COMPOSITION CONTAINING LOW-VOC, AMINOALKYL-FUNCTIONAL SILICON COMPOUNDS FOR COATING COLORS FOR THE TREATMENT OF PAPER OR FILM

Abstract

A composition has particularly good solubility in water. The composition includes an aminoalkyl-functional and/or oligo-silylated-aminoalkyl-, hydroxy-, and optionally alkoxy-functional silicon compound having reacted units of (A) an aminoalkylalkoxysilane; (B) a bis-silylated alkylamine; (C) a tri-silylated alkylamine; and (D) at least two of the alkylamines (A), (B), and (C), where the free alcohol content of the composition is less than or equal to 1% by weight, based on the composition.

Claims

1-14. (canceled)

15. A composition, comprising: an aminoalkyl-functional and/or oligo-silylated-aminoalkyl-, hydroxy-, and optionally alkoxy-functional silicon compound comprising reacted units of: (A) at least one aminoalkylalkoxysilane of formula I
NR.sub.2[(CH.sub.2).sub.2NR].sub.xYSi(R).sub.n(OR).sub.3-n (I), in which groups R, R and R are alike or different and are each a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, Y is a divalent alkylene group selected from the group consisting of CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, and [CH.sub.2CH(CH.sub.3)CH.sub.2], x is 0, 1 or 2, and n is 0 or 1, or (B) at least one bis-silylated alkylamine of formula II
(RO).sub.3-m(R).sub.mSiY[NR(CH.sub.2).sub.2].sub.yNR[(CH.sub.2).sub.2NR].sub.2YSi(R).sub.n(OR).sub.3-n (II), in which groups R, R and R are alike or different and are each a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, groups Y are alike or different and Y is a divalent alkylene group selected from the group consisting of CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, and [CH.sub.2CH(CH.sub.3)CH.sub.2], y and z independently are 0, 1 or 2, and m and n independently are 0 or 1, or (C) at least one tris-silylated alkylamine of formula III
N[YSi(R).sub.n(OR).sub.3-n].sub.3 (III), in which groups R and R are alike or different and are each a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, Y independently is a divalent alkylene group selected from the group consisting of CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, and [CH.sub.2CH(CH.sub.3)CH.sub.2], and n independently is 0 or 1, or (D) at least two of the alkylamines of formula I, II, and III, wherein the free alcohol content of the composition is less than or equal to 1% by weight, based on the composition, and wherein the reacted units are formed by partial or complete hydrolysis and also, where appropriate, condensation or cocondensation of compounds of (A), (B), (C), or (D).

16. A process for preparing the composition as claimed in claim 15, the process comprising: at least partially hydrolyzing and, where appropriate, condensing or cocondensing: (A) at least one aminoalkylalkoxysilane of formula I
NR.sub.2[(CH.sub.2).sub.2NR].sub.xYSi(R).sub.n(OR).sub.3-n (I), in which groups R, R and R are alike or different and are each a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, Y is a divalent alkylene group selected from the group consisting of CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, and [CH.sub.2CH(CH.sub.3)CH.sub.2], x is 0, 1 or 2, and n is 0 or 1, or (B) at least one bis-silylated alkylamine of formula II
(RO).sub.3-m(R).sub.mSiY[NR(CH.sub.2).sub.2].sub.yNR[(CH.sub.2).sub.2NR].sub.2YSi(R).sub.n(OR).sub.3-n (II), in which groups R, R and R are alike or different and are ach a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, groups Y are alike or different and Y is a divalent alkylene group selected from the group consisting of CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, and [CH.sub.2CH(CH.sub.3)CH.sub.2], y and z independently are 0, 1 or 2, and m and n independently are 0 or 1, or (C) at least one tris-silylated alkylamine of formula III
N[YSi(R).sub.n(OR).sub.3-n].sub.3 (III), in which groups R and R are alike or different and are each a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms, Y independently is a divalent alkylene group selected from the group consisting of CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, and [CH.sub.2CH(CH.sub.3)CH.sub.2], and n independently is 0 or 1, or (D) at least two of the alkylamines of formula I, II, and III, in the presence of water and optionally in the presence of an acid to obtain the silicon compound, and substantially removing the free alcohol from the composition.

17. The process according to claim 16, wherein said at least partially hydrolyzlng and, where appropriate, condensing or cocondensing is carried cut at a temperature of less than 100 C.

