Use of quaternised compounds in dyeing paper

The invention relates to a process for dyeing paper materials, which is characterized in that compounds of the general formula<chemistry id="chem0001" num="0001"><img file="EP0013751B1_D0001.tif" /></chemistry>used in the<ul id="ul0001" list-style="none"><li>A¹ and A² the rest of a quaternized methylene active compound and</li><li>B are a pontic.</li></ul>

The residues of the methylene-active compounds are quaternized heterocyclic residues whose methylene-active group is CH₃- or<chemistry id="chem0002" num="0002"><img file="EP0013751B1_D0002.tif" /></chemistry>is. They originate predominantly from the optionally fused pyridinium or pyrylium series or from quaternized benzthiazoles, benzimidazoles, indolenines, quinoxalones or pyrimidones.

The following are examples of the compounds of the formulas A¹H₂ or A²H₂ cited:<chemistry id="chem0003" num="0003"><img file="EP0013751B1_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0013751B1_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP0013751B1_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP0013751B1_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP0013751B1_D0007.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP0013751B1_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP0013751B1_D0009.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP0013751B1_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP0013751B1_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP0013751B1_D0012.tif" /></chemistry>and<chemistry id="chem0013" num="0013"><img file="EP0013751B1_D0013.tif" /></chemistry>

The bridge members B originate from aromatic or heterocyclic bisaldehydes, predominantly of the benzene series, which can still carry conventional substituents, such as chlorine, methyl, methoxy or ethoxy. Individual residues B are, for example:

<chemistry id="chem0014" num="0014"><img file="EP0013751B1_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP0013751B1_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP0013751B1_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP0013751B1_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP0013751B1_D0018.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP0013751B1_D0019.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP0013751B1_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP0013751B1_D0021.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP0013751B1_D0022.tif" /></chemistry><chemistry id="chem0023" num="0023"><img file="EP0013751B1_D0023.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP0013751B1_D0024.tif" /></chemistry><chemistry id="chem0025" num="0025"><img file="EP0013751B1_D0025.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP0013751B1_D0026.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP0013751B1_D0027.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP0013751B1_D0028.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP0013751B1_D0029.tif" /></chemistry><chemistry id="chem0030" num="0030"><img file="EP0013751B1_D0030.tif" /></chemistry>and<chemistry id="chem0031" num="0031"><img file="EP0013751B1_D0031.tif" /></chemistry>where RC₁- to C₄-Alkyl, β-hydroxyethyl, β-cyanoethyl or benzyl.

To prepare the compounds of the formula I, compounds of the formula A¹H₂ and A²H₂, which can be the same or different, with bisaldehydes of the formula<chemistry id="chem0032" num="0032"><img file="EP0013751B1_D0032.tif" /></chemistry>implement in a known manner.

Details of the reactions can be found in the examples, in which parts and percentages, unless stated otherwise, relate to the weight.

The compounds of the formula I are particularly suitable for dyeing sized and unsized papers in bulk, the affinities both for lignin-containing (wood pulp-containing) and lignin-free paper stocks being high. The dyes are largely substantive, the waste water after coloring is colorless to almost colorless. The nuances that can be achieved are between yellow and blue.

Compounds of the formula I in which A^I. and / or A² come from the quinolinium, y-picolinium, indolinium, benzthiazolium and quinoxalonium series and the radicals B correspond to the formulas<chemistry id="chem0033" num="0033"><img file="EP0013751B1_D0033.tif" /></chemistry>or<chemistry id="chem0034" num="0034"><img file="EP0013751B1_D0034.tif" /></chemistry>correspond with<ul id="ul0002" list-style="none"><li>B¹ represents an alkylene or aralkylene radical and</li><li>R has the meaning given.</li></ul>

Preferred residues B¹ are z. B.<chemistry id="chem0035" num="0035"><img file="EP0013751B1_D0035.tif" /></chemistry>

Compounds of formula 1 are already known from US-A-2 465 412 for photographic purposes and from DE-A-2 047 431 for dyeing acrylonitrile polymers. It was surprising and unpredictable that the compounds of the formula are very suitable for dyeing paper materials and that very good bath exhaustion is achieved with both lignin-containing and lignin-free paper pulps.

example 1

<chemistry id="chem0036" num="0036"><img file="EP0013751B1_D0036.tif" /></chemistry>

14.7 parts of diphenylpiperazine dialdehyde and 22 parts of 1,4-dimethylpyridinium methyl sulfate are refluxed in 100 parts of ethylene glycol monomethyl ether in the presence of two parts of piperidine for two hours. After cooling, it is suctioned off and washed with methanol.

