JPH04218576A - Printing ink or paint composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of an organic pigment, an organic acid salt of a pigment derivative having aminomethylene group at a terminal and an oil varnish, dispersible in a short time without using roll kneading process and giving a printed matter having excellent gloss. CONSTITUTION:The objective composition is composed of (A) an organic pigment, (B) an organic acid salt of a pigment derivative expressed by formula D-[X-(CH2)n-N(R1R2)]m [D is azo, phthalocyanine (green), quinacridone, anthraquinone, dioxazine, perylene or perinone; X is -O-, -NR3-, -S-, -CO-, -SO2-, -CR3R4-, -SO2NR3- or -CONR3- (R3 is H, alkyl or aryl; R4 is alkyl or aryl); R1 and R2 are H, (substituted) alkyl or aryl; R1 and R2 may together with N form a heterocyclic group; m and n are integer of 1-4] and (C) an oil varnish.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to printing ink or coating compositions.

0002

BACKGROUND OF THE INVENTION Conventionally, in the production of printing inks, paints, etc., it has been required to enhance the coloring effect of pigments by sufficiently dispersing them in organic media such as varnishes and resins. Pigment dispersion methods include kneading dry pigments in an organic medium, and removing some water from an aqueous suspension of pigments.
A flashing method is known in which an aqueous paste and an oil-based varnish having a pigment concentration of 25 to 45% by weight are charged into a flasher, the phase of the pigment is inverted from an aqueous phase to an oily phase, and then water is removed by decantation. In the method using dried pigments, the pigments tend to aggregate strongly during the drying process, and it is difficult to disperse them into a sufficiently fine and uniform state even by a subsequent intensive grinding process with an organic medium. On the other hand, the flushing method does not involve the pigment drying process, so
The pigment particles of the pigment dispersion are uniform and fine, and a product with excellent coloring effects such as coloring power, hue, and transparency can be obtained.

However, in the flushing method, it is necessary to use an aqueous paste with a high pigment concentration as the pigment to be flushed, and it is difficult to use an aqueous suspension of an organic pigment. That is, an aqueous paste is used, which is obtained by reducing the water content of an aqueous suspension of a synthesized pigment using a filter press or the like. Furthermore, pigment dispersions (liquid or semi-liquid) obtained by conventional flushing methods are difficult to produce with high pigment concentrations, and handling properties deteriorate as the pigment concentration increases. In the traditional flushing method,
Since a pigment dispersion can be obtained without going through a drying process, there is no problem of pigment aggregation, but after flushing,
Since it is used as it is in the production of printing ink, etc., it is generally not possible to use any type of printing ink, paint, etc., depending on the combination with the varnish during flushing and the varnish that becomes the final product. In other words, it is hard to say that it is versatile. Furthermore, Japanese Patent Publication No. 36-20215 discloses a method of drying after flushing. However, the method shown here is to use an aqueous paste of the pigment or to add additives to the pigment before flushing. Moreover, after flashing and drying, it is formed into chips, flakes, etc., and has a fairly large average particle size.

[0004] Also, Special Publication No. 49-8495, Special Publication No. 6
No. 0-35375 and JP-A-53-134032 disclose a method of adding additives in advance and then flushing;
Alternatively, a method using a high-speed stirrer is shown. Adding additives such as surfactants may have an advantageous effect on the flushing process, but the resulting colorants generally contain a significant amount of additives, such as in offset inks. When used, there is a problem with offset suitability and there is no versatility. Furthermore, in the case of lithographic ink and the like, a paste-like base ink having a relatively high pigment concentration is prepared, and a varnish is mixed with the base ink and diluted to produce the final lithographic ink. However, because it is paste-like, it is difficult to handle and it is difficult to obtain a high-density base ink suitable for printing.
Therefore, it is difficult to obtain a base ink with a high diluting ability, that is, a base ink with a high pigment concentration and a high blending ratio of lithographic ink varnish to be added. Furthermore, there is no base ink that is versatile and can be used for multiple purposes. Furthermore, in conventional lithographic inks produced by flushing, agglomeration of pigments is relatively low, but roll kneading is still required.