18. The process according to claim 16, wherein said at least partially hydrolyzing and, where appropriate, condensing or cocondensing is carried out at a temperature of from 10 C. to 80 C.

19. The process according to claim 16, which further comprises mixing the composition and applying ultrasound to the composition while mixing.

20. The process according to claim 16, wherein the acid is present and is at least one member selected from the group consisting of hydrochloric acid, aqueous acetic acid, and aqueous formic acid.

21. The process according to claim 16, wherein said at least partially hydrolyzing and, where appropriate, condensing or cocondensing, is carried out in the presence of an inert gas.

22. The composition according to claim 15, wherein the composition further comprises at least one of an organic and an inorganic acid, wherein the silicon compound comprises aminoalkyl groups and oligo-silylated aminoalkyl groups, and wherein the silicon compound has a degree of neutralization of aminoalkyl groups and oligo-silylated aminoalkyl groups of from 0% to 125%, based on the amine number of the silicon compound, the amine number determined according to DIN 32 625.

23. The composition according to claim 15, wherein the free alcohol content of the composition is less than or equal to 0.5% by weight, based on the composition.

24. The composition according to claim 15, wherein a PH of a composition is from 2 to 11.

25. The composition according to claim 15, wherein a pH of a composition is from 3.5 to 5.0.

26. The composition according to claim 15, which has a viscosity of from 2 to 1,000 mPa.Math.s, determined according to standard DIN 53 015.

27. The composition according to claim 15, which comprises wafer, present in an amount of from 99.9% to 0.5% by weight, based on the total of the composition with all components of the composition totally 100% by weight.

28. The composition according to claim 15, which further comprises at least one member selected from the group consisting of a polyvinyl alcohol, starch, gelatin, an acrylate lattice, a nanoscale metal oxide, a crosslinker, a glyoxal compound, an optical brightener, and a process assistant.

29. The composition according to claim 15, which further comprises fumed silica, wherein said fumed silica has an average particle size, determined by static light scattering, of less than 1 micron, and wherein said fumed silica is present in the composition in an amount of from 5% to 50% by weight, based on the composition.

30. The composition according to claim 15, wherein component (A) is at least one member selected from the group consisting of H.sub.2N(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, H.sub.2N(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3, H.sub.2N(CH.sub.2).sub.2NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, H.sub.2N(CH2).sub.2NH(CH.sub.2).sub.2NH(CH2).sub.3Si(OCH3).sub.3, and 3-(N-alkylamino)propyltrialkoxoxysilane, wherein alkyl is methyl, ethyl, n-propyl or n-butyl and alkoxy is methoxy or ethoxy; component (B) is at least one member selected from the group consisting of (H.sub.3CO).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, (H.sub.5C.sub.2O).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3, (H.sub.3CO).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, and (H.sub.3CO).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3; and component (C) is at least one member selected from the group consisting of N[(CH.sub.2).sub.3Si(OCH.sub.3).sub.3].sub.3 and N[CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3].sub.3.

31. The composition according to claim 15, wherein component (A) is 3-(N-alkylamino)propyltrialkoxysilane, wherein alkyl is n-butyl and alkoxy is methoxy.

32. The process according to claim 16, wherein component (A) is at least one member selected from the group consisting of H.sub.2N(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, H.sub.2N(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3, H.sub.2N(CH.sub.2).sub.2NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, H.sub.2N(CH2).sub.2NH(CH.sub.2).sub.2NH(CH2).sub.3Si(OCH3).sub.3, and 3-(N-alkylamino)propyltrialkoxysilane, wherein alkyl is methyl, ethyl, n-propyl or n-butyl and alkoxy is methoxy or ethoxy; component (B) is at least one member selected from the group consisting of (H.sub.3CO).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, (H.sub.5C.sub.2O).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3, (H.sub.3CO).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, and (H.sub.3CO).sub.3Si(CH.sub.2).sub.3NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2NH(CH.sub.2).sub.3Si(OCH.sub.3).sub.3; and component (C) is at least one member selected from the group consisting of N[(CH.sub.2).sub.3Si(OCH.sub.3).sub.3].sub.3 and N[CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3].sub.3.

33. The process according to claim 16, wherein component (A) is 3-(N-alkylamino)propyltrialkoxysilane, wherein alkyl is n-butyl and alkoxy is methoxy.

