CN1068030C - Aqueous pigment paste for offset ink, process for producing the paste, and use thereof - Google Patents
Aqueous pigment paste for offset ink, process for producing the paste, and use thereof Download PDFInfo
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- CN1068030C CN1068030C CN 95195326 CN95195326A CN1068030C CN 1068030 C CN1068030 C CN 1068030C CN 95195326 CN95195326 CN 95195326 CN 95195326 A CN95195326 A CN 95195326A CN 1068030 C CN1068030 C CN 1068030C
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Abstract
The present invention relates to pigment paste containing water, a production method thereof and printing ink for offset printing obtained by a water squeezing method, wherein the pigment paste containing water is suitable for printing ink for offset printing obtained by a water squeezing method. The pigment paste containing water for printing ink for offset printing is composed of mordant pigment of azo dye, rosin with 3 to 15 wt% of that of the azo dye, a color carrier for printing ink for offset printing with 1 to 20 wt% of that of the azo dye and 60 to 90 wt% of water, wherein the mordant pigment of the azo dye is formed by coupling diazonium salts of aromatic amine with a soluble radical group and a coupling agent; the total amount of the mordant pigment, the rosin and the color carrier accounts for 10 to 40 wt%.
Description
Technical field
The present invention relates to can be used as the aqueous monoazo laked pigment cream of flexographic ink and the flexographic ink of manufacture method and this pigment paste of use thereof.More particularly, relate to the aqueous monoazo laked pigment cream that improved aspect bronze in water squeezing adaptability, flowability, distinctiveness, gloss, nothing and the flexographic ink of manufacture method and this pigment paste of use thereof.
Background technology
With the aromatic amine with solubility group attach most importance to nitrogen component, be the various uses such as painted that monoazo laked pigment that the coupling of coupler composition forms is widely used in printing-ink, coating, plastics with β-Qiang Jinaijiasuan, 2-Naphthol etc.For the tone that makes these monoazo laked pigments is transparent and distinct, and improve its dispersiveness, often it is carried out rosin and handle.It is a kind of rosiny alkali metal salt soln (being rosined soap) that adds in the coupler composition or in the dyestuff usually that this rosin is handled, and adds color lake metal-salts such as calcium chloride then, makes rosin separate out method on surface of pigments as insoluble rosin color lake metal-salt.
Above-mentioned rosin is handled can make tinyization of pigment particles, and can improve its transparency and distinctiveness.And rosin covers on the pigment, can stop the pigment aggegation, improves its dispersiveness.But still not talkative this effect of having given full play to of existing treatment process.Especially offset printing pigment for improving its dispersiveness, needs to use a large amount of rosin.And rosiny in a large number use can produce by flowability descend or the bad printing adaptability that causes of water tolerance under the numerous drawbacks of degradation.In addition, if reduce the rosiny usage quantity, can produce degradation drawback under the transparency, distinctiveness decline, bronze increase, the water squeezing adaptability.
Thereby, need few and process for treating surface coverage pigment expeditiously of a kind of rosiny usage quantity of exploitation and develop a kind of at water squeezing adaptability, flowability, distinctiveness, gloss with there is not a monoazo laked pigment that has improved aspect bronze thus.
Therefore, the object of the present invention is to provide a kind of aqueous monoazo laked pigment cream and manufacture method and flexographic ink, described aqueous monoazo laked pigment cream is owing to use a small amount of rosin, the water squeezing time obtains shortening, draining painted few, have excellent flowability, distinctiveness and gloss, do not have bronze colour and have excellent offset printing adaptability.
Disclosure of an invention
The invention provides a kind of aqueous pigment cream that is used for flexographic ink, the pigment lake of the azoic dyestuff that this aqueous pigment cream is formed by the diazonium salt and the coupling of coupler composition of the aromatic amine with solubility group, the rosin that is equivalent to the 3-15 weight % of this azoic dyestuff, the used for offset ink chromatophore of 1-20 weight % that is equivalent to this azoic dyestuff and the water that is equivalent to the 60-90 weight % of whole composition are formed.
The present invention also provides a kind of manufacture method that is used for the aqueous pigment cream of flexographic ink, and this method comprises following operation: with have the aromatic amine of solubility group diazonium salt and operation that the coupling of coupler composition obtains azoic dyestuff, make gained azoic dyestuff color lake in the presence of rosiny obtain the operation of monoazo pigment slip, add the chromatophorous operation of used for offset ink in the gained monoazo pigment slip, be concentrated in the operation that the monoazo pigment slip that obtains in the operation of front is made the aqueous pigment cream that is used for flexographic ink.
