (water, ammonia) distillation is removed.Product characterizes with following parameters: total amine value: 174.1mgKOH/G; Tertiary amine value: 1.3mgKOH/G; Secondary amine value: 6.3mgKOH/g; Hydroxyl value: 30.2mgKOH/g; Water-content: 0.06% (weight).

In second step, the above-mentioned polyetheramine of 2840g is added in one 10 liters the stirred vessel.By repeatedly finding time and use nitrogen wash, make in the content of reactor and introduce rare gas element.The propylene oxide of weighing 500g and adding under 105 ℃ then.After the state of reacting completely (to constant pressure),, reaction vessel was found time about 20 minutes for removing any easy volatile composition.Do not need to do further aftertreatment.The polyethers amino polyol that obtains has following index: hydroxyl value: 291mgKOH/g; Amine value: 147mgKOH/g; Tertiary amine value: 36.3mgKOH/g; Secondary amine value: 102.9mgKOH/g; Water-content: 0.12% (weight); Density: 1000g/cm ³PH11.4, and viscosity 326mPa.s.

Final step with the propenoxylated polyetheramine of 2640g and mixing of 300g tetrahydrofuran (THF) and cooling, then at 0-15 ℃, was added dienone and the vigorous stirring of 523.7g (6.23mol) in 4 hours.Add finish after, product at room temperature stirred one hour, removal of solvent under reduced pressure is then still contained the light orange oil of residual solvent.Compound III

Under 40 ℃, with just expecting that the diethanolamine of 105.14g (1mol) adds the Basoplast20 enriched material of 512g (1mol) and 500g toluene to.Interpolation is removed toluene 90-95 ℃ of distillation after finishing, and obtains the light brown solid.Infrared analysis has confirmed the disappearance of dienone structure.

Dispersion 1

Add 110.4g (0.497mol) isophorone diisocyanate and 0.07g dibutyltin dilaurate to 133.3g polytetrahydrofuran (Mw2000 as the solution of 50% concentration in dimethylbenzene; 0.067mol), 13.9g (0.073mol) Compound I a, 10.7g (0.08mol) dimethylol propionic acid, 21g (0.23mol) 1, in the initial feed of 4-butyleneglycol and 43.3g methylethylketone, mixture was 90 ℃ of reactions 2.5 hours.The prepolymer that obtains is used the 200g acetone diluted then, uses the neutralization of 6.5g (0.063mol) triethylamine again.The content of isocyanide ester is 0.92g/100g (theoretical value is 0.68%) before the neutralization.By adding the water and the solution of 3g (0.029mol) diethylenetriamine in 16.7g water of the complete deionization of 500g, then remove acetone, obtain the oyster white dispersion, solids content is 37.5%, pH is 7.8.Theoretical ketone group content is 245, and theoretical salts contg is the 214mmol/kg solid.

Dispersion 1a: have carbonyl and as the polyurethane dispersions of the adipic dihydrazide of linking agent

Add the 0.82g adipic dihydrazide in the 100g dispersion 1 (mol ratio of hydrazides and carbonyl is 1: 1).

Dispersion 1b: have carbonyl and as the polyurethane dispersions of the polymine of linking agent

With 0.44g polymine Poymin ^G10 adds (amino mol ratio with ketone group is about 1: 1) in the 100g dispersion 1 to as the aqueous solution of 20% concentration.

Dispersion 2:, directly add the hexanodioic acid hydrazides as dispersion 1

Preparation process according to dispersion 1, this dispersion makes in 4-butyleneglycol, 331.23g isophorone diisocyanate, 19.43g triethylamine and the 8.94g diethylenetriamine from 400g polytetrahydrofuran 2000,41.8g Compound I a, 32.19g dimethylol propionic acid, 63.08g1.Before removing acetone, distillation adds the adipic dihydrazide (purity 78.5%) of 24.38g.Obtain the oyster white dispersion, solids content is 36.6%, and pH is 7.8.

Dispersion 3: as dispersion 2, adipic dihydrazide is added in the distillation back

The preparation of dispersion 3 is similar to dispersion 2, and different is to use compounds ib rather than Compound I a, and adds adipic dihydrazide before acetone is removed in distillation.

Make the oyster white dispersion, solids content is 36.4%, and pH is 7.8.

Dispersion 4: the polyurethane dispersions that has carbonyl

With 317.89g (1.43mol) isophorone diisocyanate and 0.2g dibutyltin dilaurate solution as 50% concentration in dimethylbenzene, under 59 ℃ temperature, add 400g polytetrahydrofuran (0.2mol), 81.7g (0.43mol) Compound I a, 32.19g (0.24mol) dimethylol propionic acid, 38.75g (0.43mol) 1 to, in the initial feed of 4-butyleneglycol and 130g methylethylketone.Mixture was 92 ℃ of reactions 5 hours.Use the 600g acetone diluted then, use the neutralization of 19.43g (0.19mol) Trimethylamine again.The content of isocyanide ester is 0.87g/100g (theoretical value 0.68%) before the neutralization.By adding the water and the solution of 8.94g (0.086mol) diethylenetriamine in 50g water of the complete deionization of 1350g, then remove acetone, distillation finishes the back and adds 44.16g adipic dihydrazide (purity 84.7%, 0.215mol), obtain the oyster white dispersion, solids content is 40%, and pH is 8.1.Theoretical ketone group content is 478, and theoretical salts contg is the 214mmol/kg solid.The mol ratio of hydrazide group and ketone group is 1: 1.

Dispersion 4a

The preparation of dispersion 4a is similar to dispersion 4, and different is not add any ADDH.In addition, in amount of solid, the DBU of dispersion 4a and 0.5% (weight) mixes.

Dispersion 5: the polyurethane dispersions of band carbonyl

With 517.96g (2.33mol) isophorone diisocyanate and 0.2g dibutyltin dilaurate solution as 50% concentration in dimethylbenzene, under 65 ℃ temperature, add 400g polytetrahydrofuran (0.2mol), 10.2g (0.58mol) compounds ib, 46.95g (0.35mol) dimethylol propionic acid, 90.12g (1mol) 1 to, in the initial feed of 4-butyleneglycol and 250g methylethylketone.Mixture was 91 ℃ of reactions 6 hours.Use the 700g acetone diluted then, use the neutralization of 28.33g (0.28mol) Trimethylamine again.The content of isocyanide ester is 0.90g/100g (theoretical value 0.79%) before the neutralization.By adding the water and the solution of 13.76g (0.13mol) diethylenetriamine in 50g water of the complete deionization of 1800g, then remove acetone, distillation finishes the back and adds 59.57g adipic dihydrazide (purity 84.7%, 0.29mol), obtain the oyster white dispersion, solids content is 41%, and pH is 7.8.Theoretical ketone group content is 480, and theoretical salts contg is the 232mmol/kg solid.