Description

EXAMPLES

[0079]

TABLE-US-00001 Technical data Determination method according to Density DIN 51 757 Viscosity DIN 53 015 Color number ISO 4630 pH DIN 19 268 (20 C., 1000 g/l) Flash point EN 22 719

[0080] The determination methods used to evaluate the present examples were in particular as follows:

[0081] Determination of Free Alcohol Content:

[0082] The alcohol determination was carried out by means of GC.

[0083] Column: RTX 200 (60 m)

[0084] Temperature program: 80-10-25-240-0

[0085] Detector: FID

[0086] Injection volume: 1.0 l

[0087] Internal standard: 2-Butanol

[0088] Dry Residue

[0089] The solids content of the aqueous silane systems is determined as follows:

[0090] 1 g of the sample is weighed out into a small porcelain dish and dried to constant weight in a drying cabinet at 105 C.

[0091] SiO.sub.2 Content:

[0092] 1.0 to 5.0 g of the sample in a 400 ml glass beaker is admixed with a Kjeldahl tablet and 20 ml of sulfuric acid, and the mixture is first slowly heated. The glass beaker is covered with a watch glass. The temperature is raised until the sulfuric acid fumes significantly and all of the organic constituents have been destroyed, the solution remaining clear and bright. The cold digestion solution is diluted to about 200 ml with distilled water and briefly boiled (water at the edge of the glass beaker allowed to flow under the acid). The residue is filtered through a white-ribbon filter and washed with hot water until the washing water indicates a pH of >4 (pH paper). The filter is dried in a platinum crucible, incinerated and calcined in a muffle furnace at 800 C. for 1 hour. After weighing, the residue is fumed off with hydrofluoric acid, the crucible is calcined by means of a fan burner, and calcined again if necessary at 800 C., and, after it has cooled, is weighed. The difference between the two weighings corresponds to the SiO.sub.2 content.

[0093] Evaluation: D100/E=% by weight SiO2

[0094] D=Weight difference before and after hydrofluoric acid removal of silicon as volatile silicon tetrafluoride, in mg

[0095] 100=Conversion to %

[0096] E=Initial mass in mg

[0097] Methanol After Hydrolysis:

[0098] About 5 g of sample are weighed accurately into a 500 ml conical flask with ground-glass joints, and are hydrolyzed with 25 ml of sulfuric acid (w=20%) with shaking until a clear solution has formed.

[0099] Following addition of 75 ml of water, the sample is neutralized with aqueous sodium hydroxide solution (w=20%) and subjected to steam distillation in a suitable apparatus. The distillate is collected in a 250 ml measuring flask. Following addition of 2-butanol as internal standard, the sample is made up to the mark with distilled water.

[0100] The alcohol determination is made by means of GC.

[0101] Column: RTX 200 (60 m)

[0102] Temperature program: 90-10-25-240-0

[0103] Detector: FID

[0104] Injection volume: 1.0 l

[0105] Internal standard: 2-Butanol

Example 1

Composition With Reduced VOC Content

[0106] A stirred apparatus with metering means and reflux condenser was charged under a nitrogen atmosphere with 470.6 g of Dynasylan 1189 [N-(n-butyl)-3-aminopropyltrimethoxysilane, manufacturer: Degussa GmbH] and 80.0 g of methanol. Subsequently, via a metering means, a mixture consisting of 28.8 g of H.sub.2O and 28.8 g of methanol was metered in over the course of 10 minutes (molar hydrolysis ratio Si:H.sub.2O=1:0.8). During this addition the temperature rose from 28 C. to 50 C. The mixture was stirred at 60 C. for 3 h. Thereafter 208.89 g of methanol were distilled off at about 200 mbar. The final weight of the residue/product was 394.87 g.

[0107] A clear, slightly yellowish liquid was obtained which is stable on storage.

[0108] SiO.sub.2 content: 29.6% (mass)

[0109] Methanol (after hydrolysis): 19.5% (mass)

[0110] Viscosity (20 C.): 26 mPa s

[0111] Density (20 C.): 0.996 g/cm.sup.3

Example 2

Composition With Reduced VOC Content

[0112] A stirred apparatus with metering means and reflux condenser was charged under a nitrogen atmosphere with 470.6 g of Dynasylan 1189 and 80.0 g of methanol. Subsequently, via the metering means, a mixture consisting of 43.20 g of H.sub.2O and 43.20 g of methanol was metered in over the course of 10 minutes (molar hydrolysis ratio Si:H.sub.2O=1:1.2). During this addition the temperature rose from 28 C. to 56 C.

