CN101128497A

CN101128497A - Pigments that are at least partially sheathed in radiation-curable polyurethane, their production and use

Info

Publication number: CN101128497A
Application number: CNA2006800060699A
Authority: CN
Inventors: C·克吕格尔; M·克卢格; C·迪勒曼
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-02-24
Filing date: 2006-02-23
Publication date: 2008-02-20
Also published as: DE102005008931A1

Abstract

Aqueous dispersion (A) comprises a pigment coated at least partially with a radiation-hardenable polyurethane obtained by reacting a di- or polyisocyanate containing an average of 1-10 allophanate and an average of 1-10 carbon-carbon double bonds per molecule; diisocyanate and a compound with at least two reactable isocyanate groups. Independent claims are included for: (1) the preparation of aqueous dispersion; (2) a substrate, colored or printed by the process; (3) an ink for ink-jet-process containing (A); (4) a process for printing on substrate using ink by the ink jet process; (5) a printed substrates, obtained by the process; (6) a radiation-hardenable polyurethane; and (7) a partially coated pigment, manufactured by dispersing the pigment and the polyurethane.

Description

Be encapsulated in pigment, Preparation Method And The Use in the radiation-curable polyurethane to small part

The present invention relates to a kind of water dispersion that comprises the pigment of being sealed to small part by at least a radiation-curable polyurethane (A) (B), at least a radiation-curable polyurethane (A) can pass through:

(a) at least a vulcabond or the polyisocyanates that comprises the average 1-10 of a per molecule allophanate groups and the two keys of average 1-10 C-C, with

(b) at least a other vulcabond, and with

(c) at least a compound with at least two isocyanate-reactive groups reacts and obtains.

The invention further relates to the pigment of sealing to small part by at least a pigment (B) and at least a radiation-curable polyurethane (A) being disperseed prepare, described radiation-curable polyurethane (A) can pass through:

(b) at least a other vulcabond and with

The invention further relates to pigment and the method for water dispersion of the present invention and their purposes that preparation the present invention seals to small part.

Usually need colo(u)rant dispersion at liquid, and especially for example write down fluid, especially printing ink so that further handle them to form in the water-bearing media.Just in this point, to being used for the printing ink of ink ejecting method (for example hot ink-jet, piezoelectric ink jet, continous inkjet, the spray of valve formula, transfer printing), there is strict especially requirement.They must have viscosity and the surface tension that is suitable for printing, they must be stablized in storage, and promptly they should be noncondensing or flocculation, and they must not cause the obstruction of printer nozzle, it is especially comprising dispersive, promptly under the situation of the printing ink of undissolved colorant particle problem is arranged.These write down fluid, especially printing ink and further require package stability, and the dispersive colorant particle does not deposit.In addition, under the situation of continous inkjet, printing ink should be stable for the adding of conducting salt, and does not improve the tendency of flocculating and with iron level.In addition, the printed matter that obtains must satisfy colorist's requirement, promptly has brightness and colourity, and has good fastness, if for example dried wear resistance, light fastness, color fastness to water and wet wear resistance are suitable for for example fixing back of aftertreatment and well dried property.

For guaranteeing good especially fastness for example dried wear resistance, wet wear resistance and the fastness to washing of printing element, printed matter can be fixed by so-called radiation curing.So-called radiation curable ink can be used for this purpose, for example sees US 5,623, and 001 and EP 0 993 495.The radiation-hardenable jetted ink comprises usually and can stand actinic radiation and the solidified material by making it.In addition, can comprise light trigger in the radiation-hardenable jetted ink.

Yet the problem of existence is that the radiation curing degree of printing element in some cases is inhomogeneous.Observe curing in some place very good, then poor in other zones, is called soft spots.Curing heterogeneous damages some regional fastness to rubbings.In addition, damage the feel of printing element, this is undesired for the printing textile substrate especially.Therefore, need provide especially evenly solidified ink jet method printing ink.

The diurethanes of radiation-hardenable and urethane are for example known from EP-B 1 144 476 and EP 1,118 627.The radiation-curable polyurethane that is described in the reference of before having quoted can for example be used to apply furniture or automobile.Exist and widely apply, yet for these application, their use properties needs to improve.

Therefore, the water dispersion that the purpose of this invention is to provide pigment.Another object of the present invention provides and is used for ink jet method and the effect by actinic radiation and solidified printing ink especially easily.Another object of the present invention provides the method that preparation is used for the printing ink of ink jet method.The last purpose of the present invention provides the printing element with good especially feel and good fastness, especially prints textile substrate.

We have found that this purpose realizes by the water dispersion that begins to define.

As used in this, statement " printing ink that is used for ink jet method " and " jetted ink " equates.

With regard to the object of the invention, urethane is interpreted as referring to the not only this polymkeric substance that only connects by carbamate groups, and more generally meaning refer to can be by making vulcabond or polyisocyanates and the compound that comprises active hydrogen atom reacts the polymkeric substance that obtains.Therefore, be used for urethane of the present invention and can not only comprise carbamate groups, also comprise urea, allophanate, biuret, carbodiimide, acid amides, ester, ether, uretonimine, urea diketone, isocyanuric acid ester or  oxazolidinyl group.As general reference, can for example quote: Kunststoffhandbuch/Saechtling, the 26th edition, Carl-Hanser-Verlag, Munich reaches each page subsequently for 1995, the 491 pages.More particularly, be used for urethane of the present invention and comprise allophanate groups.

In one embodiment of the invention, radiation-curable polyurethane (A) is not a super branched polyurethane.Super branched polyurethane is same known and for example be described in J.M.S.-Rev.Macromol.Chem.Phys.1997, and C37 (3) is in 555.

Water dispersion of the present invention comprises at least a pigment of being sealed to small part by at least a radiation-curable polyurethane (A) (B).Hereinafter, " pigment of being sealed by at least a radiation-curable polyurethane to small part " is interpreted as this pigment with particulate forms that refers to that its outer surface is sealed by radiation-curable polyurethane wholly or in part.Wherein the pigment particles of each certain percentage ratio is not covered with the outer surface of each other pigment particles wherein by radiation-curable polyurethane and covers mixture with the pigment of particulate forms wholly or in part equally in the definition of " pigment of being sealed by at least a radiation-curable polyurethane to small part " by radiation-curable polyurethane.

In one embodiment of the invention, the pigment of being sealed by at least a radiation-curable polyurethane to small part has at least 10%, preferred at least 20% or more preferably at least 30% outer surface by the radiation-curable polyurethane covering.

Degree of sealing for example can be by measuring ζDian Shi on the pigment of sealing in exsiccant to small part, for example by microscopy such as optical microscopy or electron microscopy (TEM, low temperature-TEM, SEM), and measure by freeze-fracturing technology of preparing, NMR spectrography or PES quite particularly.

Obtain by sealing to small part within the scope of the present invention to small part pigment to be encapsulated (B) according to the definition of German standard standard DIN 55944 organic or inorganic tinting material water insoluble, in small, broken bits basically.Water dispersion of the present invention is preferably prepared by the pigment dyestuff that comprises carbon black.To determine the example of particularly suitable pigment (B) now.

Pigment dyestuff:

-monoazo pigment: C.I.Pigment Brown 25; C.I.Pigment Orange 5,13,36

With 67; C.I.Pigment Red 1,2,3,5,8,9,12,17,

22、23、31、48:1、48:2、48:3、48:4、49、49:1、52:1、

52:2、53、53:1、53:3、57:1、63、112、146、170、184、

210,245 and 251; C.I.Pigment Yellow 1,3,73,74,

65,97,151 and 183;

-disazo pigment: C.I.Pigment Orange 16,34 and 44; C.I.Pigment Red

144,166,214 and 242; C.I.Pigment Yellow 12,13,

14、16、17、81、83、106、113、126、127、155、174、

176 and 188;

-anthanthrone pigment: C.I.Pigment Red 168 (C.I.Vat Orange 3);

-anthraquinone pigment: C.I.Pigment Yellow 147 and 177; C.I.Pigment Violet 31;

-anthrapyrimidine pigment: C.I.Pigment Yellow 108 (C.I.Vat Yellow 20);

-quinacridone pigment: C.I.Pigment Red 122,202 and 206; C.I.Pigment Violet

19；

-quinophthalone pigment: C.I.Pigment Yellow 138;

-two  piperazine pigment: C.I.Pigment Violet 23 and 37;

-flavanthrene pigment: C.I.Pigment Yellow 24 (C.I.Vat Yellow 1);

-indanthrene pigment: C.I.Pigment Blue 60 (C.I.Vat Blue 4) and 64 (C.I.Vat

Blue 6)；

-isoindoline pigment: C.I.Pigment Orange 69; C.I.Pigment Red 260; C.I.

Pigment Yellow 139 and 185;

-isoindolinone pigment: C.I.Pigment Orange 61; C.I.Pigment Red 257 Hes

260; C.I.Pigment Yellow 109,110,173 and 185;

-isoviolanthrone pigment: C.I.Pigment Violet 31 (C.I.Vat Violet 1);

-metal complex pigment: C.I.Pigment Yellow 117,150 and 153; C.I.Pigment

Green 8；

-purple cyclic ketones pigment: C.I.Pigment Orange 43 (C.I.Vat Orange 7); C.I.

Pigment Red 194(C.I.Vat Red 15)；

-perylene pigment: C.I.Pigment Black 31 and 32; C.I.Pigment Red 123,

149、178、179(C.I.Vat Red 23)、190(C.I.Vat Red 29)

With 224; C.I.Pigment Violet 29;

-phthalocyanine pigment: C.I.Pigment Blue 15,15:1,15:2,15:3,15:4,15:6 and

16; C.I.Pigment Green 7 and 36;

-pyranthrone pigments: C.I.Pigment Orange 51; C.I.Pigment Red 216 (C.I.Vat

Orange 4)；

-thioindigo color: C.I.Pigment Red 88 and 181 (C.I.Vat Red 1); C.I.Pigment

Violet 38(C.I.Vat Violet 3)；

-triaryl carbon  pigment: C.I.Pigment Blue 1,61 and 62; C.I.Pigment Green

1; C.I.Pigment Red 81,81:1 and 169; C.I.Pigment

Violet 1,2,3 and 27; C.I.Pigment Black 1 (aniline

Black); C.I.Pigment Yellow 101 (aldazine Huang); C.I.