Yield: 12 parts.

The dye colors paper in the mass orange. The color strength, the brilliance and the very low wastewater color of bleached fabrics are to be emphasized.

Dyes with similarly good properties are obtained with the following methylene-active components. The hue again refers to bleached fabrics.<tables id="tabl0001" num="0001"><img file="EP0013751B1_D0037.tif" /></tables>

Example 2

<chemistry id="chem0037" num="0037"><img file="EP0013751B1_D0038.tif" /></chemistry>7.5 parts of the aldehyde of the formula<chemistry id="chem0038" num="0038"><img file="EP0013751B1_D0039.tif" /></chemistry>and 3.5 parts of 1,3,3-trimethyl-2-methylene indolenine are heated in 50 parts of 30 percent acetic acid at 100 ° C for one hour. It is diluted with water and precipitated with sodium chloride solution. Yield: 12 parts.

Woody and bleached fabrics are dyed red. Wastewater staining is low.

The above aldehyde is prepared as follows: 96 parts of N-ethyl-N-β-dimethylaminoethyl aniline are dissolved in 150 parts of acetone, and 44 parts of p-xylylene dichloride, dissolved in acetone, are added dropwise. After refluxing for eight hours, the product is suctioned off in the cold and dried.

Yield: 123 parts, mp 220-222 ° C.

56 Parts of the doubled aniline derivative thus obtained are dissolved in 100 parts of dimethylformamide. 31 parts of phosphorus oxychloride are then added dropwise so that a temperature of 70 ° C. is not exceeded. The reaction is completed by heating to 90 ° C. The mixture is worked up by pouring it into water. The cationic bisaldehyde is precipitated with sodium zinc chloride solution.

Yield: 46 parts, mp 158-160 ° C.

Good paper dyes are also obtained by using the following heterocyclic methylene bases:<tables id="tabl0002" num="0002"><img file="EP0013751B1_D0040.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0013751B1_D0041.tif" /></tables>

The quaternization of N-ethyl-N-ß-dimethylaminoethylaniline was also carried out with the following bishalogen compounds:<chemistry id="chem0039" num="0039"><img file="EP0013751B1_D0042.tif" /></chemistry>CI-CH₂-CH = CH-CH₂-CI Br-CH₂CH₂-Br Br-CH₂CH₂CH₂-Br Br-CH₂CH₂CH₂CH₂-Br Br ― CH₂CH₂CH₂CH₂CH₂―Br and<chemistry id="chem0040" num="0040"><img file="EP0013751B1_D0043.tif" /></chemistry>

The dyes made from these intermediates behave similarly to those already described.

This also applies to the products obtained when the N-ethyl-N-β-dimethylethylaniline used was replaced by the following aniline derivatives:<chemistry id="chem0041" num="0041"><img file="EP0013751B1_D0044.tif" /></chemistry><chemistry id="chem0042" num="0042"><img file="EP0013751B1_D0045.tif" /></chemistry><chemistry id="chem0043" num="0043"><img file="EP0013751B1_D0046.tif" /></chemistry><chemistry id="chem0044" num="0044"><img file="EP0013751B1_D0047.tif" /></chemistry><chemistry id="chem0045" num="0045"><img file="EP0013751B1_D0048.tif" /></chemistry>

Example 3

<chemistry id="chem0046" num="0046"><img file="EP0013751B1_D0049.tif" /></chemistry>5.2 parts of 4,4'-diphenyldialdehyde and 13.8 parts of 2,3-dimethylbenzthiazolium methyl sulfate are kept in 50 parts of ethanol with the addition of one ml of piperidine at 80 ° C. for two hours. You cool down and suction.