[0113] The mixture was stirred at 60 C. for 3 h. Thereafter 263.50 g of methanol were distilled off at about 200 mbar. The final weight of the residue/product was 367.77 g.

[0114] A clear, viscose, slightly yellowish liquid was obtained which is stable on storage.

[0115] SiO.sub.2 content: 32.0% (mass)

[0116] Methanol (after hydrolysis): 9.2% (mass)

[0117] Viscosity (20C.); 187 mPa s

[0118] Density (20 C.): 1.027 g/cm.sup.3

Example 3

A Substantially VOC-free Composition

[0119] A stirred apparatus with metering means and reflux condenser was charged under a nitrogen atmosphere with 498.2 g of water and 55.0 g of formic acid (conc. HCOOH=85%). Subsequently, using the metering means, 235.7 g of Dynasylan 1189 were metered in. The pH was 4.8. The mixture was stirred at 60 C. for 3 h. Thereafter, at about 130-200 mbar, a methanol/water mixture was distilled off. The final weight of the residue was 589.0 g.

[0120] A clear, slightly yellowish liquid was obtained which has a pH of 5.3 and is stable on storage.

[0121] SiO.sub.2 content: 9.2% (mass)

[0122] Flash point: >100 C.

[0123] Free methanol: 0.5% (mass)

[0124] Viscosity (20 C.): 11 mPa s

[0125] Density (20 C.): 1.070 g/cm.sup.3

[0126] Dry residue 105 C.: 36.2% (mass)

Comparative Example 1

Dispersion with Dynasylan 1189 Incl. Methanol

N-Butylaminopropyltrimethoxysilane, (C.SUB.7.H.SUB.16.N)Si(OCH.SUB.3.).SUB.3., 235 g/mol, Methanol Releasable By Hydrolysis: 48.5%

[0127] Apparatus:

[0128] Rotor-stator systems (Ultra-Turrax)

[0129] Jacketed pot, 3 liters

[0130] Dissolver for stirred incorporation of AEROSIL 200

[0131] Polytron (rotor-stator) dispersing apparatus

[0132] Stirrer, 2 dropping funnels for dropwise addition of the silane solution and of the HCl solution

[0133] Heatable ultrasound bath (40 W ultrasound power)

[0134] 500 m sieve

[0135] 1600 g of Dl water were introduced, and 400 g of AEROSIL 200 were incorporated by stirring with the dissolver; acidification to a pH of 2.1 was carried out with 5 g of 18% strength HCl, and the batch was dispersed at 10,000 rpm for 15 min, using the Polytron. The solids content was found to be 20.07%.

[0136] Dissolver again at 2000 rpm, dropwise addition therein of 98.6 g of Dynasylan 1189 in the form of a 20% strength solution in methanol, simultaneously with the maintenance of the pH of between pH 3-4 by dropwise addition of 18% strength HCl (total of 13 g, dispersion gels at pH>4). A further 15-min reaction time at 2000 rpm, followed by 60 min in the ultrasound bath at 80 C. (with lid), cooling and filtration via a 500 m sieve.

[0137] Methanol content of the dispersion: 88.4 g=4.2%

[0138] The viscosity of the dispersions thus prepared was measured with a Brookfield viscometer after 24 h.

Example 4

Dispersion With the Composition From Example 3

[0139] Procedure analogous to that of comparative example 1, with the difference that 41.3 g of the composition from example 3 were used as a 40% strength solution in water, pH 4.1, VPS Hydrosil 2930, as silane component. Additionally 8 g of HCl were used.

[0140] Methanol content of the dispersion: no methanol detected

Comparative Example 2

Dispersion with Dynasylan Hydrosil 2627 (Substantially Free From Alcohol, cf. EP 0 716 127 A2)

[0141] Analogous to comparative example 1, with the difference that 94 g of Dynasylan Hydrosil 2627 (diluted to 20% strength solution in water) are used as silane component, 13 g of HCl are required.

Example 5

Dispersion With 1189 Oligomer From Example 1

[0142] Partially hydrolyzed VPS 1189 oligomeric, (C.sub.7H.sub.16N)SiO.sub.0.8(OCH.sub.3).sub.1.4, 203.4 g/mol, methanol releasable by hydrolysis 26.1%

[0143] Analogous to comparative example 1, with the difference that 85.3 g of oligomer (20% strength solution in water, pH 4.0) were used as silane component. 7 g of HCl were used.