Pigment Brown 22。

Mineral dye:

-white pigment: titanium dioxide (C.I.Pigment White 6), zinc white, painted zinc oxide, sulphur

Acid barium, zinc sulphide, lithopone; White lead;

-black pigment: iron oxide black (C.I.Pigment Black 11), iron-manganese black, the black (C.I. of spinel

Pigment Black 27); Carbon black (C.I.Pigment Black 7);

-coloured pigment: chromic oxide, transparent vert emeraude; Chrome green (C.I.Pigment Green 48);

Cobalt green (C.I.Pigment Green 50); Ultramarine green; Cobalt blue (C.I.Pigment

Blue 28 and 36); Ultramarine blue; Barba hispanica (C.I.Pigment Blue 27);

Manganese indigo plant; Ultramarine violet; Cobalt and manganese violet; Red iron oxide (C.I.Pigment Red

101); Cadmium sulfoselenide (C.I.Pigment Red 108); Molybdenum red (C.I.

Pigment Red 104); Ultramarine is red;

Iron oxide brown, mixing palm fibre, spinel and corundum be (C.I.Pigment Brown mutually

24,29 and 31), chrome orange;

Iron oxide yellow (C.I.Pigment Yellow 42); Nickel titanium yellow (C.I.Pigment

Yellow 53; C.I.Pigment Yellow 157 and 164); The chromium titan yellow; Sulphur

Change cadmium and Cadmium Sulfide zinc (C.I.Pigment Yellow 37 and 35); Chrome yellow (C.I.

Pigment Yellow 34), zinc yellow, chromic acid alkaline earth salt; Naples yellow;

Pucherite (C.I.Pigment Yellow 184);

-interference pigments: based on the metallic effect pigments of the tinsel that applies; Based on metal oxide-coated

The pearly pigment of sheet mica; Liquid crystal pigment.

Preferred herein pigment (B) is monoazo pigment (especially color lake BONS pigment, naphthol AS pigments), disazo pigment (especially diarylide yellow pigment, di-acetyl acetanilide N pigment, two azo pyrazolone pigments), quinacridone pigment, quinophthalone pigment, purple cyclic ketones pigment, phthalocyanine pigment, triaryl carbon  pigment (alkali blue pigment, color lake rhodamine, have the dye salt of coordination anion), isoindoline and carbon black.

The example of particularly preferred pigment (B) is specially: carbon black, C.I.Pigment Yellow 138, C.I.Pigment Red 122 and 146, C.I.Pigment Violet 19, C.I.Pigment Blue 15:3 and 15:4, C.I.Pigment Black 7, C.I.Pigment Orange 5,38 and 43, and C.I.Pigment Green 7.

Being used for radiation-curable polyurethane of the present invention (A) can pass through:

(a) at least a vulcabond or the polyisocyanates that comprises the average 1-10 of a per molecule allophanate groups and the two keys of average 1-10 C-C, wherein each mean value is preferably based on number average, with

(b) at least a other vulcabond, and with

At least a average 1-10 of per molecule of comprising, preferably 5 allophanate groups and average 1-10 are individual at the most, preferred two keys of 5 C-C at the most, mean value is separately based on weighted average, and be preferably based on the vulcabond of number average or polyisocyanates (a) for preferably in the presence of catalyzer, the compound for preparing with the compound of at least a general formula I by at least a vulcabond (a1):

Abbreviate compound (a2) here as, variable-definition is as follows:

R ¹And R ²Identical or different and be selected from hydrogen and C independently of one another ₁-C ₁₀Alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl; More preferably C ₁-C ₄Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, especially methyl;

X ¹Be selected from oxygen and N-R ³,

A ¹Be selected from C ₁-C ₂₀Alkylidene group, preferred C ₂-C ₁₀Alkylidene group is as-CH ₂-,-(CH ₂) ₁₂-,-(CH ₂) ₁₄-,-(CH ₂) ₁₆-,-(CH ₂) ₂₀-, preferred-(CH ₂) ₂-,-(CH ₂) ₃-,-(CH ₂) ₄-,-(CH ₂) ₅-,-(CH ₂) ₆-,-(CH ₂) ₈-,-(CH ₂) ₁₀-, it is not for replacing or being replaced or polysubstituted by following group list: C ₁-C ₄Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, preferable methyl, phenyl or-O-C ₁-C ₄Alkyl is as-O-CH ₃,-O-C ₂H ₅,-O-n-C ₃H ₇,-O-CH (CH ₃) ₂,-O-just-C ₄H ₉The different C of ,-O- ₄H ₉The secondary C of ,-O- ₄H ₉,-O-C (CH ₃) ₃,

The C that replaces ₁-C ₂₀Alkylidene group can for example be mentioned-CH (CH ₃)-,-CH (C ₂H ₅)-,-CH (C ₆H ₅)-,-CH ₂-CH (CH ₃)-, is suitable-and anti--CH (CH ₃)-CH (CH ₃)-,-(CH ₂)-C (CH ₃) ₂-CH ₂-,-CH ₂-CH (C ₂H ₅)-,-CH ₂-CH (n-C ₃H ₇)-,-CH ₂-CH (different C ₃H ₇)-,

Replacing or unsubstituted C ₁-C ₂₀In the alkylidene group, one or more not contiguous CH ₂Group can be replaced by oxo, and example is-CH ₂-O-CH ₂-,-(CH ₂) ₂-O-(CH ₂) ₂-,

-[(CH ₂) ₂-O] ₂-(CH ₂) ₂-、-[(CH ₂) ₂-O] ₃-(CH ₂) ₂-，

X ²Be selected from NH-R ³, preferred oxygen,

R ³Different or preferred identical and for example be selected from hydrogen, phenyl and C under every kind of situation ₁-C ₁₀Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl; More preferably C ₁-C ₄Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, especially methyl.

The compound of general formula I very particularly preferably is 2-hydroxyethyl (methyl) acrylate and 3-hydroxypropyl (methyl) acrylate.

Radiation-curable polyurethane can be not or preparation in the presence of at least a catalyzer.

Useful catalysts for example comprises that all are generally used for the catalyzer of polyurethane chemistry.

The common used preferred organic amine of catalyzer in the polyurethane chemistry, especially uncle's aliphatic series, cyclic aliphatic or aromatic amine and Lewis acid organometallic compound.

Useful Lewis acid organometallic compound for example comprises tin (II) salt of tin compound such as organic carboxylic acid, example is tin acetate (II), stannous octoate (II), thylhexoic acid tin (II) and tin laurate (II), with dialkyl tin (IV) derivative of organic carboxyl acid, example is oxalic acid tin methide, dibutyltin diacetate, two butyric acid dibutyl tins, two (2 ethyl hexanoic acid) dibutyl tin, dibutyl tin laurate, toxilic acid dibutyl tin, two lauric acid dioctyl tins and oxalic acid dioctyl tin.The acetylacetonate of the acetylacetonate of the acetylacetonate of the acetylacetonate of metal complex such as iron, the acetylacetonate of titanium, aluminium, the acetylacetonate of zirconium, manganese, the acetylacetonate of nickel and cobalt also is possible.Other useful metallic compounds are described in Progress in Organic Coatings by Blank etc., and 1999,35,19 and subsequently in each page.

Preferred Lewis acid organometallic compound is oxalic acid tin methide, two butyric acid dibutyl tins, two (2 ethyl hexanoic acid) dibutyl tin, dibutyl tin laurate, two lauric acid dioctyl tins, zirconium acetylacetonate and 2,2,6,6-tetramethyl--3,5-heptadione acid zirconium.

Similarly, bismuth and cobalt catalyst and cesium salt can be used as the wetting ability catalyzer.Useful cesium salt comprises and utilizes following anionic Cesium compound: F ^-, Cl ^-, ClO ^-, ClO ₃ ^-, ClO ₄ ^-, Br ^-, I ^-, IO ₃ ^-, CN ^-, OCN ^-, NO ₂ ^-, NO ₃ ^-, HCO ₃ ^-, CO ₃ ^2-, S ^2-, SH ^-, HSO ₃ ^-, SO ₃ ^2-, HSO ₄ ^-, SO ₄ ^2-, S ₂O ₂ ^2-, S ₂O ₄ ^2-, S ₂O ₅ ^2-, S ₂O ₆ ^2-, S ₂O ₇ ^2-, S ₂O ₈ ^2-, H ₂PO ₂ ^-, H ₂PO ₄ ^-, HPO ₄ ^2-, PO ₄ ^3-, P ₂O ₇ ^4-, (OC _nH _2n+1) ^-, (C _nH _2n-1O ₂) ^-, (C _nH _2n-3O ₂) ^-(C _N+1H _2n-2O ₄) ^2-, wherein n represents 1 to 20 integer.

Preferred anionic meets formula (C _nH _2n-1O ₂) ^-And (C _N+1H _2n-2O ₄) ^2-And n is 1 to 20 carboxylic acid caesium.Particularly preferred cesium salt comprises general formula (C _nH _2n-1O ₂)-as negatively charged ion, wherein n represents the monocarboxylate of the integer of 1-20.Here must mention formate, acetate, propionic salt, hexanoate and 2-ethylhexoate especially.

As conventional organic amine, for example can mention: triethylamine, 1,4-diazabicylo [2,2,2] octane, Tributylamine, dimethyl benzyl amine, N, N, N ', N '-tetramethylethylened, N, N, N ', N '-4-methyl-butane-1, the 4-diamines, N, N, N ', N '-tetramethyl-hexane-1, the 6-diamines, dimethylcyclohexylam,ne, the dimethyl lauryl amine, the pentamethyl-dipropylenetriamine, five methyl diethylentriamine, 3-methyl-6-dimethylamino-3-azepine pentol, dimethylaminopropyl amine, 1, the two dimethylamino butane of 3-, two (2-dimethyl aminoethyl) ether, N-ethylmorpholine, N-methylmorpholine, N-cyclohexyl morpholine, 2-dimethylamino ethoxy ethanol, dimethylethanolamine, the tetramethyl-hexamethylene-diamine, dimethylamino-N-Mono Methyl Ethanol Amine, the N-Methylimidazole, N-formyl-N, N '-dimethyl butylene diamine, N-dimethyl aminoethyl morpholine, 3,3 '-two dimethylaminos-two-n-propyl amine and/or 2,2 '-two piperazine Di Iso Propyl Ethers, lupetazin, three (N, the N-dimethylaminopropyl)-the s-Hexahydrotriazine, imidazoles is as 1, the 2-methylimidazole, 4-chloro-2,5-dimethyl-1-(N-methylamino ethyl) imidazoles, 2-aminopropyl-4,5-dimethoxy-1-Methylimidazole, 1-aminopropyl-2,4,5-tributyl imidazoles, 1-amino-ethyl-4-hexyl imidazoles, the amino butyl-2 of 1-, the 5-methylimidazole, 1-(3-aminopropyl)-2-ethyl-4-methylimidazole, 1-(3-aminopropyl) imidazoles and/or 1-(3-aminopropyl)-glyoxal ethyline.