Comparing embodiment 1 (V): not with the polyurethane dispersions of carbonyl

Step according to preparation dispersion 1, with 400g (0.2mol) polytetrahydrofuran, 32.1g (0.24mol) dimethylol propionic acid, 90.1g (1mol) butyleneglycol and 348.2g (1.565mol) isophorone diisocyanate, with 0.2g dibutyl alkene dilaurate, in 160 methylethylketone, react.Use the 600g acetone diluted then, the content of isocyanide ester is 0.8g/100g (theoretical value 0.64%).Product neutralizes with 19.4g (0.192mol) triethylamine, with the water-dispersion of the complete deionization of 1500g, 8.6g (0.083mol) triethylenediamine (0.083g) that is used further in the 50g water is crosslinked, obtains the polyurethane dispersions of oyster white outward appearance, solids content is 37.5%, and pH is 7.9.Theoretical salts contg is the 214mmol/kg solid.

Comparing embodiment 2 (V): repeat the embodiment 8 of EP-A-332 326, do not add adipic dihydrazide

With methylethylketone and acetone rather than NMP as solvent, because with regard to purpose relatively, dispersion must be solvent-free.

Active keto compounds at first is to make from (0.207mol) diethanolamine of the 21.75g the 35.05g methylethylketone and 35.05g (0.207mol) diacetone-acryloamide(DAA).

In prepolymer subsequently synthetic, product C apa210 is used to replace Oxyflex S1063-120, because do not provide the characteristic of this more approaching polymer blend.Capa210 is to be the polycaprolactone of 1000g/mol (example is 910g/mol) by the molecular weight that Interox provides.Prepolymer is to make from 400g (0.4mol) Capa210, addition solution (0.207mol), 51.18gDMPA (0.389MOL) and the 437.93g the 201g methylethylketone (1.97mol) isophorone diisocyanate under the condition of catalyst-free, at 45 minutes postcooling to 35 of 90 ℃ of reactions ℃, isocyanide ester content is 6.88g/100g (theoretical value 6.83%).Neutralize with 40g (0.395mol) triethylamine, with the water-dispersion of the complete deionization of 1480g, prepolymer is carried out chainpropagation again with 45.3g (0.906mol) hydrazine hydrate that is dissolved in the 92g water.Obtain oyster white behind the solvent distillation, slightly with the dispersion of lacteous, solids content is 38.3%, pH is 8.1, theoretical base content is 377, and theoretical ketone group content is the 201mmol/kg solid.

Dispersion itself has violent stink, in distillation and treating processes subsequently, shows enhanced foaming trend.

Comparing embodiment 2a (V): handle the dispersion that obtains from comparing embodiment 2 (V) with adipic dihydrazide

From the dispersion that comparing embodiment 2 (V) obtains, add 0.67g adipic dihydrazide (mol ratio of hydrazide group and ketone group is 1: 1) at 100g.

Comparing embodiment 3 (V): from the affixture of diethanolamine/diacetone-acryloamide(DAA), prepare PUD

Under nitrogen atmosphere, 23.13g (0.22mol) diethanolamine and 37.23g (0.22mol) diacetone-acryloamide(DAA) were reacted 7 hours in the 40g methylethylketone in 85 ℃.Do not carry out other processing and use this solution.

Affixture, 32.19g (0.24mol) dimethylol propionic acid, 57.68g (0.64mol) butyleneglycol and the 317.89g the 130g methylethylketone (1.43mol) isophorone diisocyanate from 400g (0.2mol) polytetrahydrofuran, 60.36g (0.22mol) diethanolamine and diacetone-acryloamide(DAA), with the solution of 0.2g dibutyl alkene dilaurate, the preparation prepolymer.Use the 600g acetone diluted then, the content of isocyanide ester is 0.88g/100g (theoretical value 0.68%).Product is used the neutralization of 19.43g (0.192mol) triethylamine subsequently, and the water that adds the complete deionization of 150g disperses.The same 8.94g diethylenetriamine of adding is carried out crosslinked.Be with many raggle-taggle white dispersion except that staying after desolvating.Some urethane of back overnight settles down.Theoretical ketone group content is 245, and theoretical salts contg is the 214mmol/kg solid.Comparing embodiment 4 (V): from otan, prepare PUD

Step according to preparation dispersion 1, from 400g (0.2mol) polytetrahydrofuran, 19.82g (0.22mol) otan, 32.19g (0.24mol) dimethylol propionic acid, 69.39g (0.77mol) butyleneglycol and the 346.79g the methylethylketone of 130g (1.56mol) isophorone diisocyanate, with 0.2g dibutyl alkene dilaurate solution, preparation prepolymer (reaction times: 4 hours).Pre-polymer solution is brown.Use the 600g acetone diluted then, the content of isocyanide ester is 0.79g/100g (theoretical value 0.68%).Product disperses with 19.43g (0.19mol) triethylamine neutralization, the water of the complete deionization of interpolation 1500g.Add the 8.94g diethylenetriamine solution that is dissolved in the 50g water subsequently.Obtain the yellow-white dispersion except that after desolvating.Solids content is 37.1%, and pH is 8.1.Theoretical ketone group content is 245, and theoretical salts contg is the 214mmol/kg solid.By blade coating, said composition is coated on the sheet glass, obtain the yellow film that dried film thickness is about 50 μ m band tangerine peel structure.

Comparing embodiment 5 (V):

Attempt to prepare a kind of dispersion with the addition polymer of diethanolamine and diacetone-acryloamide(DAA), the ketone group content of Theoretical Calculation is that 335mmol/kg solid dispersion makes by being used for prepolymer synthetic following ingredients: the pre-adduct of 34.7g diethanolamine and 55.85g diacetone-acryloamide(DAA) reacted 7 hours in 85 ℃ at the 60g N-Methyl pyrrolidone.Add 400g by hexanodioic acid, m-phthalic acid and 1, the molecular weight that the 6-hexylene glycol makes is 2000 the polyester glycol (Lupraphen that is provided by BASF AG ^VP9206), 40.24g dimethylol propionic acid, 57.68g 1,4-butyleneglycol, 90g methylethylketone, 362.35g isophorone diisocyanate and 0.2g dibutyl alkene dilaurate solution.90 ℃ the reaction 2 hours after, the prepolymer gelling.For this reason, all the other compositions (water of 600g acetone, 24.3g triethylamine, the complete deionization of 1550g and 8.8g diethylenetriamine) are not added.