[0005]

[Problems to be Solved by the Invention] The present inventors have discovered that by using a dye derivative having an aminomethylene group at the end, the dispersion time can be shortened using a mixer such as a roll mill, attritor, sand mill, ball mill, or dissolver. It has been found that it is possible to obtain a printing ink which does not require roll milling in, for example, lithographic ink. It has also been found that by using rosin or modified rosin as the organic acid salt, the resulting printing inks, paints, etc. have excellent coloring power, fluidity, etc.

[0006]

The present invention relates to a printing ink or coating composition characterized by comprising an organic pigment, an organic acid salt of a dye derivative represented by the following general formula, and an oil-based varnish. D-[X-(CH2)n-N(R1,
R2)]m (1) (wherein D is at least one organic dye residue selected from azo, phthalocyanine, phthalocyanine green, quinacridone, anthraquinone, dioxazine, perylene, perinone, and X is -
O-, -NR3-, -S-, -CO-, -SO2-
, -CR3 R4 -, -SO2 NR3 -, -CO
a divalent bonding group selected from NR3 - (wherein R3 is a hydrogen atom, an alkyl group or an aryl group, and R4 is an alkyl group or an aryl group); R1 and R2 have a hydrogen atom and a substituent; m is an integer of 1 to 4, and n is an integer of 1 to 4. )

The printing ink or coating composition of the present invention is an oil-based varnish containing an organic acid salt obtained by adding an alkaline aqueous solution of an organic acid to an aqueous pigment suspension containing a pigment derivative represented by the general formula (1). It can be manufactured by mixing with At this time, it is preferred that the organic acid salt of the pigment derivative (1) be flushed with an appropriate amount of oil-based varnish in advance to produce an easily dispersible pigment. Regarding the pigment concentration of pigment aqueous suspension,
If the as-synthesized pigment aqueous suspension can be used as is, it is used as is. In this case, dehydration is not as necessary as in aqueous pastes, but it is adjusted to 30% by weight or less, preferably about 5 to 25% by weight. The pigment concentration is generally around what is called an aqueous slurry. If the aqueous pigment suspension as synthesized can be used as it is, it is advantageous in terms of the manufacturing process, and at a concentration of about 5 to 25% by weight, it is advantageous in the dehydration process compared to an aqueous paste. It should be noted that if the pigment concentration of the aqueous pigment suspension is too low or too high, the effort and time required for the flushing step will increase, which is not preferable. Therefore, if the pigment concentration of the as-synthesized pigment aqueous suspension is too low or high, the pigment concentration can be adjusted as necessary. Further, the pigment concentration in the aqueous pigment suspension varies depending on the type of pigment, but is generally 5 to 25% by weight. The pigment can be dehydrated to achieve the desired pigment concentration in the aqueous suspension. In addition, additives already contained in the aqueous pigment suspension at the time of pigment synthesis are usually left as they are. If necessary, it is also possible to remove the additives already contained, and it is also possible to use an aqueous pigment suspension that has been washed with water, dehydrated, etc.

[0008] The amount of the pigment derivative (1) added varies depending on the type and use of the pigment, but is 0.5 to 30% by weight based on the pigment. If it is less than 0.5% by weight, the dispersibility is insufficient, and if it exceeds 30% by weight, the tinting strength is likely to decrease. Preferably it is 2 to 10% by weight. Examples of the organic acids according to the present invention include benzoic acid, beta-oxynaphthoic acid, rosin, modified rosin, and carboxylic acid type resins having an acid value of 70 or more. The amount of the organic acid added is 0.3 to 5 times the mole, preferably 0.7 to 2 times the mole of the dye derivative (1). If it is less than 0.3 mol, the dispersibility is insufficient,
Moreover, if the amount exceeds 5 times the molar amount, flushing due to the addition of an oil-based varnish becomes difficult to occur.