Preferred organic amine is for having two C independently ₁-C ₄Alkyl and the trialkylamine with alkyl or cycloalkyl of 4-20 carbon atom, for example a dimethyl-C ₄-C ₁₅Alkylamine such as dimethyl lauryl amine or dimethyl-C ₃-C ₈Cycloalkyl amine.If same preferred organic amine is the suitable Wyovin that comprises other heteroatomss such as oxygen or nitrogen for example, as 1,4-diazabicyclo [2,2,2] octane.

Especially preferably use ammonium acetate or triethylamine, most preferably use 2 ethyl hexanoic acid N, N, N-trimethylammonium-N-(2-hydroxypropyl) ammonium.

The mixture that is to be understood that two or more above-claimed cpds is useful as catalysts equally also.

Preferred especially the use is selected from this catalyzer that above-claimed cpd dissolves in organic solvent such as acetone, tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone and/or N-ethyl pyrrolidone.

Catalyzer is preferably with based on vulcabond (a1), and the amount of 0.0001-10 weight % is more preferably used with the amount of 0.001-5 weight %.

The composition that depends on a kind of catalyzer or multiple catalyzer can add a kind of catalyzer or multiple catalyzer with solid or liquid form or with solution.Useful solvent comprises the solvent with water immiscibility, for example aromatics or aliphatic hydrocrbon such as toluene, ethyl acetate, hexane and hexanaphthene, and carboxylicesters such as ethyl acetate, useful solvent comprises acetone, THF and N-Methyl pyrrolidone and N-ethyl pyrrolidone in addition.A kind of catalyzer or multiple catalyzer most preferably add with the solution in organic solvent such as acetone, tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone or N-ethyl pyrrolidone preferably with solid or liquid form.

Vulcabond (a1) for example is selected from aliphatic series, aromatics and cycloaliphatic diisocyanates.Aromatic diisocyanate for example be 2,4 toluene diisocyanate (2,4-TDI), 2,4 '-diphenylmethanediisocyanate (2,4 '-MDI) and so-called TDI mixture (2,4 toluene diisocyanate and 2, the mixture of 6-tolylene diisocyanate).

The example of aliphatic vulcabond is 1,4-butylidene vulcabond, 1,12-ten dimethylene diisocyanates, 1,10-decamethylene vulcabond, 2-butyl-2-ethyl pentamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate or 2,2,4-trimethyl hexamethylene diisocyanate, especially hexamethylene diisocyanate (HDI).

The example of cycloaliphatic diisocyanates is isophorone diisocyanate (IPDI), 2-isocyanato-propyl group cyclohexyl isocyanate, 2,4 '-methylene-bis (cyclohexyl) vulcabond and 4-methylcyclohexane 1,3-vulcabond (H-TDI).

Other examples of isocyanic ester with group of differential responses are 1,3-phenylene vulcabond, 1,4-phenylene vulcabond, l,5 naphthylene diisocyanate, diphenyl diisocyanate, tolidine vulcabond and 2, the 6-tolylene diisocyanate.

Certainly, can use the mixture of above-mentioned vulcabond.

Vulcabond (a1) and compound (a2) can be for example with 10: 1-1: 1, preferred 5: 1-5: 4 mol ratio is used.

In one embodiment of the invention, vulcabond (a1) and compound (a2) can be at 20-150 ℃, react to each other under preferred 50-130 ℃.

In one embodiment of the invention, vulcabond (a1) can preferably react organic solvent such as toluene, acetone or tetrahydrofuran (THF) or its mixture at solvent with compound (a2) in the mixture of organic solvent or organic solvent.In another embodiment of the invention, vulcabond (a1) does not use solvent with the reaction of compound (a2) and carries out.

In one embodiment of the invention, the reaction conditions of the reaction of vulcabond (a1) and compound (a2) for example the selection of vulcabond (a1) and the mol ratio of compound (a2) make vulcabond (a) have 2 isocyanate groups and 1-10 allophanate groups and 1-10 C-C pair of keys but do not have the O-CO-NH group.In another embodiment of the invention, the reaction conditions of the reaction of vulcabond (a1) and compound (a2) for example selection of vulcabond (a1) and the mol ratio of compound (a2) makes vulcabond (a) have 2 isocyanate groups and 1-9 allophanate groups and 1-9 C-C pair of keys and one or more O-CO-NH group.

After the reaction of vulcabond (a1) and compound (a2) had finished, vulcabond or polyisocyanates (a) for example can be by removing unconverted starting raw material such as vulcabond (a1) or compound (a2) separates.The appropriate methodology of removing unconverted starting raw material such as vulcabond (a1) or compound (a2) is that they are preferably distilled out under the pressure that reduces.Thin-film evaporator is for very particularly suitable.Unconverted vulcabond (a1) is not preferably removed by distillation.

In one embodiment of the invention, vulcabond or polyisocyanates (a) dynamic viscosity under 23 ℃ is 500-2000mPas, preferred 600-1800mPas, most preferably 700-1500mPas.

In one embodiment of the invention, vulcabond or polyisocyanates (a) for example can be 8-20 weight % by the NCO content of titration measuring, preferred 12-17 weight %.

Radiation-curable polyurethane (A) prepares by making vulcabond or polyisocyanates (a) and at least a other vulcabond (b) reaction.Vulcabond (b) can be selected from above-mentioned aliphatic series, aromatics and cycloaliphatic diisocyanates.Vulcabond (b) is different from vulcabond (a), and therefore is called " other vulcabond " in the scope of the invention.

In one embodiment of the invention, the selection of vulcabond (b) makes it to be different from vulcabond (a1).

In one embodiment of the invention, the selection of vulcabond (b) makes it to be similar to vulcabond (a1).After finishing, the preparation that a specific embodiments of the present invention is included in vulcabond (a) do not separate the vulcabond (b) of selecting to be similar to vulcabond (a1) by the vulcabond (a1) that will not consume.

By preparing with at least a compound (c) reaction with at least two isocyanate-reactive groups, this compound is also referred to as compound (c) to radiation-curable polyurethane (A) in the scope of the invention in addition.Be easy to isocyanate-reactive group especially and for example comprise SH group, hydroxyl, NH ₂Group and NHR ³Group, wherein R ³As above definition.

Compound (c) can be wetting ability or hydrophobic.

At least a compound (c) is preferably selected from 1,1,1-trishydroxymethyl-C ₁-C ₄Alkyl carboxylic acid is as 1,1,1-trishydroxymethyl acetate, 1,1,1-trishydroxymethyl propionic acid, 1,1,1-trishydroxymethyl butyric acid, citric acid, 1,1-dihydroxymethyl-C ₁-C ₄Alkyl carboxylic acid is as 1,1-dihydroxymethyl acetate, 1,1-dimethylol propionic acid, 1,1-dimethylolpropionic acid, 1,1-dihydroxymethyl-C ₁-C ₄Alkylsulphonic acid, average per molecule have the poly--C of 3-300 oxyalkylene units ₂-C ₃Aklylene glycol, especially average (number average) per molecule have the polyoxyethylene glycol of 3-300 ethylene oxide unit and on average the molar fraction of (number average) per molecule with 3-300 ethylene oxide unit and ethylene oxide be higher than the ethylene oxide of molar fraction of propylene oxide and the polyaddition products of propylene oxide;

Have COOM or SO ₃The wetting ability diamines of M group, for example:

Wherein M is selected from alkalimetal ion, especially Na ⁺, and ammonium ion,

The polyester glycol that can prepare by the polycondensation of following component:

At least a aliphatic series or cycloaliphatic diol, preferred ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, suitable-1,4-cyclohexanediol, anti--1,4-cyclohexanediol, suitable-and anti--1,4-dihydroxyl methylcyclohexane (cyclohexanedimethanol),

With at least a aliphatic series, aromatics or cycloaliphatic dicarboxylic acid, for example succsinic acid, pentanedioic acid, hexanodioic acid, hexanaphthene-1, the polycondensation of 4-dicarboxylic acid, terephthalic acid, m-phthalic acid.

One embodiment of the invention comprise that selection is used to prepare the dicarboxylic acid of polyester glycol at least for two kinds, wherein a kind of is aromatics, another kind is an aliphatic series, and example is succsinic acid and m-phthalic acid, pentanedioic acid and m-phthalic acid, hexanodioic acid and m-phthalic acid, succsinic acid and terephthalic acid, pentanedioic acid and terephthalic acid, hexanodioic acid and terephthalic acid.

In order to use two or more dicarboxylic acid to prepare polyester glycol, can use any required mol ratio.

When using aromatic dicarboxylic acid and aliphatic dicarboxylic acid, preferred 10: 1-1: 10 mol ratio, particularly 1.5: 1-1: 1.5 mol ratio.

In one embodiment of the invention, the hydroxyl value that has as the polyester glycol of compound (c) is determined as 20-200mg KOH/g according to German standard standard DIN 53240, preferred 50-180mgKOH/g, most preferably 100-160mg KOH/g.

In one embodiment of the invention, be used as the molecular weight M of the polyester glycol of compound (c) _wBe 500-100 000g/mol, preferred 700-50 000g/mol, more preferably 30 000g/mol at the most.

Other compounds (c) that are fit to are thanomin, diethanolamine, dimethyltrimethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,1-dihydroxy methylpropane.

One embodiment of the invention comprise and two kinds of compounds (c) reaction, wherein a kind of thanomin, diethanolamine, dimethyltrimethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,1-dihydroxy methylpropane of being selected from least.

One embodiment of the invention comprise synthetic by the following method radiation-curable polyurethane (A):

(a) other compound with at least a general formula I adds in the following reaction:

(b) at least a vulcabond or the polyisocyanates that comprises the average 1-10 of a per molecule allophanate groups and the two keys of average 1-10 C-C, with

(c) at least a other vulcabond, and with

(d) at least a reaction with compound of at least two isocyanate-reactive groups.

The compound of general formula I as mentioned above.

As the compound (d) of general formula I, can use the compound that is different from the general formula I that is used to prepare the vulcabond that comprises the average 1-10 of a per molecule allophanate groups and average 1-10 C-C pair keys or polyisocyanates (a).Yet preferred compound (d) is identical with compound (a2).