Comparing embodiment 6 (V): prepare PUD from diacetone alcohol

At first boost in the force container 4, under 86 ℃ of autogenous pressures, 400g (0.2mol) polytetrahydrofuran, 32.19g (0.24mol) dimethylol propionic acid, 81.11g (0.9mol) butyleneglycol, 13.42gTMP and the 393.47g in 160g acetone (1.77mol) isophorone diisocyanate and 0.2g dibutyl alkene dilaurate solution are reacted.Add 34.85 parts of (0.3mol) diacetone alcohols then, be reflected at 118 ℃ and continued 3 hours.After the 600g acetone diluted, the isocyanide ester value is 0.81g/100g (theoretical value 0.64%).Add 19.43g (0.192mol) triethylamine and be used for neutralization.Form dispersion by the water that adds 1650 parts of complete deionizations, use 8.94g (0.09mol) diethylenetriamine of solvent in 50g water to carry out crosslinked after this.Remove behind the acetone slightly with the oyster white dispersion of lacteous, the solids content of dispersion is 37.4%, and pH is 7.9.Theoretical ketone group content is 308, and theoretical salts contg is the 197mmol/kg solid.Said composition is coated on the sheet glass by blade coating, and the dried film thickness during no film coalescence aid is about 50 μ m, and film has many stress cracks that point to the center from the edge.Drip the butyl glycol of pH neutral lentamente, just form coagulum after only dripping initial several.

The method preparation that embodiment 6 to 10 and comparative example 7 (V) are described with embodiment 3 with the listed monomer of table 1 to the dispersion of 10 (V).

The preparation (weight part of raw material) of table 1:PUD

Dispersion	????6 ¹⁾	????7	????8	????9	????10	????7(V)	????8(V)	????9(V)	????10(V)
Dispersion	????6 ¹⁾	????7	????8	????9	????10	????7(V)	????8(V)	????9(V)	????10(V)	????P-THF ????2000	????400	????400	????400	????400	????400	????403	????403	????400	????400
????DMPA	????54	????32	????32	????32	????32	????31	????31	????31	????31	????P-THF ????2000	????400	????400	????400	????400	????400	????403	????403	????400	????400
????DMPA	????54	????32	????32	????32	????32	????31	????31	????31	????31	??BD-1，4	????87	????77	????63	????63	????39	????-	????-	????108	????108
??PD-1，3	????-	????-	????-	????-	????-	????152	????152	????-	????-	??BD-1，4	????87	????77	????63	????63	????39	????-	????-	????108	????108
??PD-1，3	????-	????-	????-	????-	????-	????152	????152	????-	????-	????BHAA	????190	????21	????42	????42	????82	????-	????-	????-	????-
????IPDI	????627	????340	????331	????331	????318	????568	????568	????568	????568	????BHAA	????190	????21	????42	????42	????82	????-	????-	????-	????-
????IPDI	????627	????340	????331	????331	????318	????568	????568	????568	????568	????TEA	????-	????20	????20	????20	????20	????-	????-	????-	????-
????DMEA	????29	????-	????-	????-	????-	????21	????21	????21	????21	????TEA	????-	????20	????20	????20	????20	????-	????-	????-	????-
????DMEA	????29	????-	????-	????-	????-	????21	????21	????21	????21	????DETA	????17	????9	????9	????9	????9	????9	????-	????9	????-
????ADDH	????-	????10	????19	????19	????37	????-	????-	????-	????-	????DETA	????17	????9	????9	????9	????9	????9	????-	????9	????-
????ADDH	????-	????10	????19	????19	????37	????-	????-	????-	????-	????SC	????38.9	????38.3	????38.6	????37.4	????38.6	????43.3	????46.0	????42.2	????39.1
Outward appearance	Muddy	Opaque	Opaque	Opaque	Opaque	Muddy-opaque	Opaque	Opaque	Muddy	????SC	????38.9	????38.3	????38.6	????37.4	????38.6	????43.3	????46.0	????42.2	????39.1
Outward appearance	Muddy	Opaque	Opaque	Opaque	Opaque	Muddy-opaque	Opaque	Opaque	Muddy	????pH	????7.8	????7.8	????7.7	????-	????-	????8.1	????7.2	????8.4	????8.6
????VCD	????121	????99	????97	????97	????92	????70	????0	????73	????0	????pH	????7.8	????7.8	????7.7	????-	????-	????8.1	????7.2	????8.4	????8.6
????VCD	????121	????99	????97	????97	????92	????70	????0	????73	????0	????NCD	????0	????121	????244	????244	????459	????0	????0	????0	????0

1) embodiment 6a and 6b: in the dispersion that 400g makes as the method for preparing dispersion 6, add 9.64gADDH (embodiment 6a) and, in turn add the NaOH of 24ml 1N, the polyethyleneimine: amine aqueous solution of 48g 10% concentration (amino mol ratio with carbonyl is about 1: 1) (embodiment 6b).

Dispersion 11

Prepare dispersion 11 with the mode identical, but do not add ADDH with dispersion 6.

Solids content: 39.6%

PH value: 7.9

Dispersion 11a

By dispersion 11 is mixed with 0.5% DBU in solid resin, make dispersion 11a.

Dispersion 11b

By being mixed (mol ratio of hydrazide group and carbonyl is 1: 1) with 2.45 parts of adipic dihydrazides, 100 parts dispersion 11 makes dispersion 11b.

Dispersion 12

Method with dispersion 11 prepares dispersion 12.

Solids content: 40.8%

pH：7.9。

Dispersion 12a

By being mixed (mol ratio of hydrazide group and carbonyl is 1: 1) with 2.52 parts of adipic dihydrazides, 100 parts of dispersions 12 make dispersion 12a.

Dispersion 13

The step of describing with embodiment 3 prepares dispersion from following ingredients: 678.4g Compound I I, 53.65g DMPA, 87.42g 1,4-butyleneglycol, 537.97g IPDI, 40.48g TEA and 17.2g DETA.Product is that solids content is 23.9%, pH is 8.4 lacteous dispersion.Theoretical ketone group content is 952, and theoretical salts contg is the 228mmol/kg solid.