In addition, the present invention also provides a kind of by the flexographic ink that the aqueous pigment cream water squeezing of above-mentioned used for offset ink obtained with the used for offset ink chromatophore and the manufacture method of this flexographic ink.
Implement best mode of the present invention
In the present invention, monoazo laked pigment be meant dyestuff color lakeization that azo composition and the coupling of coupler composition are formed and pigment, the aromatic amine diazotization that described azo composition system will have the solubility group forms.
In the present invention, it is as follows to have an example of aromatic amine of solubility group.1-amino-4-methylbenzene-2-sulfonic acid (p-Tolylamine-m-sulfonic acid), 1-amino-4-methyl-5-chloro benzene-2-sulfonic acid, 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid, 1-amino-4-methylbenzene-3-sulfonic acid, 2-amino naphthalenes-1-sulfonic acid, 1-amino-3-methylbenzene-4-sulfonic acid etc.
The representative example of coupler is a β-Qiang Jinaijiasuan, also can be 2-Naphthol, acetoacetanilide.In addition, also can be the compound of derivative as being replaced of above-mentioned coupler composition by low alkyl group, alkoxyl group or halogen atom.
In the present invention, monoazo laked pigment can be made by the manufacture method of known monoazo laked pigment so far.That is, can will have the aromatic amine diazotization of solubility group by well-established law, and prepare above-mentioned coupler composition by well-established law in addition, after both usefulness well-established law couplings, the metal that uses pigment color lake usefulness is with gained dyestuff color lakeization.In addition, the in addition coupling of metal that also can be in advance adds pigment color lake usefulness in the diazonium composition.The example of the metal of pigment color lake usefulness comprises calcium, barium, strontium, manganese etc.
Rosin is made soluble salts such as sodium salt, sylvite, ammonium salt, added to during dyestuff or coupler become to grade, make it to be present in the process of color lakeization.
Aqueous pigment cream of the present invention is characterised in that, has mixed the used for offset ink chromatophore in the pigment syrup of color lakeization.Preferably the used for offset ink chromatophore commonly used that will be made up of resin for printing ink and solvent etc. is again with mixing behind the solvent cut.
The example of the resin that printing ink is used comprises rosin modified phenolic resin, Synolac etc.Wherein, preferred rosin modified phenolic resin.The used for offset ink chromatophore that uses among the present invention is made up of the solvent of the vegetables oil of the resin of 20-50 weight % such as rosin modified phenolic resin, 0-30 weight % such as Toenol 1140, tung oil, soybean oil, 10-60 weight % such as normal paraffin, different alkane, aromatic solvent, cycloalkanes, alpha-olefin etc.The boiling point of solvent for use is preferably in about 270-320 ℃ the scope.
The example of rosin modified phenolic resin is as follows.
(a) p-alkylphenol, paraformaldehyde and rosin are dissolved in the toluene, after reaction in the presence of acid or the alkaline catalysts, with the rosin modified phenolic resin of gained after the polyvalent alcohol esterification.The example of p-alkylphenol has p-octyl phenol, p-nonyl phenol etc.The example of polyvalent alcohol has glycerine, tetramethylolmethane etc.
(b) rosin is added phenol-formaldehyde A after 200 ℃ of fusions and react, then with the rosin modified phenolic resin of gained behind the glycerine esterification.
(c) in rosiny glyceryl ester, add the rosin modified phenolic resin that phenol-formaldehyde A reacts the back gained.
(d) with the rosin modified phenolic resin of gained behind rosin modified alkyd resin and the reactive modified phenolic resin.
Can dilute the chromatophorous solvent of used for offset ink No. 0 solvent, No. 5 solvents, No. 7 (Nippon Oil Co., Ltd's products) such as solvents are arranged.These solvents are to be generally used for the chromatophorous solvent of used for offset ink.
Be equivalent to the 1-20 weight % of azoic dyestuff at the chromatophorous incorporation of aqueous pigment cream used for offset ink that is used for flexographic ink, be preferably 5-15 weight %.If the chromatophorous incorporation of used for offset ink is less than above-mentioned lower limit, the water squeezing adaptability variation of aqueous pigment cream then, thus, it is bad that the flowability of flexographic ink and distinctiveness also become.And if surpass the above-mentioned upper limit, the adhesion of gained aqueous pigment cream, handling property variation.
In addition, the rosiny incorporation is equivalent to the 3-15 weight % of azoic dyestuff, is preferably 6-12 weight %.If less than above-mentioned lower limit, pigment particles crystalline growth during the pigment color lake then, it is big that particle becomes, pigment concentration decline.And if surpass the above-mentioned upper limit, then printing ink descends to the emulsive adaptability that is caused by wetting water during offset printing.That is, printing adaptability descends.