The synthetic of radiation-curable polyurethane (a) can be undertaken by the ordinary method of polyurethane chemistry.

One embodiment of the invention are used vulcabond or polyisocyanates (a) with following weight ratio, other vulcabond (b) and compound (c) and if the compound of suitable other general formula Is (d), separately based on whole radiation-curable polyurethane (A):

0.1-10 weight %, preferred 1-6 weight % vulcabond or polyisocyanates (a),

20-60 weight %, preferred other vulcabond of 30-55 weight % (b),

3-20 weight %, preferred 5-15 weight % compound (c),

0-20 weight %, the compound (d) of preferred 5-15 weight % general formula I.

Each weight % is based on whole radiation-curable polyurethane to be synthesized (A).

A preferred version of the present invention comprises by making not only vulcabond or polyisocyanates (a), other vulcabond (b) and compound (c) and if the compound of suitable other general formula Is (d), and can be used as terminator and hereinafter be appointed as at least a nucleophilic alcohol or the amine of terminator (e) in addition with under every kind of situation, preferred single alcohol or monoamine reaction and prepare radiation-curable polyurethane (A).The terminator (e) that is fit to is singly-and two-C ₁-C ₄Alkylamine, especially diethylamine.Can use based on radiation-curable polyurethane to be synthesized (A), at the most the terminator of 10 weight % (e).

By vulcabond or polyisocyanates (a), other vulcabond (b), compound (c) and if the compound of suitable other general formula Is (d), and if suitable terminator (e) preparation radiation-curable polyurethane (A) can in one or more stages, carry out.For example, vulcabond or polyisocyanates (a), other vulcabond (b) can be in first stage with compound (c), preferably in the presence of catalyzer, react, reaction stops, thereafter again with the compound (d) of vulcabond (b) and general formula I and if suitable terminator (e) add.For example also can use excessive other vulcabond (b) to make vulcabond or polyisocyanates (a), other vulcabond (b) and compound (c) react to each other, the stopped reaction by adding terminator (e).

In one embodiment of the invention vulcabond or polyisocyanates (a), other vulcabond (b), compound (c) and if the compound of suitable other general formula Is (d) and if suitable terminator (e) in solvent, preferably in the mixture of organic solvent or organic solvent, react organic solvent such as toluene, acetone or tetrahydrofuran (THF) or its mixture.In another embodiment of the invention, vulcabond or polyisocyanates (a), other vulcabond (b), compound (c) and if the compound of suitable other general formula Is (d) and if the reaction of suitable terminator (e) do not use solvent and carry out.

One embodiment of the invention comprise make vulcabond or polyisocyanates (a), other vulcabond (b) and compound (c) and if the compound of suitable other general formula Is (d) and if suitable terminator (e) under 20-150 ℃, preferably 20-80 ℃ of reaction down.

For quickening vulcabond or polyisocyanates (a), other vulcabond (b), compound (c) and if the compound of suitable other general formula Is (d) and if the reaction of suitable terminator (e), can use one or more advantageously to be selected from the catalyzer of above-mentioned catalyzer.

At vulcabond or polyisocyanates (a), other vulcabond (b), compound (c) and if the compound of suitable other general formula Is (d) and if after the reaction of suitable terminator (e) finishes, if radiation-curable polyurethane (A) for example can be separated by removing with unconverted starting raw material such as vulcabond (b), compound (c) if with the compound (d) of suitable other general formula Is with suitable terminator (c).With unconverted starting raw material as (b), (c) and if suitable (d) and the appropriate methodology (e) removed for preferably under the pressure that reduces, they being distilled out.Thin-film evaporator is for very particularly suitable.Preferably unconverted vulcabond (b) is not distilled out.

Be ready to use in the molecular weight M of radiation-curable polyurethane of the present invention (A) _wFor example can be for 500 to no more than 50 000g/mol, preferred 1000-30 000g/mol, more preferably 2000-25 000g/mol, most preferably 2000g/mol at least for example measures by gel permeation chromatography (GPC).

In a preferred embodiment of the invention, radiation-curable polyurethane (A) does not comprise free NCO group.

At vulcabond or polyisocyanates (a), other vulcabond (b) and compound (c) and if suitable (d) and if after the reaction of suitable terminator (e) carries out, can be with water for example with 1: 1-1: 10 radiation-curable polyurethane (A) adds with the weight ratio of water.

At vulcabond or polyisocyanates (a), other vulcabond (b) and compound (c) and if after the reaction of suitable (d) and terminator (e) carries out, the group available bases that comprises enough acid hydrogen atoms is handled they are changed into corresponding salt.Useful alkali for example comprises oxyhydroxide and the supercarbonate or the alkali-metal carbonate of basic metal or alkaline-earth metal.Useful alkali comprises volatile amine in addition, and promptly under atmospheric pressure boiling point is 180 ℃ a amine at the most, and example is ammonia, methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, thanomin or N methyldiethanol amine.Similarly, basic group usable acid such as alpha-hydroxy carboxylic acid compounds or a-amino acid or the acid of Alpha-hydroxy semi-annular jade pendant change into corresponding salt.

At vulcabond or polyisocyanates (a), other vulcabond (b) and compound (c) and if after the reaction of suitable (d) and terminator (e) carried out, any used solvent can for example separate by distillation.

After preparing radiation-curable polyurethane (A), add one or more pigment (B) and if suitable water.Preferably solids content is set at 3-40%, preferably to 35%, more preferably 5-30%.

Radiation-curable polyurethane (A) can change in wide region with the weight ratio of pigment (B).In one embodiment of the invention, the weight ratio of radiation-curable polyurethane (A) and pigment (B) is 5: 1-1: 3, preferred 3: 1-1: 2, more preferably 2: 1-2: 3.

Subsequently radiation-curable polyurethane (A) and pigment (B) are disperseed.Dispersion can be carried out in the dispersive equipment any being suitable for.For example mention as wobbler from Skandex.Preferred radiation-curable polyurethane (A) and pigment (B) are for example at ultrasonic equipment, high-pressure homogenizer, 2-, 3-, 4-or 5-roller mill, miniature grinding machine, Henschel mixer (Henschel mixers), shake grinding machine, the Ang grinding machine, the gear grinding machine, ball mill, wet wheeling machine, sand mill, bowl chopper, colloidal mill, in the ultrasonic homogenizer, with Ultra Turrax agitator, and especially for example at 2-, 3-, 4-or 5-roller mill, miniature grinding machine, shake grinding machine, the Ang grinding machine, the gear grinding machine, ball mill, wet wheeling machine, sand mill, colloidal mill, disperse by grinding in the ball mill, particularly agitating ball mill.

The jitter time that is fit to for example is 10 minutes to 48 hours, and the longer time also is possible.Preferred jitter time is 15 minutes to 24 hours.

Pressure and temperature condition between dispersed phase is not crucial usually, has for example found that barometric point is what be fit to.As temperature, for example found 10-100 ℃ for being fit to, preferably at the most 80 ℃.

Disperse to provide water dispersion of the present invention.In one embodiment of the invention, the solids content of water dispersion of the present invention is 3-40%, preferably at the most 35%, and more preferably 5-30%.

Can add conventional grinding aid between dispersed phase.

After the dispersion, the mean diameter of the pigment of being sealed to small part by radiation-curable polyurethane (A) (B) is 20nm to 1.5 μ m, preferred 60-500nm, more preferably 60-350nm, and ordinary representation volume averaging for the present invention.The useful measuring appliance that is used to measure median size for example comprises CoulterCounters such as Coulter LS 230.

When needs carbon black used according to the invention during as pigment (B), particle diameter is based on the mean diameter of primary particle.

Water dispersion of the present invention does not comprise thermal initiator, promptly be not included in 60 ℃ of half-life at least 1 hour and split into the compound of radical in the method, the example superoxide, hydroperoxide, hydrogen peroxide, persulphate, azo-compound such as Diisopropyl azodicarboxylate (AIBN) or water-soluble AIBN derivative, high replacement, especially hexabasic ethane derivative or redox catalyst.

In one embodiment of the invention, water dispersion of the present invention comprises at least a urethane (C).Urethane (C) for example can obtain by vulcabond (b) and compound (c) reaction, does not preferably comprise allophanate groups.Special preferred pigments (B), and is sealed by urethane (C) to small part by radiation-curable polyurethane (A) for not only.

In one embodiment of the invention, water dispersion of the present invention is with 10: 1-1: 2, preferred 8: 1-1: 1 (weight ratio) comprises radiation-curable polyurethane (A) and urethane (C).

In one embodiment of the invention, water dispersion of the present invention comprises at least a light trigger (D).Can be before dispersion or alternatively in disperseing the back to add with light trigger (D).

The light trigger (D) that is fit to for example comprises light trigger well known by persons skilled in the art, example is at " Advances in Polymer Science ", the 14th volume, Springer Berlin 1974 or at K.K.Dietliker, Chemistry and Technology 0f UV-and EB-Formulationfor Coatings, Inks and Paints, the 3rd volume; Photoinitiators for Free Radicaland Cationic Polymerization, P.K.T.Oldring (Eds), SITA TechnologyLtd, those that mention among the London.