Dispersion 13a

In 100 parts of dispersions 13, add 1.96 parts of adipic dihydrazides (mol ratio of hydrazide group and carbonyl is 1: 1).

Dispersion 14

Step with embodiment 3 describes prepares dispersion from following ingredients: 400g polytetrahydrofuran 2000,368.33g compound III, 83.16g DMPA, 36.05g 1,4-butyleneglycol, 455.72g IPDI, 50.19g TEA and 17.2g DETA.Product is that solids content is 24.9%, pH is 8.0 lacteous dispersion.Theoretical ketone group content is 400, and theoretical salts contg is the 352mmol/kg solid.

A. as the performance test of coating material

Result as the performance test of coating material is reproduced among table 2a, 2b, the 2c, 3,4 and 5.

B. the preparation of printing-ink and performance test

Dispersion in the table 6 is mixed with pigment and other auxiliary agent of specified volume in this table, promptly by stirring, following ingredients being added in the dispersion with following order:

1. ammonia solution and water

2. the solution that forms by Basophob and remainder water

3. Virahol

4. pigment slurry

After optional the storage, by blade coating, the surface tension that printing-ink is coated to after the corona treatment is on the polyethylene of 38mN/m, then 90 ℃ or 60 ℃ of forced dryings 2 minutes.Dried film thickness is≤6 μ m.

The results are shown in Table 7 for the printing-ink performance test.

Table 2a: according to the test result of the coatingsurface that a) makes

Dispersion	The amount of required solvent (% weight)	Pd hardness ¹⁾Hour 0.5 (number of times)	Pd hardness ¹⁾1 hour (number of times)	Pd hardness ¹⁾3 hours (number of times)	Pd hardness ¹⁾5 hours (number of times)	Pd hardness ¹⁾1 day (number of times)
Dispersion	The amount of required solvent (% weight)	Pd hardness ¹⁾Hour 0.5 (number of times)	Pd hardness ¹⁾1 hour (number of times)	Pd hardness ¹⁾3 hours (number of times)	Pd hardness ¹⁾5 hours (number of times)	Pd hardness ¹⁾1 day (number of times)	????1	????/	????37	????45	????46	????46	????46
????1a	????/	????47	????48	????49	????51	????52	????1	????/	????37	????45	????46	????46	????46
????1a	????/	????47	????48	????49	????51	????52	????1(V)	????7	????11	????39	????42	????45	????45
????2(V)	????/	????37	????61	????61	????61	????67	????1(V)	????7	????11	????39	????42	????45	????45
????2(V)	????/	????37	????61	????61	????61	????67	????2a(V)	????/	????60	????74	????69	????60	????67
????4	????/	????41	????62	????62	????62	????62	????2a(V)	????/	????60	????74	????69	????60	????67
????4	????/	????41	????62	????62	????62	????62	????5	????1	????9	????88	????101	????101	????108
????6	????1	????24	????79	????79	????95	????105	????5	????1	????9	????88	????101	????101	????108
????6	????1	????24	????79	????79	????95	????105	????6a	????2	????18	????86	????98	????109	????124
????6b	????4	????9	????69	????93	????99	????118	????6a	????2	????18	????86	????98	????109	????124
????6b	????4	????9	????69	????93	????99	????118	????12	????7	????40	????63	????94	????102	????103
????12a	????5	????64	????100	????111	????119	????131	????12	????7	????40	????63	????94	????102	????103
????12a	????5	????64	????100	????111	????119	????131	????13	????2		????19	????25	????31	????56
????13a	????2		????18	????61	????65	????77	????13	????2		????19	????25	????31	????56

¹⁾Pd hardness: the surface strength that records according to (c)

Table 2b

According to e) test-results of the film that makes

Dispersion	Swelling in THF	????AV?THF	Swelling in ethanol (50%)	AV ethanol (50%)
Dispersion	Swelling in THF	????AV?THF	Swelling in ethanol (50%)	AV ethanol (50%)	????1	????881％	????18.6％	????767％	????14.2％
????1a	????401％	????4.0％	????222％	????0.4％	????1	????881％	????18.6％	????767％	????14.2％
????1a	????401％	????4.0％	????222％	????0.4％	????1b	????610％	????6.7％	????166％	????1.3％
????1(V)	Dissolving	?????/	Dissolving	?????/	????1b	????610％	????6.7％	????166％	????1.3％
????1(V)	Dissolving	?????/	Dissolving	?????/	????2(V)	The height swelling ^*	?????/	????952％	????15.9％
????2a(V)	The height swelling ^*	?????/	????1011％	????20.0％	????2(V)	The height swelling ^*	?????/	????952％	????15.9％
????2a(V)	The height swelling ^*	?????/	????1011％	????20.0％	????4	????488％	????6.0％	????196％	????1.9％
????5	????295％	????0.0％	????179％	????0.0％	????4	????488％	????6.0％	????196％	????1.9％

^*Very sticking table 2c steam test f)

Dispersion	Visual-immediately ^*	Nail hardness-immediately ^*	Visual-1 hour ^*	Nail hardness-1 hour ^*
Dispersion	Visual-immediately ^*	Nail hardness-immediately ^*	Visual-1 hour ^*	Nail hardness-1 hour ^*	????1	????3	????3	????3	????2
????1a	????2	????3	????2	????2	????1	????3	????3	????3	????2
????1a	????2	????3	????2	????2	????1(V)	????3	????5	????3	????2
????2(V)	????5	????5	????5	????2	????1(V)	????3	????5	????3	????2
????2(V)	????5	????5	????5	????2	????2a(V)	????5	????5	????5	????2
????4	????3	????5	????1	????2	????2a(V)	????5	????5	????5	????2
????4	????3	????5	????1	????2	????5	????3	????5	????1	????2
????6	????4	????5	????4	????3	????5	????3	????5	????1	????2
????6	????4	????5	????4	????3	????6a	????2	????2	????1	????2
????6b	????4	????5	????2	????2	????6a	????2	????2	????1	????2
????6b	????4	????5	????2	????2	????12	????2	????2	????2	????2
????12a	????1	????2	????1	????1	????12	????2	????2	????2	????2
????12a	????1	????2	????1	????1	????13	????2	????4	????1	????2
????13a	????2	????4	????1	????1	????13	????2	????4	????1	????2

^*0=is best to be divided; The difference of 5=

These results show that even without linking agent, the novel tolerance performance that contains the dispersion of carbonyl also improves.And, for contrast product, added linking agent and can not improve its tolerance.