The water ratio of used for offset ink aqueous pigment cream is adjusted in 60-90 weight %.
Preferably the used for offset ink chromatophore is added in the pigment lake with following method.With the used for offset ink chromatophore 10-50 ℃ temperature range by stirring and dissolving or be dispersed in the used for offset ink solvent, again with in this solution or the suspension pigment syrup after 10-90 ℃ temperature range adds to the color lakeization.Use behind the most handy used for offset ink solvent cut of used for offset ink chromatophore.More particularly, with Toenol 1140 20 weight parts, (Nippon Oil Co., Ltd: the used for offset ink solvent) 30 weight parts add to Tamanol 361 (Japanese Arakawa Chemical Industries, Ltd. product: rosin modified phenolic resin) in 50 weight parts to No. 5 solvents, then 200 ℃ of heating for dissolving, the gained chromatophore is suspended in No. 5 solvents (Nippon Oil Co., Ltd's product) as the used for offset ink solvent.Then, this suspension is added in the pigment syrup after the color lakeization, by condensing pigment of means such as filtrations.
Solvent usage quantity during dilution used for offset ink chromatophore is equivalent to the 1-20 weight % of azoic dyestuff (the following pigment that also claims), is preferably 5-15 weight %, is equivalent to the chromatophorous 1-300 weight of used for offset ink %, is preferably 50-200 weight %.With the solvent cut chromatophore is in order to improve the chromatophorous flowability of used for offset ink, to make itself and contacting of pigment syrup become easy.The solvent of dilution usefulness can be identical or different with the solvent that uses in the used for offset ink chromatophore.
The used for offset ink aqueous pigment cream that makes with aforesaid method is made into used for offset ink printing ink by the water squeezing method.That is, used for offset ink aqueous pigment cream is added to carry out water squeezing in the used for offset ink chromatophore.The chromatophorous example of used for offset ink is as follows.
The chromatophore of forming by the solvent of the vegetables oil of the resin of 20-50 weight % such as rosin modified phenolic resin, petroleum resin, Synolac or their siccative oil modified resin, 0-30 weight % such as Toenol 1140, tung oil, soybean oil, 10-60 weight % such as normal paraffin, different alkane, aromatic solvent, cycloalkanes, alpha-olefin.In addition, add other printing ink solvents, siccative, levelling modifying agent, various known printing ink and make the offset printing ink composite with additive etc.
Below, the present invention will be described in more detail in conjunction with the embodiments.If do not particularly point out, among the embodiment, part expression weight part, % represents weight %.
Embodiment 1
1-amino-4-methylbenzene-90.6 parts of 2-sulfonic acid, 1-amino-4-methylbenzene-2.9 parts of 3-sulfonic acid, 2-amino naphthalenes-1-sulfonic acid are dissolved in by in 1500 parts in water and 20 parts of solution of forming of sodium hydroxide for 1.8 parts.Add in this mixed solution after 124 parts of 35% hydrochloric acid carry out acid out, add 1000 parts in ice again, mixture is cooled to 0 ℃.Add then by 100 parts in water and 35 parts of solution of forming of Sodium Nitrite,, obtain the diazonium composition stirring 30 minutes below 3 ℃.