Useful light trigger for example comprises for example as EP-A 0 007 508, EP-A 0 057 474, DE-A 196 18 720, EP-A 0 495 751 and EP-A 0 615 980 described monoacyl phosphine oxide or two acylphosphine oxide; example is 2; 4; 6-Three methyl Benzene formyl diphenyl phosphine oxide, ethyl 2; 4; 6-Three methyl Benzene formylphenyl phosphinate, two (2; 4,6-Three methyl Benzene formyl) mixture of phenylphosphine oxide, benzophenone, hydroxyacetophenonum, phenyl oxoethanoic acid and derivative or above-mentioned light trigger.Can mention benzophenone as an example; methyl phenyl ketone; the acetyl naphthoquinones; methyl ethyl ketone; the benzene pentanone; the benzene hexanone; α-phenyl phenyl propyl ketone; to the morpholinyl Propiophenone; dibenzosuberone; 4-morpholine benzophenone; 4-morpholinyl phenylbenzyl ketone; to diacetyl benzene; the 4-aminobenzophenone; 4 '-methoxyacetophenone; β-Jia Jienkun; tertiary butyl anthraquinone; the anthraquinone carboxylic acids ester; phenyl aldehyde; α-Tetralone an intermediate of Sertraline; 9-ethanoyl phenanthrene; 2-ethanoyl phenanthrene; the 10-thioxanthone; 3-ethanoyl phenanthrene; 3-ethanoyl indoles; the 9-Fluorenone; the 1-indone; 1; 3; 4-triacetyl benzene; Thiaxanthene-9-ketone; xanthene-9-ketone; 2; 4-dimethyl thioxanthone; 2; the 4-diethyl thioxanthone; 2; 4-di-isopropyl thioxanthone; 2; 4-two clopenthixal ketones; bitter almond oil camphor; the bitter almond oil camphor isobutyl ether; the chlorine xanthone; bitter almond oil camphor THP trtrahydropyranyl ether; benzoin methylether; the bitter almond oil camphor ethyl ether; the bitter almond oil camphor butyl ether; the bitter almond oil camphor isopropyl ether; the 7-H-benzoin methyl ether; phenyl [taking off] anthracene-7-ketone; the 1-naphthaldehyde; 4; 4 '-two (dimethylamino) benzophenone; the 4-phenyl benzophenone; the 4-chlorobenzophenone; Michler's keton (Michler ' s ketone); the 1-acetonaphthone; the 2-acetonaphthone; 1-benzoyl hexamethylene-1-alcohol; 2-hydroxyl-2; the 2-dimethyl acetophenone; 2; 2-dimethoxy-2-phenyl methyl phenyl ketone; 2; 2-diethoxy-2-phenyl methyl phenyl ketone; 1; the 1-dichloroacetophenone; the 1-hydroxy acetophenone; the methyl phenyl ketone dimethyl ketal; the O-methoxy benzophenone; triphenylphosphine; three adjacent toluene phosphines; phenyl [a] anthracene-7; the 12-diketone; 2; the 2-diethoxy acetophenone; benzil ketals such as benzil dimethyl ketal; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl third-1-ketone; anthraquinone such as 2-methylanthraquinone; 2-ethyl-anthraquinone; 2-tertiary butyl anthraquinone; 1-chloroanthraquinone; 2-amyl anthraquinone and 2, the 3-dimethyl diketone.

The non-flavescence or the minimum flavescence light trigger that also have the phenyl glyoxylic acid ester type that are fit to are as described in DE-A198 26 712, DE-A 199 13 353 or WO 98/33761.

Preferred light trigger (D) for example comprises once the light trigger that activates the so-called α-disintegrating agent of splitted (spiltter), for example light trigger of benzil dialkyl group ketal type.Other examples of useful α-disintegrating agent are the derivative of bitter almond oil camphor; isobutyl-benzoin ether, phosphine oxide; especially monoacyl phosphine oxide and two acylphosphine oxide; benzoyl diphenyl phosphine oxide, 2 for example; 4; 6-Three methyl Benzene formyl diphenyl phosphine oxide, Alpha-hydroxy alkylbenzene ethyl ketone such as 2-hydroxy-2-methyl phenyl-acetone (D.1):

2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methyl isophthalic acid-acetone (D.2):

Phosphine sulfide and 4-dimethylaminobenzoic acid ethyl ester and (D.3):

Preferred light trigger (D) comprises for example hydrogen-capture-type light initiator in addition, as replacing or unsubstituted methyl phenyl ketone, anthraquinone, thioxanthone, benzoic ether type or replacement or unsubstituted diphenyl ketone type.Particularly preferred example is isopropyl thioxanthone, benzophenone, phenylpropiophenone, 4-methyldiphenyl ketone, the benzophenone of halomethylation, anthrone, Michler's keton (4,4 '-two-N, N-dimethylamino benzophenone), 4-chlorobenzophenone, 4,4 '-dichloro benzophenone, anthraquinone.

In one embodiment of the invention, enough light triggers (D) are added in the water dispersion of the present invention, making the weight ratio of radiation-curable polyurethane (A) and light trigger (D) is 3: 1-10 000: 1, preferred 5: 1-5000: 1, most preferably 10: 1-1000: 1.

If necessary, the effectiveness of light trigger (D) in water dispersion of the present invention can be by adding for example at least a amine of at least a synergistic agent, especially at least a tertiary amine and strengthening.Useful amine for example comprises triethylamine, N, the polyether acrylate of N-dimethylethanolamine, N-Mono Methyl Ethanol Amine, trolamine, amino acrylates such as amine modification.When for example amine such as tertiary amine in synthetic radiation-curable polyurethane (A) as catalyzer and synthetic after when not removed, tertiary amine also can be used as the catalyzer that serves as synergistic agent.Similarly, be used for and acidic-group such as COOH group or SO ₃The tertiary amine of H group can serve as synergistic agent.Based on used light trigger (A), can be added to the synergistic agent of many twices molar weight.

Water dispersion of the present invention can add at least a stopper (E) as UV absorption agent or free-radical scavengers.The UV absorption agent changes into heat energy with the UV radiation.Useful UV absorption agent for example comprises oxanilide, triazine and benzotriazole, and (latter can be used as Tinuvin ^Trade mark is obtained by Ciba-Spezialit  tenchemie), benzophenone, dihydroxy benaophenonel, quinhydrones, quinhydrones monoalky lether such as Hydroquinone monomethylether.Free-radical scavengers is in conjunction with free radical intermediate.Useful free-radical scavengers for example comprises the known bulky amine as HALS (hindered amine as light stabilizer).The example is 2,2,6, and 6-tetramethyl piperidine, 2,6-di-t-butyl piperidines or derivatives thereof, example are two (2,2,6,6-tetramethyl--4-piperidyl) sebates.

For example, can add 5 weight % at the most, the more preferably stopper of 0.5 weight % (E) at the most based on (A) and summation (B).

Dispersion of the present invention can add one or more other compounds (F) with the two keys of C-C, and it is called unsaturated compound (F) hereinafter.Particularly suitable unsaturated compound (F) for example comprises the compound of general formula I.Other particularly suitable unsaturated compounds (F) are F.1 those of general formula:

Wherein

R ¹And R ²Identical or different and be independently selected from hydrogen and C ₁-C ₁₀Alkyl,

M is the integer of 0-2, preferred 1;

A ²When m=0 CH ₂Or-CH ₂-CH ₂-or R ⁸-CH or to C ₆H ₄,

When m=1 CH, C-OH, C-O-C (O)-CH=CH ₂, C-O-CO-C (CH ₃)=CH ₂,

R ⁸-C or 1,3,5-C ₆H ₃,

When m=2 carbon;

R ⁸Be selected from C ₁-C ₄Alkyl such as positive C ₄H ₉, positive C ₃H ₇, different C ₃H ₇, preferred C ₂H ₅And CH ₃, or phenyl,

A ³, A ⁴And A ⁵Identical or different and be selected from separately:

C ₁-C ₂₀Alkylidene group is as-CH ₂-,-CH (CH ₃)-,-CH (C ₂H ₅)-,-CH (C ₆H ₅)-,-(CH ₂) ₂-,-(CH ₂) ₃-,-(CH ₂) ₄-,-(CH ₂) ₅-,-(CH ₂) ₆-,-(CH ₂) ₇-,-(CH ₂) ₈-,-(CH ₂) ₉-,-(CH ₂) ₁₀-,-CH (CH ₃)-(CH ₂) ₂-CH (CH ₃)-;

Along or anti-C ₄-C ₁₀Ring alkylidene group such as suitable-1,3-cyclopentylidene, anti--1,3-cyclopentylidene, suitable-1,4-cyclohexylidene, anti--1,4-cyclohexylidene;

C ₁-C ₂₀Alkylidene group, wherein 1 to 7 non-conterminous separately carbon atom is replaced by oxo in each case, as-CH ₂-O-CH ₂-,-(CH ₂) ₂-O-CH ₂-,-(CH ₂) ₂-O-(CH ₂) ₂-,-[(CH ₂) ₂-O] ₂-(CH ₂) ₂-,-[(CH ₂) ₂-O] ₃-(CH ₂) ₂-;

The C that replace by 4 hydroxyls at the most ₁-C ₂₀Alkylidene group, wherein 1 to 7 non-conterminous separately carbon atom is replaced by oxo, for example-CH ₂-O-CH ₂-CH (OH)-CH ₂-,-CH ₂-O-[CH ₂-CH (OH)-CH ₂] ₂-,-CH ₂-O-[CH ₂-CH (OH)-CH ₂] ₃-; C ₆-C ₁₄-arylidene is as to C ₆H ₄

The particularly preferred example of general formula compound F.1 is three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate and tetramethylolmethane four (methyl) acrylate of trimethylolpropane tris (methyl) acrylate, triple ethoxylated trimethylolpropane.

Other of unsaturated compound (F) are very useful is represented as ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propylene glycol (methyl) acrylate, dipropylene glycol two (methyl) acrylate and tripropylene glycol two (methyl) acrylate.

Other very useful typical examples of unsaturated compound (F) are as being the polyvalent alcohol of partially or completely (methyl) acroleic acid esterification as the dimerization TriMethylolPropane(TMP) of (methyl) acroleic acid esterification partially or completely, partially or completely dimerization trimethylolethane, the dipentaerythritol of (methyl) acroleic acid esterification partially or completely of (methyl) acroleic acid esterification.

For example, can add, amount to 100 weight % at the most, preferred 50 weight % at the most, the more preferably unsaturated compound of 25 weight % (F) at the most based on (A) and summation (B).

Water dispersion of the present invention as or be used to dye or the preparaton of printing element for preparation, for example be used for the staining fluid of pigment dyeing for preparation or printing slurry that preparation is used for color-printed very useful.

Therefore, the present invention further provides water dispersion of the present invention as or be used to prepare and be used to dye or the purposes of the preparaton of printing element.It is a kind of by using at least a water dispersion of the present invention to be used to dye or the method for printing element that the present invention provides equally.

Useful base material comprises:

Cellulose materials such as paper, cardboard, card, timber and wooden base material, its can respectively do for oneself painted or coating,

Paper tinsel, sheet material or the workpiece of metallic substance as comprising aluminium, iron, copper, silver, gold, zinc or its alloy, its can respectively do for oneself painted or coating,

Silicate material such as glass, porcelain and pottery, its coating of can respectively doing for oneself,

The polymeric material of any kind of such as polystyrene, polymeric amide, polyester, polyethylene, polypropylene, melamine resin, polyacrylic ester, polyacrylonitrile, urethane, polycarbonate, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone and comprise multipolymer, biodegradable polymers and natural polymer such as the gelatin of segmented copolymer accordingly

With the natural and imitation leather of smooth leather, nappa leather or velour form, foods and cosmetics, and especially

Fiber, yarn, silk thread, cloth, weaven goods, non-woven fabric and the clothes of textile substrate as comprising polyester, modified poly ester, polyester blend fabric, cellulose materials is as cotton, cotton blended fabric, jute, flax, hemp and ramie, viscose glue, wool, silk, polymeric amide, polymeric amide BLENDED FABRIC, polyacrylonitrile, triacetate, acetic ester, polycarbonate, polypropylene, polyvinyl chloride, and BLENDED FABRIC such as polyester-polyurethane BLENDED FABRIC are (as Lycra ^), polyethylene-polypropylene BLENDED FABRIC, polyester microfiber and glasscloth.