Yield: 9 parts.

Woody and bleached fabrics are dyed bright golden yellow. Only four or two percent of the dye used remains in the wastewater. The dye is very strong in color.

The corresponding dyes were also obtained with the following components:<tables id="tabl0004" num="0004"><img file="EP0013751B1_D0050.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0013751B1_D0051.tif" /></tables>

Example 4

<chemistry id="chem0047" num="0047"><img file="EP0013751B1_D0052.tif" /></chemistry>10.9 parts of 1,4-dimethylpyridinium methyl sulfate and 11.2 parts of the aldehyde of the formula<chemistry id="chem0048" num="0048"><img file="EP0013751B1_D0053.tif" /></chemistry>are two in 100 parts of alcohol in the presence of 0.5 parts of piperidine^; Hours cooked. It is diluted with water and the dye is precipitated by adding zinc chloride.

Yield: 19 parts.

Papers containing wood are colored reddish yellow with good wastewater behavior.

The following methylene-active heterocycles were also used:<tables id="tabl0006" num="0006"><img file="EP0013751B1_D0054.tif" /></tables>The following aldehydes were used with similar results: Anion Cl in each case<chemistry id="chem0049" num="0049"><img file="EP0013751B1_D0055.tif" /></chemistry><chemistry id="chem0050" num="0050"><img file="EP0013751B1_D0056.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP0013751B1_D0057.tif" /></chemistry><chemistry id="chem0052" num="0052"><img file="EP0013751B1_D0058.tif" /></chemistry><chemistry id="chem0053" num="0053"><img file="EP0013751B1_D0059.tif" /></chemistry><chemistry id="chem0054" num="0054"><img file="EP0013751B1_D0060.tif" /></chemistry><chemistry id="chem0055" num="0055"><img file="EP0013751B1_D0061.tif" /></chemistry><chemistry id="chem0056" num="0056"><img file="EP0013751B1_D0062.tif" /></chemistry><chemistry id="chem0057" num="0057"><img file="EP0013751B1_D0063.tif" /></chemistry><chemistry id="chem0058" num="0058"><img file="EP0013751B1_D0064.tif" /></chemistry>and<chemistry id="chem0059" num="0059"><img file="EP0013751B1_D0065.tif" /></chemistry>

Example 5

<chemistry id="chem0060" num="0060"><img file="EP0013751B1_D0066.tif" /></chemistry><chemistry id="chem0061" num="0061"><img file="EP0013751B1_D0067.tif" /></chemistry>20 Parts of the aldehyde of the formula<chemistry id="chem0062" num="0062"><img file="EP0013751B1_D0068.tif" /></chemistry>and 31 parts of 1,4-dimethylpyridinium methyl sulfate are stirred in 50 parts of methyl glycol under piperidine catalysis for two hours at 120 ° C. It is diluted with alcohol and suctioned off.

Yield: 28 parts.

Woody and lignin-free fabrics are dyed orange if the bathroom is well exhausted.

The dyes also provide practically colorless waste water from the following methylene-active components:<tables id="tabl0007" num="0007"><img file="EP0013751B1_D0069.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0013751B1_D0070.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0013751B1_D0071.tif" /></tables>

Also very good wastewater-resistant paper dyes with high brilliance are obtained with the following aldehydes:<chemistry id="chem0063" num="0063"><img file="EP0013751B1_D0072.tif" /></chemistry><chemistry id="chem0064" num="0064"><img file="EP0013751B1_D0073.tif" /></chemistry><chemistry id="chem0065" num="0065"><img file="EP0013751B1_D0074.tif" /></chemistry><chemistry id="chem0066" num="0066"><img file="EP0013751B1_D0075.tif" /></chemistry><chemistry id="chem0067" num="0067"><img file="EP0013751B1_D0076.tif" /></chemistry><chemistry id="chem0068" num="0068"><img file="EP0013751B1_D0077.tif" /></chemistry><chemistry id="chem0069" num="0069"><img file="EP0013751B1_D0078.tif" /></chemistry>and<chemistry id="chem0070" num="0070"><img file="EP0013751B1_D0079.tif" /></chemistry>