β-Qiang Jinaijiasuan is dissolved in by in 3000 parts in water and 51 parts of solution of forming of sodium hydroxide, is cooled to 15 ℃ then as the coupler composition.With 20 fens clock times the diazonium composition is dropped in the coupler composition, carry out coupled reaction, mixed liquid 30 minutes, obtain azoic dyestuff.Then, add 84.8 parts of 25% rosined soaps (resin solid content be equivalent to dyestuff 10%), transfer to pH11.5 with 1% sodium hydroxide.Add 300 parts of 35% calcium chloride waters in this mixture, continuously stirring 1 hour reacts completely the color lakeization.Then, with adding the solution of making by at 21.2 parts of 21.2 parts of 20 ℃ of stirring, dispersion used for offset ink chromatophore (be equivalent to pigment 10%) and No. 5 solvents (be equivalent to pigment 10%) in 20 fens clock times pigment syrup after this color lakeization, and pigment used for offset ink chromatophore is synthesized at 200 ℃ by 361,20 parts of Toenol 1140s of 50 parts of Tamanol and 30 parts of No. 5 solvents.The pH of mixture at this moment is 11.0.With this mixture heating up to 70 ℃, filter, washing, obtain the monoazo laked pigment (pigment content is 27.5%, and moisture content is 72.5%) that pigment content accounts for 254 parts moisture paste.In the pigment content, pigment is 212 parts, and rosin is 21.2 parts (are equivalent to pigment 10%), and chromatophore is 21.2 parts (are equivalent to pigment 10%).Comparative example 1
Except that not adding the suspension of used for offset ink chromatophore, used for offset ink solvent in the pigment syrup after the color lakeization of embodiment 1, all the other are by operating with above-mentioned same method.That is, the pigment syrup after the color lakeization after 70 ℃ of heating, is filtered, washes, obtain the monoazo laked pigment (pigment content is 27.0%, and moisture content is 73.0%) of moisture paste.Comparative example 2
Remove in comparative example 1,25% rosined soap that adds in the azoic dyestuff is changed into outside 169.6 parts (are equivalent to pigment 20%) by 84.8 parts, all the other are by operating with the same method of comparative example 1, obtain the monoazo laked pigment (pigment content is 27.0%, and moisture content is 73.0%) of moisture paste.The flexographic ink test
Use pigment to carry out the flexographic ink test by embodiment 1 and comparative example 1,2 gained.In 50 parts of Tamanol 361 (rosin modified phenolic resin that waste river KCC produces), add 30 parts of 20 parts, No. 5 solvents of Toenol 1140 (printing ink solvent that Nippon Oil Co., Ltd produces), dissolve 200 ℃ of heating.In 98 parts of this chromatophores, add 2 parts of aluminium octoates, make the used for offset ink chromatophore, to carry out following test.(water squeezing adaptability)
Be in 1 liter the water squeezing testing apparatus with the used for offset ink chromatophore 200g capacity of inserting, be adjusted to 60 ℃ after, adding pigment content is the aqueous pigment cream of 106g, stirs.The pigment of comparative example 1 in 16 minutes, pigment water squeezing in 14 minutes of comparative example 2 finishes, the pigment of embodiment 1 then in 11 minutes water squeezing finish.In addition, the degree of staining of the draining that water squeezing produces is a minimum with the pigment of embodiment 1, and other are then bigger.This shows that after handling with the used for offset ink chromatophore, pigment is improved to chromatophorous wettability.After the draining, add used for offset ink chromatophore 84g,, remove moisture in the removal ink and the crystal water in the pigment 110 ℃, 70mmHg decompression heated and stirred 1 hour.After the cooling, add 110.5 parts of used for offset ink chromatophores, printing ink solvent 78.5g (No. 5 solvents).This mixture is mediated with three-roll grinder and disperseed, add used for offset ink chromatophore and printing ink solvent (No. 5 solvents) 45g altogether then, the binding property of gained printing ink is adjusted to 7.0.(flowability)
With the expansion determinator with 60 seconds value (radius) flowability is quantized.The pigment of comparative example 1 is 19.2, and the pigment of comparative example 2 is 18.4, and the pigment of embodiment 1 is 19.8, its good fluidity.(distinctiveness)
5.0g mixes with each dark ink 0.2g and white ink (be dispersed in the above-mentioned chromatophore form titanium oxide), makes light color inks.Measure chroma with chroma instrument (∑ 80 that Japanese electric look Co., Ltd. produces), their Munsell C value relatively, comparative example 1 is 12.12, comparative example 2 is 12.55, and embodiment 1 is 12.32.The comparative result of comparative example 1 and embodiment 1 shows, under the identical situation of rosin usage quantity, still can handle the distinctiveness that improves printing ink by chromatophore.(offset printing compatibility test)
Preparation contains the water soluble component that ink emulsification is formed in water printing ink extracts water, measures surface tension.The pigment of comparative example 1 is 61.5 dyne/cm, the pigment of comparative example 2 then drops to 56.7 dyne/cm, and the pigment of embodiment 1 is 61.5 dyne/cm, with comparative example 1 indifference, infers that thus handling pigment lake with the used for offset ink chromatophore has no adverse effects to offset printing adaptability.
(glossiness test and range estimation are bronze)
On enamelled paper, (Japanese Suga trier Co., Ltd. product: 60 ° of gloss) measure their gloss, comparative example 1 is 74.5%, and comparative example 2 is 72.9%, and embodiment 1 is the highest, is 78.3% with the RI tstr with the color development of saturated colour printing ink.In addition, visual observation shows, the pigment of embodiment 1 bronze minimum.Industrial possibility of its application
According to the present invention, the surface treatment method of the novelty by necessary limit that the rosin usage quantity is minimized, can improve aqueous monoazo laked pigment cream to the chromatophorous wettability of used for offset ink, water squeezing adaptability, flowability, distinctiveness, gloss with do not have bronze colour, the flexographic ink that the present invention also provides the manufacture method of this pigment paste and uses this pigment paste.