Water dispersion of the present invention as or be used for the printing ink of ink jet method for preparation, particularly useful in particular for the aqueous ink of ink jet method.It is very particularly useful that water dispersion of the present invention is used for containing for the pigment aqueous ink of ink jet method for preparation.Therefore the present invention provides water dispersion of the present invention to be used for the purposes of the printing ink of ink jet method in preparation.The present invention further provides and use at least a water dispersion preparation of the present invention to be used for the method for the printing ink of ink jet method a kind of comprising.

In the scope of the invention, the printing ink that is used for ink jet method also will be called jetted ink or abbreviate printing ink as.

In one embodiment of the invention, jetted ink of the present invention comprises 1-40 weight %, and preferred 2-35 weight % water dispersion of the present invention, weight % are separately based on the gross weight of the relevant printing ink of the present invention.

Water dispersion of the present invention also can directly be used as jetted ink.

In another embodiment, jetted ink of the present invention can comprise at least a additional material (G).

In one embodiment of the invention, if jetted ink of the present invention is by preparing water dispersion dilute with water of the present invention and suitable the mixing with one or more additional materials (G).

In one embodiment of the invention, the solids content of jetted ink of the present invention is set at 5-40%, and preferably at the most 35%, more preferably 10-30%.

Jetted ink of the present invention can comprise one or more organic solvents as additional material (G).Lower molecular weight polytetrahydrofuran (poly-THF) is preferred additional material (G), and it can use separately or preferred mixture use with or water miscibility solvent water-soluble with one or more high boiling points.

The molecular-weight average M of preferred lower molecular weight polytetrahydrofuran _wBe generally 150-500g/mol, preferred 200-300g/mol, more preferably from about 250g/mol (consistent) with molecular weight distribution.

Polytetrahydrofuran prepares by the cationoid polymerisation of tetrahydrofuran (THF) in known manner.Product is linear polytetramethylene glycol.

When polytetrahydrofuran with the mixture of other organic solvents during as additional material (G), other used organic solvents usually will for high boiling product (promptly usually under atmospheric pressure boiling point＞100 ℃) and therefore be water soluble or can with water-soluble mixed water conservation organic solvent.

Useful solvent comprises polyvalent alcohol, preferably have 2-8, especially the non-branching of 3-6 carbon atom and branching polyvalent alcohol, ethylene glycol, 1 for example, 2-propylene glycol, 1, ammediol, glycerol, tetrahydroxybutane, tetramethylolmethane, pentitol such as arabitol, ribitol and Xylitol and hexitol such as Sorbitol Powder, mannitol and galactitol.

Useful solvent comprises polyoxyethylene glycol and polypropylene glycol in addition, comprises their oligopolymer (dipolymer, trimer and tetramer) and their list (C especially ₁-C ₆Especially C ₁-C ₄) alkyl oxide.Preferred molecular weight M _nBe 100-6000g/mol, especially to 1500g/mol, the particularly polyoxyethylene glycol of 150-500g/mol and polypropylene glycol.Example can be mentioned Diethylene Glycol, triethylene glycol and TEG, diethylene glycol monomethyl ether, TC, Diethylene Glycol monoisopropyl ether, Diethylene Glycol list propyl ether, Diethylene Glycol list n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethyl ether, triethylene glycol list n-propyl ether, the triethylene glycol monoisopropyl ether, triethylene glycol list n-butyl ether, two-, three-and four--1,2-and-1, ammediol, with two-, three-and four--1,2-and-1, ammediol monomethyl, single ethyl, single n-propyl, single sec.-propyl and single n-butyl ether.

Useful solvent comprises that in addition pyrrolidone and alkyl chain preferably comprise 1-4, especially the N-alkyl pyrrolidone of 1 or 2 carbon atom.The example of useful alkyl pyrrolidone is N-Methyl pyrrolidone, N-ethyl pyrrolidone and N-(2-hydroxyethyl) pyrrolidone.

The example of particularly preferred solvent is 1,2-propylene glycol, 1, ammediol, glycerol, Sorbitol Powder, Diethylene Glycol, polyoxyethylene glycol (M _wBe 300-500g/mol), Diethylene Glycol single-butyl ether, triethylene glycol single-butyl ether, pyrrolidone, N-Methyl pyrrolidone and N-(2-hydroxyethyl) pyrrolidone.

Polytetrahydrofuran also can with one or more (for example two kinds, three kinds or four kinds) above-mentioned solvent.

In one embodiment of the invention, ink jet method printing ink of the present invention can comprise 0.1-80 weight %, preferred 2-60 weight %, more preferably 5-50 weight %, most preferably 10-40 weight % non-aqueous solvent.

As the non-aqueous solvent of additional material (G), comprise that the particularly preferred solvent combination of especially determining can preferably augment (usually with the weight based on colorant preparations, 0.5-3 weight %) water retention with further enhancing solvent mixture with urea.

Ink jet method printing ink of the present invention can comprise other additional materials of conventional kind (G) that are particularly useful for moisture jetted ink and printing and coatings industry.Example for example comprises sanitas as 1,2-benzisothiazole-3-ketone (commercial by Avecia Lim. as the Proxel trade mark) and its an alkali metal salt, glutaraldehyde and/or tetramethylol acetylene diurea, Protectols ^Antioxidant, air release agent/defoamer such as acetylenediol and common every mole of acetylenediol comprise 20-40 mole ethylene oxide and also can dispersing ethoxylation acetylenediol, viscosity modifier, flowing agent, wetting agent is (for example based on the wetted surface promoting agent of ethoxylation or propoxylated fatty alcohol or oxo alcohol, propylene oxide-ethylene oxide segmented copolymer, oleic ethoxylate or alkylphenol, alkyl phend ether sulfate, APG, alkyl phosphonate, the alkyl phenyl phosphonate, alkylphosphonic, alkyl phenyl phosphoric acid salt or preferred, polyethers silicone copolymers, especially usually comprise 7-20, the block and the 2-20 of preferred 7-12 ethylene oxide unit, the block of preferred 2-10 propylene oxide unit and can be contained in alkoxylate 2-(3-hydroxypropyl) seven methyl trisiloxanes in the colorant preparations with the amount of 0.05-1 weight %), anti-sedimentation agent, gloss modifier, glidant, bonding improver, anti, flatting agent, emulsifying agent, stablizer, hydrophobizing agent, the light guide additive, feel improving agent, static inhibitor, alkali such as trolamine or acid, especially carboxylic acid such as lactic acid or citric acid are to adjust pH.When these reagent during for the integral part of jetted ink of the present invention, their total amount will be usually based on colorant preparations of the present invention, is 2 weight % in particular for the weight of the printing ink of the present invention of ink jet method, especially 1 weight %.

Useful additional material (G) comprises alkoxylate or non-oxyalkylated acetylenediol in addition, as general formula I I:

Wherein

The oxyalkylene units that AO representative is identical or different, for example propylene oxide unit, oxybutylene unit and especially ethylene oxide unit,

R ⁴, R ⁵, R ⁶And R ⁷Identical or different separately and be selected from the C of branching or non-branching ₁-C ₁₀Alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl, more preferably C ₁-C ₄Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl; And hydrogen;

Identical or different and be selected from 0 to 50, preferred 0 or 1 to 30 when b occurs at every turn, more preferably 3 to 20 integer;

In a preferred embodiment of the invention, R ⁵Or R ⁷Be methyl.

In a preferred embodiment of the invention, R ⁵And R ⁷Be methyl and R ⁴And R ⁶Be isobutyl-.

Alkoxylate that other preferred additional material is a general formula III or non-alkoxylate silicon compound:

[(CH ₃) ₃Si-O] ₂-Si(CH ₃)-O(CH ₂CH ₂O) _b-H III

Wherein b as above defines.

Ink jet method printing ink of the present invention can comprise in addition and is selected from light trigger as defined above but is different from the light trigger that can be used for the light trigger (D) in the water dispersion preparation of the present invention.

In one embodiment of the invention, the dynamic viscosity of ink jet method printing ink of the present invention is determined as 2-80mPas according to German standard standard DIN 53018 under 23 ℃, preferred 3-40mPas, more preferably 25mPas at the most.

In one embodiment of the invention, the surface tension of ink jet method printing ink of the present invention is determined as 24-70mN/m according to German standard standard DIN 53993 under 25 ℃, especially 25-60mN/m.

In one embodiment of the invention, the pH of ink jet method printing ink of the present invention is 5-10, preferred 7-9.

Ink jet method printing ink of the present invention has total favourable serviceability, especially well start to print performance and good sustained use properties (fouling (kogation)) and, especially when using particularly preferred group of solvents fashionable, have well dried performance, and to produce high quality be high brightness and colourity and the high level cadre is wear-resisting, fast light, water-fast and the printed images of wet wear resistance.They are particularly useful for printed coating and common paper and textile substrate.

Another aspect of the present invention is a kind of method for preparing ink jet method printing ink of the present invention.If the present invention preparation is used for the method for the printing ink of ink jet method and for example comprises and in one or more steps at least a water dispersion of the present invention, water and suitable at least a additional material (G) being mixed mutually.

Useful hybrid technology for example for example comprises and to stir in ball mill or agitating ball mill and acutely to shake and to disperse.

With water dispersion of the present invention, water suitable if (C) if suitable (D) if suitable (E) if suitable (F) and if suitable (G) when mixing, the order of adding is not crucial equally.

Therefore, in a scheme of the present invention, can at first synthesize at least a radiation-curable polyurethane (A), use pigment (B) to disperse then, with one or more desired additives (C), (D), (E), (F) and/or (G) mix dilute with water before or after mixing thereafter.

In another scheme of the present invention, synthetic at least a radiation-curable polyurethane (A) and at least a urethane (C) are used (B) dispersion then, dilute with water and mix with one or more desired additives (D), (E), (F) and/or (G).