Table 3:

According to b) test-results on the surface that makes

Dispersion	????11 ²	????11a	????11b
Dispersion	????11 ²	????11a	????11b	(j) 60 ℃ 70 ℃ 80 ℃ 90 ℃ of acetone tests (number of times)	? ?????50 ?????60 ?????75 ????＞100	? ??????50 ????＞100	? ????＞100
Impact hardness ¹⁾(number of times) (c) 60 ℃ 70 ℃ 80 ℃ 90 ℃	? ?????126 ?????126 ?????124 ?????114	? ? ??????131 ??????128 ??????122 ??????122	? ????123 ????124 ????135 ????137	(j) 60 ℃ 70 ℃ 80 ℃ 90 ℃ of acetone tests (number of times)	? ?????50 ?????60 ?????75 ????＞100	? ??????50 ????＞100	? ????＞100
Impact hardness ¹⁾(number of times) (c) 60 ℃ 70 ℃ 80 ℃ 90 ℃	? ?????126 ?????126 ?????124 ?????114	? ? ??????131 ??????128 ??????122 ??????122	? ????123 ????124 ????135 ????137	The Erichsen indentation test ¹⁾????[mm](i) ????60℃ ????????70℃ ????????80℃ ????????90℃	? ? ?????＞10 ?????＞10 ?????＞10 ?????＞10	? ? ????＞10 ????＞10 ????＞10 ????＞10	? ? ????＞10 ????＞10 ????＞10 ????＞10
The test of mark signature lattice ¹⁾[score ^*](h) ????60℃ ????????70℃ ????????80℃ ????????90℃	? ? ???????1 ???????1 ??????0-1 ???????0	? ? ?????0-1 ?????0-1 ?????0-1 ?????0-1	? ? ???????1 ???????1 ??????0-1 ??????0-1		? ? ?????＞10 ?????＞10 ?????＞10 ?????＞10	? ? ????＞10 ????＞10 ????＞10 ????＞10	? ? ????＞10 ????＞10 ????＞10 ????＞10
	? ? ???????1 ???????1 ??????0-1 ???????0	? ? ?????0-1 ?????0-1 ?????0-1 ?????0-1	? ? ???????1 ???????1 ??????0-1 ??????0-1	Wear test [mg] (g)	????23.9/23.6	???25.8/24.5	????26/24.7

^*0=is best to be divided, the difference of 5=

¹⁾The film of gradient ground blade coating on the baking oven plate;

²⁾Thin rust 40

The result of table 3 shows that the result that the basic catalyst of use catalytic amount obtains is similar to the result who obtains with stoichiometric linking agent.Add DBU (dispersion 11a) and ADDH (dispersion 11b) and can prevent thin rust.

Table 5: the test result on the film surface that on gradient baking oven model, makes by dispersion 4a according to (b)

Temperature (℃)	??60	????70	??80	??90	??100	????110	????120	????130	????140	????150	????160
Temperature (℃)	??60	????70	??80	??90	??100	????110	????120	????130	????140	????150	????160	Thickness (μ m)	??37	????34	??30	??34	??33	????35	????32	????33	????35	????35	????34
Visual gloss (%) (v)	??98										????97	Thickness (μ m)	??37	????34	??30	??34	??33	????35	????32	????33	????35	????35	????34
Visual gloss (%) (v)	??98										????97	Impact hardness (second) (c)	??161	????164	?161	?162	?157	????155	????140	????125	????127	????136	????122
Mark signature lattice test (score ^*〕(h)	??0	????0	??0	??0	??0	????0	????0	????0	????0	????0	????0	Impact hardness (second) (c)	??161	????164	?161	?162	?157	????155	????140	????125	????127	????136	????122
Mark signature lattice test (score ^*〕(h)	??0	????0	??0	??0	??0	????0	????0	????0	????0	????0	????0	Erichsen indentation test [mm] (i)	＞10	??＞10	＞10	＞10	＞10	??＞10	??＞10	??＞10	??＞10	??＞10	??＞10
Acetone double direction impulse (number of times) (j)	??16	????17	??18	??19	??23	????27	????35	????42	??＞50	??＞50	????42	Erichsen indentation test [mm] (i)	＞10	??＞10	＞10	＞10	＞10	??＞10	??＞10	??＞10	??＞10	??＞10	??＞10
Acetone double direction impulse (number of times) (j)	??16	????17	??18	??19	??23	????27	????35	????42	??＞50	??＞50	????42	Methylethylketone double direction impulse (number of times) (j)	??90	????90	＞100	＞100	＞100	??＞100	??＞100	??＞100	??＞100	??＞100	??＞100
The H of 38% concentration ₂SO ₄Test (I) 24 hours, room temperature (score)	??0		??1		??1		????1		????0		????0		??90	????90	＞100	＞100	＞100	??＞100	??＞100	??＞100	??＞100	??＞100	??＞100
	??0		??1		??1		????1		????0		????0	The NaOH test (I) of 1% concentration 24 hours, room temperature (score ^*〕	??0		??0		??0		????0		????0		????0
The NaOH test (I) of 5% concentration 24 hours, room temperature (score ^*〕	??5		??5		??5		????5		????3		????0		??0		??0		??0		????0		????0		????0

^*0=is best to be divided; The difference of 5=

These results show that along with temperature rises, it is better that the tolerance of varnish coating becomes.In about 150 ℃ of best combination that reach performance.

Table 6: the preparation of marking ink preparation (weight part)

Dispersion	Umber	The ammonia of 25% concentration	Virahol	Basophob ????WE	Water	Wacoblau
Dispersion	Umber	The ammonia of 25% concentration	Virahol	Basophob ????WE	Water	Wacoblau	????2	??49.2	????2.0	????5.0	????5.0	??38.8	????25
????4	??45.0	????2.0	????5.0	????5.0	??43.0	????25	????2	??49.2	????2.0	????5.0	????5.0	??38.8	????25
????4	??45.0	????2.0	????5.0	????5.0	??43.0	????25	????6	??46.3	????2.0	????5.0	????5.0	??41.7	????25
????7	??47	????2.0	????5.0	????5.0	???41	????25	????6	??46.3	????2.0	????5.0	????5.0	??41.7	????25
????7	??47	????2.0	????5.0	????5.0	???41	????25	????8	??46.5	????2.0	????5.0	????5.0	??41.5	????25
????9	??49.2	????2.0	????5.0	????5.0	??38.8	????25	????8	??46.5	????2.0	????5.0	????5.0	??41.5	????25
????9	??49.2	????2.0	????5.0	????5.0	??38.8	????25	????10	??46.2	????2.0	????5.0	????5.0	??41.8	????25
????7(V)	??39.1	????2.0	????5.0	????5.0	??38.9	????25	????10	??46.2	????2.0	????5.0	????5.0	??41.8	????25
????7(V)	??39.1	????2.0	????5.0	????5.0	??38.9	????25	????8(V)	??41.6	????2.0	????5.0	????5.0	??46.4	????25
????9(V)	??42.7	????2.0	????5.0	????5.0	??45.3	????25	????8(V)	??41.6	????2.0	????5.0	????5.0	??46.4	????25
????9(V)	??42.7	????2.0	????5.0	????5.0	??45.3	????25	????10(V)	??52.6	????2.0	????5.0	????5.0	??35.4	????25