Claims (9)
1. the aqueous pigment cream that is used for flexographic ink, the pigment lake of the azoic dyestuff that is formed by the diazonium salt and the coupling of coupler composition of the aromatic amine with solubility group, the rosin that is equivalent to the 3-15 weight % of this azoic dyestuff, the used for offset ink chromatophore that contains resin for printing ink and solvent of 1-20 weight % that is equivalent to this azoic dyestuff and the water of 60-90 weight % are formed, and wherein said pigment lake, rosin and chromatophore sum are 10-40 weight %.
2. the aqueous pigment cream that is used for flexographic ink as claimed in claim 1 is characterized in that, described used for offset ink chromatophore contains the resin of 20-50 weight %, the vegetables oil of 0-30 weight % and the solvent of 10-60 weight %.
3. the aqueous pigment cream that is used for flexographic ink as claimed in claim 2 is characterized in that, described resin is to be selected from least a in rosin modified phenolic resin, Synolac, petroleum resin and their the siccative oil modified resin.
4. the aqueous pigment cream that is used for flexographic ink as claimed in claim 2 is characterized in that, described vegetables oil is to be selected from least a in Toenol 1140, tung oil and the soybean oil.
5. the aqueous pigment cream that is used for flexographic ink as claimed in claim 2 is characterized in that, described solvent is to be selected from least a in normal paraffin, different alkane, aromatic solvent, cycloalkanes and the alpha-olefin.
6. the manufacture method of the aqueous pigment cream that is used for flexographic ink of claim 1, this method comprise diazonium salt and the operation that the coupling of coupler composition obtains azoic dyestuff that will have the aromatic amine of solubility group, make gained azoic dyestuff color lake in the presence of rosiny obtain the operation of monoazo pigment slip, add the chromatophorous operation of used for offset ink that contains resin for printing ink and solvent in the gained monoazo pigment slip, be concentrated in the operation that the monoazo pigment slip that obtains in the operation of front is made the aqueous pigment cream that is used for flexographic ink.
7. the manufacture method that is used for the aqueous pigment cream of flexographic ink as claimed in claim 6 is characterized in that described used for offset ink chromatophore is further used the solvent cut mistake.
8. the manufacture method that is used for the aqueous pigment cream of flexographic ink as claimed in claim 6 is characterized in that, concentrating of described monoazo laked pigment undertaken by filtration.
9. flexographic ink is characterized in that, is used for the aqueous pigment cream water squeezing of flexographic ink and obtains claim 1 is described with the used for offset ink chromatophore.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95195326 CN1068030C (en) | 1995-06-28 | 1995-06-28 | Aqueous pigment paste for offset ink, process for producing the paste, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95195326 CN1068030C (en) | 1995-06-28 | 1995-06-28 | Aqueous pigment paste for offset ink, process for producing the paste, and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1158631A CN1158631A (en) | 1997-09-03 |
| CN1068030C true CN1068030C (en) | 2001-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95195326 Expired - Lifetime CN1068030C (en) | 1995-06-28 | 1995-06-28 | Aqueous pigment paste for offset ink, process for producing the paste, and use thereof |
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| Country | Link |
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| CN (1) | CN1068030C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425656C (en) * | 2001-08-14 | 2008-10-15 | 科莱恩产品（德国）有限公司 | Pigmented 1-naphtholsulphonic acid-based monoazo pigments |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101142288B (en) * | 2005-03-22 | 2011-05-11 | 阪田油墨株式会社 | Process for producing ink composition for offset printing, and ink composition for offset printing produced by said production process |
| US20090211489A1 (en) * | 2005-03-31 | 2009-08-27 | Sakata Inx Corp. | Process for producing ink composition for offset printing and ink composition for offset printing produced by said production process |
| JP2011068856A (en) * | 2009-08-31 | 2011-04-07 | Canon Inc | Color particle |
| JP5784954B2 (en) | 2011-04-21 | 2015-09-24 | 理想科学工業株式会社 | Non-aqueous pigment ink |
| CN109593384B (en) * | 2018-12-25 | 2020-09-25 | 宇虹颜料股份有限公司 | Preparation method of pre-dispersed pigment for offset printing ink |
-
1995
- 1995-06-28 CN CN 95195326 patent/CN1068030C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425656C (en) * | 2001-08-14 | 2008-10-15 | 科莱恩产品（德国）有限公司 | Pigmented 1-naphtholsulphonic acid-based monoazo pigments |
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| Publication number | Publication date |
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| CN1158631A (en) | 1997-09-03 |
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