In another scheme of the present invention, synthetic at least a radiation-curable polyurethane (A) is used pigment (B) and desired additives (C), (D), (E), (F) and one of (G) dispersion at least then.

In another scheme of the present invention, synthetic at least a radiation-curable polyurethane (A) and at least a urethane (C) are used pigment (B) and desired additives (D), (E), (F) and one of (G) dispersion at least then.

Another aspect of the present invention is a kind of method of using at least a ink jet method printing ink of the present invention by ink jet method printing sheet or three-dimensional substrates, hereinafter be also referred to as printing process of the present invention.For putting into practice printing process of the present invention, at least a jetted ink of the present invention is printed to base material.Preferred version of the present invention comprises at least a jetted ink of the present invention is printed to base material, uses photochemical radiotreatment then.

In ink ejecting method, usually aqueous ink directly is sprayed on the base material as small droplets.The method that has continuous form, wherein make printing ink press nozzle with uniform rate, and depend on that pattern to be printed aims at jet on the base material by electric field, there is interruption or drips China ink (drop-on-demand) method as required, wherein only printing ink is mapped to and will the place of colored spots occurs, the method for back one form use piezoquartz or hot hollow needle (Bubble or Thermal Jet method) with ink system is exerted pressure and therefore ink jet drip.These technical descriptions are in Text.Chem.Color, the 19th (8) volume, and the 23-29 page or leaf, the 1987 and the 21st (6) volume, the 27-32 page or leaf is in 1989.

Printing ink of the present invention is for the bubble jet method and use the method for piezoquartz particularly useful.

Jetted ink of the present invention can solidify by actinic radiation.For example wavelength is that the actinic radiation of 200-450nm is useful.For example energy is 70-2000mJ/cm ²Actinic radiation be useful.Actinic radiation for example can advantageously be used continuously or with the form of flash of light.

In one embodiment of the invention, can be with printing back and for example hot or inner dry with the IR radiation with the base material before the photochemical radiotreatment.The example of the condition that is fit to is 30-120 ℃ a temperature 10 seconds to 24 hours, preferably at the most 30 minutes, more preferably at the most 5 minutes during.Useful IR radiation for example comprises that the ripple district is the above IR radiation of 800nm.Useful inside drying plant for example comprises and is used for the loft drier that hot inner exsiccant comprises vacuum drying oven, and the IR lamp.

Similarly, use the heat that actinic radiation comprised and to have inner drying effect.

The present invention further provides by one of the invention described above printing process printing and significantly part especially be base material, the especially textile substrate of printed images clearly or pattern and excellent feel.In addition, printing element of the present invention has few soft spots.

In other embodiments of the present invention, can be with two or more, preferred three kinds or multiple different ink jet method ink combination of the present invention are complete, in this case, each self-contained different pigment that have different colours separately of different printing ink of the present invention.

The present invention further provides the pigment of sealing to small part for preparing by distribution of at least one pigment (B) and at least a radiation-curable polyurethane (A), described radiation-curable polyurethane (A) can pass through:

(b) at least a other vulcabond, and with

The present invention especially provides the above-mentioned pigment of sealing to small part, and wherein said vulcabond or polyisocyanates (a) prepare by the compound reaction of at least a vulcabond or polyisocyanates (a1) and at least a general formula I:

Wherein

X ¹Be selected from oxygen and N-R ³,

A ¹Be selected from not and replace or by C ₁-C ₄Alkyl, phenyl or O-C ₁-C ₄The alkyl list replaces or polysubstituted and wherein one or more non-conterminous CH ₂Group can be by the displaced C of oxygen ₁-C ₂₀Alkylidene group,

X ²Be selected from hydroxyl and NH-R ³,

R ³Identical or different in each case and be selected from hydrogen, C ₁-C ₁₀Alkyl and phenyl.

The present invention especially provides the pigment of sealing to small part, and wherein radiation-curable polyurethane (A) passes through:

(b) at least a other vulcabond, and with

(c) at least a compound with at least two isocyanate-reactive groups and

(d) compound of at least a general formula I reacts and obtains:

Wherein

X ¹Be selected from oxygen and N-R ³,

X ²Be selected from hydroxyl and NH-R ³,

A kind of the present invention of preparation forms theme part of the present invention as mentioned above and equally to the method for the pigment that small part is sealed.

The pigment that the present invention seals to small part for example can for example be obtained by drying, lyophilize, filtration or its combination by removing to anhydrate by water dispersion of the present invention.

The pigment that the present invention seals to small part is particularly useful for the printing ink that preparation is used for ink jet method.

The present invention further provides the radiation-curable polyurethane for preparing by following reaction:

(b) at least a other vulcabond, and with

(C) at least a compound with at least two isocyanate-reactive groups and

(d) reaction of the compound of at least a general formula I.

In one embodiment of the invention, two key density of radiation-curable polyurethane of the present invention (A) for example can be by measuring the hydrogenation iodine number and passing through ¹H NMR spectrographic determination is 0.1-5mol/kg (A), preferred 0.2-3mol/kg (A), most preferably 0.3-2mol/kg (A).

The method for preparing radiation-curable polyurethane of the present invention forms theme part of the present invention as mentioned above equally.

Radiation-curable polyurethane of the present invention is particularly useful for preparation jetted ink of the present invention and preparation water dispersion of the present invention.

The present invention illustrates by work embodiment.

Usually preparation:

Under every kind of situation NCO content according to German standard standard DIN 53185 titrimetries measure.

The degree of sealing of pigment of the present invention uses the freeze-fracturing technical measurement by the projection electron microscope method.

Tetrahydrofuran (THF) (THF) is dry by distillation on sodium/benzophenone before use.

Solids content: the % in the scope of the invention is weight %.Solids content in the scope of the invention all by measuring down at 150 ℃ in dry 30 minutes.

I. prepare the pigment of sealing to small part of the present invention

I.1 prepare radiation-curable polyurethane (A.1)

I.1.1 preparation comprises the vulcabond (a.1) of allophanate and the two keys of C-C

Repeat the embodiment 1.1 of EP 1,144 476 B1.Hexamethylene diisocyanate (HDI) (a.1.1) is mixed in stirred flask with 2-hydroxyethylmethacry,ate and nitrogen and be heated to 80 ℃.With 200 ppm by weight 2-ethyl base caproic acid N, N, N-trimethylammonium-N-(2-hydroxypropyl) ammonium

Add, thereafter temperature is risen to 120 ℃ in half an hour.Thereafter, the reaction mixture that obtains being remained on 120 ℃ of NCO content of measuring until titrimetry under continuously stirring is 25 weight % based on total reaction mixture.Reaction is by adding based on (a.1.1), 250 ppm by weight di-(2-ethylhexyl)phosphoric acid esters and stopping.Therefore available mixture is removed unconverted HDI subsequently under 135 ℃ and 2.5 millibars in thin-film evaporator.Therefore the NOC content of available vulcabond (a.1) is 15 weight %, and the dynamic viscosity under 23 ℃ is 1200mPas.Remaining HDI content is 0.5 weight %.The two key density of C-C are the two keys of 2 C-C of per molecule.

I.1.2 (a.1) changed into radiation-curable polyurethane of the present invention (A.1)

With 239.7g by m-phthalic acid, hexanodioic acid and 1, the molecular weight M that 4-dihydroxyl methylcyclohexane (isomeric mixtures) prepares with 1: 1: 2 mol ratio polycondensation _wFor the polyester glycol of 800g/mol is heated to 120 ℃.The melt transfer that obtains to 21 reactors that agitator, reflux exchanger, inlet pipe and dropping funnel are housed, and is heated to 130 ℃ under nitrogen.In case polyester glycol exists as limpid melt, just its stirring is cooled to 80 ℃.Be cooled to 60 ℃ before add 31.2g neopentyl glycol and 101.9g1,1-dimethylol propionic acid thereafter.Add 630g tetrahydrofuran (THF) (THF), 85.2g vulcabond (a.1) and 234g hexamethylene diisocyanate (HDI) (a.2.1) thereafter.Adding 1000ppm di-n-butyltin dilaurate (based on HDI) after this and being reduced to based on total reaction mixture at the NCO content that 60 ℃ of following stirrings are measured until titrimetry is 1.2 weight %.Thereafter, use ice bath that reaction mixture is cooled to room temperature, reaction stops by the diethanolamine that adding 39.9g is dissolved among the 39.9g THF.Acid groups neutralizes to obtain radiation-curable polyurethane of the present invention (A.1) with the triethylamine that 76.9g is dissolved among the 76.9gTHF subsequently.

I.2 prepare radiation-curable polyurethane of the present invention (A.2)

(IPDI) mixes with 46.7gTHF with the 15.6g isophorone diisocyanate, with mixture heating up to 50 ℃ and add based on IPDI130 ppm by weight two lauric acid two positive fourth tin.Be added in the 8.1g2-hydroxyethylmethacry,ate (d.1) among the 24.4gTHF after this.Being reduced to the reaction soln NCO content that stirring is measured until titrimetry under 50 ℃ that obtains based on total reaction soln is 3.1 weight %, add 596.1g radiation-curable polyurethane (A.1) this moment, add based on total reaction soln 0.1 weight % two lauric acid two positive fourth tin in addition after this.Then with mixture heating up to 60 ℃ and stir until NCO and no longer can titrimetry measure.Add 965g water then, distilling out THF to be left by the dynamic light scattering measurement median size is the water dispersion (solids content: 25 weight %) of the radiation-curable polyurethane of the present invention (A.2) of 15nm.

I.3 prepare radiation-curable polyurethane of the present invention (A.3)

(IPDI) mixes with 138.4gTHF with the 44.5g isophorone diisocyanate, with mixture heating up to 50 ℃ and add based on IPDI 130 ppm by weight, two lauric acid, two positive fourth tin.Be added in the 23.292-hydroxyethylmethacry,ate (d.1) among the 69.7gTHF after this.Being reduced to the reaction soln NCO content that stirring is measured until titrimetry under 50 ℃ that obtains based on total reaction mixture is 3.1 weight %, add 425.8g radiation-curable polyurethane (A.1) this moment, add based on total reaction soln 0.2 weight % two lauric acid two positive fourth tin in addition after this.Then with mixture heating up to 60 ℃ and stir until NCO and no longer can titrimetry measure.Add 841g water then, distilling out THF to be left by the dynamic light scattering measurement median size is the water dispersion (solids content: 25 weight %) of the radiation-curable polyurethane of the present invention (A.3) of 30nm.