Table 7: the test-results of printing-ink

Printing-ink from	Store	Viscosity (second) (m)	Dry	Tesa tears [%] (n)	Wet smear intensity ^*????(o)	Wet rubbing crease resistance after 30 minutes ^*??(p)	Wet rubbing crease resistance after 1 day ^*????(p?)	Wet cohesiveness (q) after 30 minutes	Wet cohesiveness (q) after 1 day	Gloss under 60 ° (r)	Levelling property (s)
Printing-ink from	Store	Viscosity (second) (m)	Dry	Tesa tears [%] (n)	Wet smear intensity ^*????(o)	Wet rubbing crease resistance after 30 minutes ^*??(p)	Wet rubbing crease resistance after 1 day ^*????(p?)	Wet cohesiveness (q) after 30 minutes	Wet cohesiveness (q) after 1 day	Gloss under 60 ° (r)	Levelling property (s)	Dispersion 2	?3d-50℃	About 22	??2′-60℃	??0/0	????1	????3	????3	Well	Well	Light	Streak slightly
Dispersion 2	?3d-50℃	About 22	??2′-90℃	??0/0	????1	????1	????1	Well	Well	Light	Streak slightly	Dispersion 2	?3d-50℃	About 22	??2′-60℃	??0/0	????1	????3	????3	Well	Well	Light	Streak slightly
Dispersion 2	?3d-50℃	About 22	??2′-90℃	??0/0	????1	????1	????1	Well	Well	Light	Streak slightly	Dispersion 4	Room temperature	????11.7	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well
Dispersion 4	?3d-50℃	????12.2	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well	Dispersion 4	Room temperature	????11.7	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well
Dispersion 4	?3d-50℃	????12.2	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well	Dispersion 6	Room temperature	????11.6	??2′-60℃	??0/0	????1	????5	????5	Well	Well	Light	Well
Dispersion 7	Room temperature	????11.4	??2′-60℃	??0/1	????1	????4-5	????4-5	Well	Well	Light	Well	Dispersion 6	Room temperature	????11.6	??2′-60℃	??0/0	????1	????5	????5	Well	Well	Light	Well
Dispersion 7	Room temperature	????11.4	??2′-60℃	??0/1	????1	????4-5	????4-5	Well	Well	Light	Well	Dispersion 7	?3d-50℃	About 55	??2′-60℃	??0/0	????1	????4-5	????4-5	Well	Well	Light	Streak slightly
Dispersion 7	?3d-50℃	About 55	??2′-90℃	??0/0	????1	????1	????4	Well	Well	Light	Streak slightly	Dispersion 7	?3d-50℃	About 55	??2′-60℃	??0/0	????1	????4-5	????4-5	Well	Well	Light	Streak slightly
Dispersion 7	?3d-50℃	About 55	??2′-90℃	??0/0	????1	????1	????4	Well	Well	Light	Streak slightly	Dispersion 8	Room temperature	????11.4	??2′-60℃	??1/0	????1	????1	????1	Well	Well	Light	Well
Dispersion 8	?3d-50℃	????13.3	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well	Dispersion 8	Room temperature	????11.4	??2′-60℃	??1/0	????1	????1	????1	Well	Well	Light	Well
Dispersion 8	?3d-50℃	????13.3	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well	Dispersion 9	Room temperature	????11.5	??2′-60℃	??0/0	????1	????1-2	????1-2	Well	Well	Light	Well
Dispersion 9	?3d-50℃	????15.3	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Streak slightly	Dispersion 9	Room temperature	????11.5	??2′-60℃	??0/0	????1	????1-2	????1-2	Well	Well	Light	Well
Dispersion 9	?3d-50℃	????15.3	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Streak slightly	Dispersion 10	Room temperature	????11.6	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well