[0144] Methanol content of the dispersion: 4.45 g=0.2%

Example 6

Dispersion With 1189 Oligomer From Example 2

[0145] Partially hydrolyzed VPS 1189 oligomeric, (C.sub.7H.sub.16N)SiO.sub.1.2(OCH.sub.3).sub.0.4, 183.4 g/mol, methanol releasable by hydrolysis 8.3%

[0146] Analogous to comparative example 1, with the difference that 77.0 g of oligomer (20% strength solution in water, pH 4.2) were used as silane component, 7.5 g of HCl were used.

[0147] Methanol content of the dispersion: 1.28 g=0.06%

TABLE-US-00002 TABLE 1 Data of the modified silica dispersions from comparative examples 1 and 2 and also examples 1 to 3; cf. examples 4 to 6 Dispersion 1 with Dispersion 2 with Dispersion 3 with Dispersion 4 with Dispersion 5 with composition from composition from composition from composition from composition from comparative example 1: example 3: comparative example 2: example 1: example 2: 4.25% MeOH VOC-free VOC-free 0.2% MeOH 0.06% MeOH pH 2.4 3.3 2.1 3.0 3.0 Solids content w 0.21 0.23 0.20 0.22 0.23 20 rpm; Sp. 2 104 mPa s 132 mPa s 84 mPa s 160 mPa s 184 mPa s 50 rpm; Sp. 2 88 mPa s 116 mPa s 88 mPa s 164 mPa s 188 mPa s 100 rpm; Sp. 2 120 mPa s 124 mPa s 96 mPa s 160 mPa s 172 mPa s rpm = Revolutions per minute of the Brookfield viscometer

Application Example

Preparation of Art Inkjet Coating Color

[0148] Inkjet coating colors were produced from the aqueous dispersions: cf. table 1.

[0149] The dispersions from the examples and comparative example were mixed on a dissolver at 500 rpm with a 13% strength solution of polyvinyl alcohol (solid, abbreviation PVA) Mowiol 40-88 from Clariant over the course of 10 minutes. The ratio on combining was calculated so as to give a dispersion C with a strength of 18 percentbased on the solid (pyrogenic oxide+PVA), in a ratio of 4:1 (100:25 Aerosil to PVA, and addition of water if appropriate). The viscosity of this dispersion C, the inkjet coating color, was measured by means of a Brookfield viscometer after 24 h.

TABLE-US-00003 TABLE 2 Viscosity of the coating colors measured after 24 h: Coating color 1 Coating color 2 Coating color 3 Coating color 4 Coating color 5 from dispersion 1 from dispersion 2 from disperison 3 from dispersion 4 from dispersion 5 (4.25% MeOH) (VOC-free) (VOC-free) (0.2% MeOH) (0.6% MeOH) Solids content of the 17.45 18.64 Not 18.21 17.93 coating color (pyrogenic possible oxide with silane + PVA) to produce! % by weight Viscosity [mPa s] 480 360 n.a. 430 330 at 100 rpm and 50 C.

[0150] These coating colors were applied by means of a profiled bar coater to a photographic base paper (thickness 300 micrometers). The wet film thickness of the coating color was 110 micrometers. The coating was dried at 105 C. for 8 minutes.

[0151] The papers with the applied coating were printed on an Epson Stylus Photo R240 at maximum resolution.

TABLE-US-00004 TABLE 3 Evaluation of the print outcome: Coating 1 from Coating 2 from Coating 3 from Coating 4 from Property coating color 1 coating color 2 coating color 4 coating color 5 evaluated Evaluation Rating Evaluation Rating Evaluation Ratin Evaluation Note Color intensity Good 2 Good 2 Good 2 Good 2 Resolution Good 2 Good 2 Good 2 Good 2 Ink run No 1 No 1 No 1 No 1 (bleeding) bleeding bleeding bleeding bleeding Color shift Good 2 Good 1.5 Good- 1.5 Good- 1.75 very good very good Average Good 1.75 Good 1.625 Good 1.625 Good 1.688 Best rating 1, poorest rating 6

[0152] In the total of all of the properties of the coatings, all the coatings exhibited approximately the exact same values.

[0153] The viscosities of the coating colors produced with the various dispersions were substantially comparable. Here there was no apparent disadvantage from the reduction in methanol.

[0154] With the composition and dispersion/coating color of the invention it is therefore possible to provide a coating which, despite a significant reduction in the VOC fraction, produces an equally good print with an inkjet printer.