II. Application Example

II.1 prepares water dispersion of the present invention, general prescription

Water dispersion of the present invention prepares on the Skandex shaking machine that uses the 60g diameter as the glass sphere of 0.25-0.5mm.Prescription is summarized in the table 1.After composition and glass sphere have been weighed among the Skandex, the time that the mixture that obtains is shaken in the table 1 to be reported.Sample taken out and measure the mean diameter (Coulter Counter LS230) and the measurement degree of sealing of dispersed color thereafter.Measure pH, and if necessary it is adjusted to 7.5 with trolamine.Obtain water dispersion WD.2.1 to WD.2.3 of the present invention.

Table 1: the composition of water dispersion WD.2.1 to WD.2.3 of the present invention and formulation parameter

Composition	WD.2.1	WD.2.2	WD.2.3
Composition	WD.2.1	WD.2.2	WD.2.3	(B) according to C.I.	P.R.122	P.BK.7	P.Y.138
(B)[g]	6	6	6	(B) according to C.I.	P.R.122	P.BK.7	P.Y.138
(B)[g]	6	6	6	(A.2)[g]	24	24	24
Propylene glycol [g]	3	4	3	(A.2)[g]	24	24	24
Propylene glycol [g]	3	4	3	Biocide 1[g]	0.3	0.3	0.3
Three normal-butyl phosphoric acid ester [g]	0.05	0.05	0.05	Biocide 1[g]	0.3	0.3	0.3
Three normal-butyl phosphoric acid ester [g]	0.05	0.05	0.05	Distilled water [g]	32.65	31.65	32.65
Jitter time [h]	2	1	3	Distilled water [g]	32.65	31.65	32.65
Jitter time [h]	2	1	3	Degree of sealing
The mean diameter of pigment [nm]	120	77	140	Degree of sealing

Except as otherwise noted, the amount of composition is always reported with g.

(A.2) calculate with solids content.

Biocide 1 is 1 of 20 weight %, the solution of 2-benzisothiazole-3-ketone in propylene glycol.

Other water dispersions of the present invention program as mentioned above obtain, and difference is under every kind of situation (A.2) to be replaced by (A.1) and (A.3) respectively.Obtain following water dispersion of the present invention:

WD.1.1 (scarlet is used (A.1)),

WD.1.2 (black uses (A.1)),

WD.1.3 (yellow is used (1.2)),

WD.3.1 (scarlet is used (A.3)),

WD.3.2 (black uses (A.3)),

WD.3.3 (yellow is used (A.3)).

II.2 preparation the present invention is used for the printing ink of ink jet method

II.2.1 preparation the present invention is used for the scarlet printing ink T2.1.1 of ink jet method

Following component is mixed mutually by stirring in glass beaker:

30gWD.2.1，

The 1g urea,

0.16g light trigger (D.1),

6g molecular-weight average M _nBe the poly-THF of 250g/mol,

7g M _nThe polyoxyethylene glycol of=400g/mol,

9.2g glycerol,

0.8920 the solution of the benzisothiazole-3-ketone of weight % in propylene glycol,

0.5g formula [(CH ₃) ₃Si-O] ₂Si (CH ₃)-O (CH ₂CH ₂O) ₈The ethoxylation trisiloxanes of-H,

51.34g distilled water.

Printing ink T2.1.1 of the present invention obtains after filtering by glass fibre filter (by size 1 μ m).The pH of printing ink T2.1.1 of the present invention is 7.5, and dynamic viscosity is 4.2mPas.

II.2.2 preparation the present invention is used for the printing ink T2.1.2 of ink jet method

Following component is mixed mutually by stirring in glass beaker:

30gWD.2.1，

The 1g urea,

0.16g light trigger (D.1),

6g molecular-weight average M _nBe the poly-THF of 250g/mol,

7g M _nThe polyoxyethylene glycol of=400g/mol,

9.2g glycerol,

0.35g propylene glycol diacrylate,

51.04g distilled water.

Printing ink T2.1.2 of the present invention obtains after filtering by glass fibre filter (by size 1 μ m).The pH of printing ink T2.1.2 of the present invention is 7.5, and dynamic viscosity is 4.2mPas.

III. the printing ink that is used for ink jet method with the present invention prints test

Pack into printing ink T2.1.1 of the present invention and T2.1.2 in the tube separately and use Mimaki TX2 720dpi to print to paper.Obtain five pages of A4 paper, do not have nozzle blockage.The wear resistance test obtains good value.

In addition, use Mimaki TX2 720dpi press printing separately to cotton goods printing ink T2.1.1 of the present invention and T2.1.2.

After this, fix according to three variation schemes: variation scheme 1 is exposed under the light subsequently for heated drying, and variation scheme 2 is for being exposed under the actinic radiation heated drying subsequently, and variation scheme 3 is for being exposed to apyrexia drying under the actinic radiation.

Heated drying is included in the loft drier following dry 5 minutes at 100 ℃.

Use two the different UV lamps that have from IST with impinge actinic radiation: the UV irradiator of Eta PlusM-400-U2H, Eta Plus M-400-U2HC carries out.Input 1000mJ/cm ²Energy, the phase of exposing to the open air is 10 seconds.

Obtain the printing element S2.1.1 to S2.3.1 of the present invention (printing ink T2.1.1) and the S2.1.2 to S2.3.2 (printing ink T2.1.2) of table 2 and 3, and measure wear resistance, measure fastness to washing according to ISO 105-C06:1994 according to ISO-105-D02:1993.

Table 2: the fastness of the cotton goods of the present invention's printing

Base material	Wear resistance (doing)	Fastness to washing	Wear resistance (wetting)
Base material	Wear resistance (doing)	Fastness to washing	Wear resistance (wetting)	S2.1.1	3	3-4	2-3
S2.2.1	3	4	3	S2.1.1	3	3-4	2-3
S2.2.1	3	4	3	S2.3.1	3	4	3
S2.1.2	3	4-5	3	S2.3.1	3	4	3
S2.1.2	3	4-5	3	S2.2.2	3	4-5	3
S2.3.2	3	4-5	3	S2.2.2	3	4-5	3

Claims

1. water dispersion that comprises the pigment of sealing to small part by at least a radiation-curable polyurethane (A) (B), described at least a radiation-curable polyurethane (A) can pass through:

(b) at least a other vulcabond, and with

2. according to the water dispersion of claim 1, wherein said vulcabond or polyisocyanates (a) prepare by the compound reaction of at least a vulcabond or polyisocyanates (a1) and at least a general formula I:

Wherein

R ¹And R ²Identical or different and be selected from hydrogen and C independently of one another ₁-C ₁₀Alkyl,

X ¹Be selected from oxygen and N-R ³,

X ²Be selected from hydroxyl and NH-R ³,

3. according to the water dispersion of claim 1 or 2, wherein at least a compound (c) with at least 2 isocyanate-reactive groups is selected from 1,1,1-trishydroxymethyl-C ₁-C ₄Alkyl carboxylic acid, citric acid, 1,1-dihydroxymethyl-C ₁-C ₄Alkyl carboxylic acid, 1,1-dihydroxymethyl-C ₁-C ₄Alkylsulphonic acid, average per molecule have 3-300 C ₂-C ₃Poly--the C of oxyalkylene units ₂-C ₃Aklylene glycol has COOM or SO ₃The wetting ability polyamines of M group, wherein M is selected from alkalimetal ion and ammonium ion, the polyester glycol that can prepare by at least a aliphatic series or cycloaliphatic diol and at least a aliphatic series, aromatics or cycloaliphatic dicarboxylic acid's polycondensation.

4. according to each water dispersion among the claim 1-3, it comprises at least a urethane (C) that obtains by vulcabond (b) and compound (c) reaction with at least two isocyanate-reactive groups in addition.

5. according to the water dispersion of claim 4, wherein said pigment (B) is sealed by urethane (C) part.

6. according to each water dispersion among the claim 1-5, it comprises at least a light trigger (D).

7. according to the water dispersion of claim 6, wherein said at least a light trigger (D) is for α-disintegrating agent or take the hydrogen light trigger by force.

8. according to each water dispersion among the claim 1-7, wherein said radiation-curable polyurethane (A) passes through:

(b) at least a other vulcabond, and with

(c) at least a compound with at least two isocyanate-reactive groups and

(d) compound of at least a general formula I reacts and prepares.

9. one kind prepares according at least one the method for water dispersion among the claim 1-8, it comprise at least a pigment (B) disperseed with at least a radiation-curable polyurethane (A) and, if suitable at least a urethane (C) and/or at least a light trigger (D) of before or after described dispersion, adding.

10. according to the method for claim 9, wherein said being dispersed in the ball mill carried out.

11. according among the claim 1-8 each water dispersion as or be used to prepare and be used to dye or the purposes of the preparaton of printing element.

12. one kind is used to dye or the method for printing element, it comprise use at least a according to each water dispersion among the claim 1-8.

13. base material that dyes or print by method according to claim 12.

14. a method for preparing the printing ink that is used for ink jet method, it comprise use at least a according to each water dispersion among the claim 1-8.

15. a printing ink that is used for ink jet method, it comprises at least a according to each water dispersion among the claim 1-8.

16. the method for a printing element, it comprises the printing ink that is used for ink jet method of use according to claim 15.

17. base material that passes through according to the available printing of method of claim 16.

18. the pigment of sealing to small part by at least a pigment (B) and at least a radiation-curable polyurethane (A) being disperseed prepare, described radiation-curable polyurethane (A) can pass through:

(b) at least a other vulcabond, and with

19. according to the pigment of sealing to small part of claim 18, wherein said vulcabond or polyisocyanates (a) prepare by the compound reaction with at least a general formula I of at least a vulcabond or polyisocyanates (a1):

Wherein

X ¹Be selected from oxygen and N-R ³,

X ²Be selected from hydroxyl and NH-R ³,

20. according to the pigment of sealing to small part of claim 18 or 19, wherein said radiation-curable polyurethane (A) passes through:

(b) at least a other vulcabond, and with

(c) at least a compound with at least two isocyanate-reactive groups and

(d) compound of at least a general formula I reacts and prepares:

Wherein

X ¹Be selected from oxygen and N-R ³,

X ²Be selected from hydroxyl and NH-R ³,

21. the radiation-curable polyurethane for preparing by following reaction:

(b) at least a other vulcabond, and with

(c) at least a compound with at least two isocyanate-reactive groups and

(d) reaction of the compound of at least a general formula I.