Printing-ink from	Store	Viscosity (second) (m)	Dry	Tesa tears [%] (n)	Wet smear intensity ^*????(o)	Wet rubbing crease resistance after 30 minutes ^*????(p)	Wet rubbing crease resistance after 1 day ^*????(p)	Wet cohesiveness (q) after 30 minutes	Wet cohesiveness (q) after 1 day	Gloss under 60 ° (r)	Levelling property (s)
Printing-ink from	Store	Viscosity (second) (m)	Dry	Tesa tears [%] (n)	Wet smear intensity ^*????(o)	Wet rubbing crease resistance after 30 minutes ^*????(p)	Wet rubbing crease resistance after 1 day ^*????(p)	Wet cohesiveness (q) after 30 minutes	Wet cohesiveness (q) after 1 day	Gloss under 60 ° (r)	Levelling property (s)	Dispersion 10	?3d-50℃	????15.0	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well
Dispersion 7 (v)	Room temperature	????11.2	??2′-60℃	??-/1	????1	????4	????4	Difference	Difference	Light	Well	Dispersion 10	?3d-50℃	????15.0	??2′-60℃	??0/0	????1	????1	????1	Well	Well	Light	Well
Dispersion 7 (v)	Room temperature	????11.2	??2′-60℃	??-/1	????1	????4	????4	Difference	Difference	Light	Well	Dispersion 7 (v)	Room temperature	????11.2	??2′-90℃	??-/1	????1	????3-4	????4	Well	Medium	Light	Well
Dispersion 7 (v)	?3d-50℃	????11.2	??2′-60℃	??D/2	????1	????4	????4	Medium	Medium	Light	Well	Dispersion 7 (v)	Room temperature	????11.2	??2′-90℃	??-/1	????1	????3-4	????4	Well	Medium	Light	Well
Dispersion 7 (v)	?3d-50℃	????11.2	??2′-60℃	??D/2	????1	????4	????4	Medium	Medium	Light	Well	Dispersion 7 (v)	?3d-50℃	????11.2	??2′-90℃	??0/0	????1	????3	????4	Well	Medium	Light	Well
Dispersion 8 (v)	Room temperature	????11.5	??2′-60℃	??-/1	????1	????5	????4-5	Difference	Difference	Light	Well	Dispersion 7 (v)	?3d-50℃	????11.2	??2′-90℃	??0/0	????1	????3	????4	Well	Medium	Light	Well
Dispersion 8 (v)	Room temperature	????11.5	??2′-60℃	??-/1	????1	????5	????4-5	Difference	Difference	Light	Well	Dispersion 8 (v)	Room temperature	????11.5	??2′-90℃	??./0	????2	????4	????4-5	Medium	Difference	Light	Well
Dispersion 9 (v)	?3d-50℃	????11.6	??2′-60℃	??-/0	????1	????4	????4	Medium	Medium	Light	Well	Dispersion 8 (v)	Room temperature	????11.5	??2′-90℃	??./0	????2	????4	????4-5	Medium	Difference	Light	Well
Dispersion 9 (v)	?3d-50℃	????11.6	??2′-60℃	??-/0	????1	????4	????4	Medium	Medium	Light	Well	Dispersion 9 (v)	?3d-50℃	????11.6	??2′-90℃	??-/1	????1	????3-4	????3-4	Well	Medium	Light	Well
Dispersion 9 (v)	Room temperature	????11.7	??2′-60℃	??0/10	????1	????4	????5	Well	Medium	Light	Well	Dispersion 9 (v)	?3d-50℃	????11.6	??2′-90℃	??-/1	????1	????3-4	????3-4	Well	Medium	Light	Well
Dispersion 9 (v)	Room temperature	????11.7	??2′-60℃	??0/10	????1	????4	????5	Well	Medium	Light	Well	Dispersion 9 (v)	Room temperature	????11.7	??2′-90℃	??0/3	????1	????3	????4	Well	Difference	Light	Well
Dispersion 10 (v)	Room temperature	????11.9	??2′-60℃	??-/20	????1	????3-4	????3-4	Well	Well	Light	Well	Dispersion 9 (v)	Room temperature	????11.7	??2′-90℃	??0/3	????1	????3	????4	Well	Difference	Light	Well
Dispersion 10 (v)	Room temperature	????11.9	??2′-60℃	??-/20	????1	????3-4	????3-4	Well	Well	Light	Well	Dispersion 10 (v)	Room temperature	????11.9	??2′-90℃	??-/0	????1	????4	????4	Medium	Medium	Light	Well
Dispersion 10 (v)	?3d-50℃	????11.5	??2′-60℃	??0/0	????1	????4	????4-5	Medium	Medium	Light	Well	Dispersion 10 (v)	Room temperature	????11.9	??2′-90℃	??-/0	????1	????4	????4	Medium	Medium	Light	Well
Dispersion 10 (v)	?3d-50℃	????11.5	??2′-60℃	??0/0	????1	????4	????4-5	Medium	Medium	Light	Well	Dispersion 10 (v)	?3d-50℃	????11.5	??2′-90℃	??0/0	????1	????4	????4	Well	Medium	Light	Well

^*0=is best to be divided, the difference of 5=

Novel dispersion is better than the dispersion of prior art, especially aspect the wet rubbing crease resistance.Testing method

A) formation of film on glass

The dispersion agent that does not contain additive with the dried film thickness blade coating of about 50 μ m on sheet glass, and dry under standard conditions.After the drying, by the visual assessment film.If there is defective (variegated, stress crack, blushing, tangerine peel structure, shrinkage cavity etc.) in the film, just in dispersion, add butyl glycol then, the quantity of being added just in time be make that dried film surface is pure, light and do not have defective.The quantity of the butyl glycol that requires is represented with the weight percent of solvent load.

B) formation of film on the model

Dispersion agent is drawing the frame stretching with film on the standard metal model or on gradient baking oven model, and its wet coating thickness is generally 150-200 μ m, and at room temperature dry 10 minutes, oven dry then.

C) surface hardness (Pd hardness) is determined according to DIN53157 with the Konig device.Table 1 illustrates the impact number of times.Times different after the blade coating dispersion measure, shown in table 2a.

D) thickness: measure according to DIN50982

E) swell test

In order to obtain comparable result, the butyl glycol of 5% (weight) is joined in all dispersion agents, so that promote the formation of film.The film that about 2mm is thick is come out by flow coat.After 10 days, the fragment of film is placed the ethanol swelling 24 hours of tetrahydrofuran (THF) (THF) or 50% concentration.After the drying, lixiviate loss (AV) and swelling value have just been determined again.

F) water vapor test

Steam test is carried out about the standard of the two coating systems on wood substrate according to DIN68860B.Carry out visual assessment and nail hardness test immediately, carry out once again after 1 hour.

G) wear test

With high speed speed change dispersion machine the butyl glycol of 50g dispersion and definite addition was stirred 5 to 10 minutes, placed one day, it is coated on the Abraser test plate with the steel wire blade coating device of 200 μ m.After the room temperature conditioning one day, 60 ℃ of conditionings 16 hours, conditioning at least 48 hours in controlled climatic chamber then was that 503 Taber abrader carries out following wear test: grinding stone CS10 with the instrument model; Load 2 * 1kg; Rotating speed 1000 under 80% the suction.

H) mark signature lattice test: the standard of experimental evidence DIN53 151 is carried out

I) Erichsen indentation test: the standard of experimental evidence ISO1520 is carried out

J) acetone/methylethylketone test: the irony model of grade St1405 is with treating that test recipe or dispersion apply.After the drying, pressure a little is with a cotton that is soaked with acetone friction before and after being coated with on the selected position of model (1 time forward, constitute 1 double direction impulse DS 1 time backward).DS is carried out in test 50-100 time.Crosslinked or completely solidified are promptly thought in the place that above-mentioned test caudacoria is worn away not yet.

K) sulfuric acid test of 28% concentration: Dr.Kurt Herbert (DKB) is pressed in this test, and Wuppertal method as described below is carried out: one little cotton that will be soaked with above-mentioned acid is placed on the test piece.Place after 4 hours in 60 ℃ convection oven, according to the standard of DIN53 230 tables 1, the grading system with 0 to 5 (0=is fine, and 5=is poor) is assessed sample.

L) sodium hydroxide solution of the sulfuric acid test of 38% concentration and 1% and 5% concentration test: this test is by method i) standard carry out after at room temperature storing 24 hours.

M) viscosity:

According to the standard of DIN53 211, measure flowing time with the DIN4 cup.

N) bond strength:

Tear method assessment bond strength by Tesa, represent with %.In this test, the adhesive tape (Tesafilm 104-Beiersdorf AG) that width is 20-25mm is bonded on the printed matter to be measured, evenly presses then and tears rapidly.Test is at first carried out after drying, carries out after secondly storing in water.

O) wet smear intensity:

Be placed on the slick solid substrate remaining wet printed matter.Same direction wiping 50 times is pressed with the wet paper cloth of a softish in the light back of pressing.Whether visual assessment this paper be colored and dyeed what degree and/or whether what degree printed matter wipes and clip from substrate.

P) wet rubbing crease resistance

After wet cementation test, with the film of blade coating with an identical film " under water " circulation wipe mutually 20 times, carry out this test.

Q) wet cohesiveness

With dried scrape to film be placed in one barrel of water.With leniently rub coating in the water of thumb, whether wet coating can be wiped from substrate in assessment.Be stored in and carry out this test in the water after 30 minutes and 24 hours.

R) gloss: gloss is by visual assessment.

S) levelling property: levelling property is by visual assessment.

Claims

1, a kind of water dispersion that contains urethane (A), urethane (A) has from the structural unit of the compound deriving of general formula (I) R wherein ¹, R ²And R ³Each is hydrogen, C naturally ₁-C ₂₄Alkyl or C ₆-C ₂₄Alkenyl, R ⁴Be hydrogen, R ⁵And R ⁶Be a) to be C jointly ₄-C ₁₀Alkane 2 basis,

C) each hydroxy-end capped naturally poly-(C ₂-C ₄Alkylene oxide), or

D) R ⁵Or R ⁶One of just like (a) to (c) defined, another group is hydrogen or general formula I I

Group:

Wherein: X is C ₂-C ₆Alkane 2 basis, and R ⁷As R ⁵Or R ⁶Defined, but be not the group of general formula I I, wherein-R ⁵And R ⁶In each situation of (d), have 2-5 hydroxyl that is connected on the aliphatic carbons at (a) altogether, and-R ⁵And/or R ⁶Can have 1 or 2 hydroxyl that is connected on the aromatic structure in case of necessity, or have itrile group, tertiary amine groups, carboxyl or a sulfo group, they exist with the form of its salt in case of necessity.

2, the water dispersion of claim 1 contains from the structural unit of the compound deriving of general formula (I), in compound (I), is connected on the aliphatic carbons and by R ⁵And R ⁶The hydroxyl value sum of carrying is that 2 (Compound I a).

3, claim 1 or 2 water dispersion wherein in urethane, for the urethane (A) of every 100g, are 3 to 140mmol from the carbonyl content of the structural unit of the compound deriving of general formula (I).

4, a kind of method that is used to prepare the water dispersion of claim 1 to 3 comprises the following steps:

I. by with following substance reaction, prepare a kind of urethane or contain the polyurethane prepolymer of isonitrile acid group group:

A) with the multifunctional isocyanide ester of 4 to 30 carbon atoms,

B) following polyvalent alcohol:

B1) in total consumption of polyvalent alcohol (b), 10-100% (mole) molecular weight is 500 to arrive

5000 polyvalent alcohol, and

B2) in total consumption of polyvalent alcohol (b), the dual functional and molecular weight of 0-90% (mole)

Be 62 to the polyvalent alcohol of 500g/mol,

C) compound of general formula I and/or have alcoholic hydroxyl and have from the knot of the compound deriving of general formula I

The unitary condensation product of structure (condenses I),

D) if desired, in addition, be different from monomer (b) and polyfunctional compound (c),

It has the reactive group that is selected from alcoholic hydroxyl, primary amino and secondary amino group, and

E) be different from a), (b), (c) and monomer (d), it is with at least one isonitrile acid

Foundation group or at least one group to responding property of isonitrile acid group group, and have thus

At least one can make urethane be dispersed in hydrophilic radical or potential hydrophilic radical in the water,

II. urethane that step I is obtained or the polyurethane prepolymer that contains isonitrile acid group group are dispersed in water

In.

5, a kind of method that is used to prepare the water dispersion of claim 2-3, this method comprise, as condenses (I) be that molecular weight is the polyester polyol that contains carbonyl of 300-5000, it obtains by following material is carried out polycondensation:

X) compound of general formula (I) wherein is connected on the aliphatic carbons and by substituent R ⁵And R ⁶Jointly

The hydroxyl sum of carrying be 2 (Compound I a), and

Y) if desired, molecular weight is a dibasic alcohol (two 62-500g/mol, that be different from Compound I a

The unit pure y), with

Z) dicarboxylic acid,

Wherein, the mol ratio of compound (Ia) and dibasic alcohol (y) sum and dicarboxylic acid is 2: 1 to 1.05: 1.

6, the water dispersion of claim 1; except that urethane (A); also contain linking agent (B) in addition, linking agent (B) has at least one aldehyde radical or at least 2 sense substituents that are selected from isonitrile acid group base, N-methylol and the amino oxygen base of primary amino, secondary amino group, diazanyl, hydrazide group, isonitrile acid group base, protection.

7, the water dispersion of claim 6, wherein composition (A) and consumption (B) are selected like this, and promptly the carbonyl from the structural unit of the compound deriving of general formula (I) and the mol ratio of the sense substituent in the linking agent (B) they are 0.5: 1 to 5: 1.

8, the water dispersion of claim 1-7 contains

(I) binding agent that constitutes by urethane (A) and linking agent (B) basically of 15-30% (weight)

(II) pigment of 7-15% (weight)

(III) alcohol that is suitable as solvent of 2-5% (weight)

(IV) typical additives of 4.5-10% (weight)

(V) water of 45-70% (weight).

9, a kind of water dispersion of claim 8 contains the polyhydrazide as linking agent (B).

10, a kind of method that applies timber, glass, plastics, leather, paper or metal comprises that water dispersion with claim 6 to 9 is coated on described substrate a kind of, and dry this coating.

11, the method for a kind of printing paper or tinsel or polymeric film, this method comprise with a kind of dispersion of claim 8 or 9 prints above-mentioned materials.

12, a kind of method of claim 11, the base material that wherein is printed are that surface tension is the polymeric film of 30-50mN/m.

13, a kind of goods that obtain with the method for claim 10-12.