[0009] Regarding the composition of the oil-based varnish, it is preferable to use a resin or the like that allows the obtained easily dispersible pigment to be used for general purposes. That is, from easily dispersible pigments to printing inks,
When obtaining colored paints and resins, or pigment concentrates for these, materials that can be mixed with various varnishes and resins are preferred. It is also possible to use it as a final printing ink, paint, etc. instead of using it as a pigment concentrate. In general, when preparing easily dispersible pigments similar to final printing inks and paints, it is desirable that they can be mixed with various varnishes or vehicles. Examples of oil-based varnish resins used for flushing include polyester resin (alkyd resin),
Petroleum resin, phenolic resin, rosin modified phenolic resin, epoxy resin, ketone resin, rosin, rosin derivative,
These include rosin-modified maleic acid resin, polyamide, urethane resin, acrylic resin, and salt-vinyl acetate resin. It may be a varnish containing a drying oil or a non-drying oil. Examples of the solvent include organic solvents such as normal paraffin, isoparaffin, naphthene (cycloparaffin), alkylbenzene, α-olefin, and other aliphatic hydrocarbons. Boiling point 2 as a solvent
A high boiling point solvent of 00°C or higher is preferred. The composition of the oil-based varnish is a resin/solvent weight ratio of 10 to 70/30.
~90.

An example of the composition of an oil-based varnish for lithographic ink is rosin-modified phenolic resin/petroleum-based high boiling point solvent, with a weight ratio of 40/60. Note that the granular colorant for lithographic ink of the present invention does not contain drying oil,
It may also be a granular colorant for lithographic ink obtained from a resin and a solvent. It may also be obtained from a resin and a drying oil, a resin and a high boiling point solvent. For example, rosin modified phenolic resin/linseed oil (weight ratio 40/60)
) and rosin-modified phenolic resin/petroleum-based high boiling point solvent (weight ratio 50/50). The viscosity of oil-based varnish is
It is in the range of 100 to 30,000 ps, preferably 300 to 10,000 cps at room temperature (25°C).

[0011] The ratio of the pigment content of the pigment aqueous suspension to the oil-based varnish is such that the pigment concentration as an easily dispersible pigment that has been flushed and isolated (dried) is 30 to 80% by weight. . That is, it is determined by the pigment content of the pigment aqueous suspension and the solid content of the oil-based varnish. A high pigment concentration as an easily dispersible pigment is advantageous in terms of dilution ability, but if it is too high, the mixability with a varnish will be poor when used as a final ink, paint, etc. Moreover, if it is too low, the dilution ability will be poor. Note that the mixing of the easily dispersible pigment and varnish of the present invention does not require grinding of pigment particles, and the easily dispersible pigment and varnish are simply mixed uniformly using a mixer, and printing ink, paint, etc. can be obtained. Flushing is carried out at room temperature to 80°C, preferably 50°C.
Perform at ~70°C.

As for flushing, it is possible to use a flasher, but it is also possible to use the reaction vessel (tank) used for pigment synthesis as it is, or to use an aqueous suspension of the synthesized pigment at a pigment concentration of 5 to 5. Oil-based varnish is added to a tank containing an aqueous pigment suspension that has been dehydrated to a concentration of 30% by weight, mixed with stirring, phase conversion from O/W to W/O is carried out, and dehydration (suction, vacuum (dehydration, etc.) to produce easily dispersible pigments. In flushing, a varnish made of a highly versatile resin is added little by little to an aqueous pigment suspension, and immediately after conversion from O/W to W/O, it is rapidly cooled to around room temperature, and after dehydration. , it is preferred to obtain an easily removable and dispersible pigment. In addition, the particle size of the easily dispersible pigment is
It can be adjusted by adjusting the amount of varnish, temperature, etc. The particle size (diameter) of the easily dispersible pigment is 2 mm or less, usually 0.1 to 1.8 mm. If it is too large, miscibility with added varnish etc. will be poor.

[0013] In the present invention, the easily dispersible pigment is mixed with an appropriate amount of oil-based varnish, etc. to form a paste-like pigment concentrate, and then mixed with a printing ink or an oil-based varnish for paint to obtain a printing ink or paint composition. can. To produce this pigment concentrate, for example, a lithographic ink varnish is added to the easily dispersible pigment so that the pigment concentration is 10 to 50% by weight, and the mixture is mixed using a planetary mixer or the like for about 30 minutes to 1 hour. This makes it possible to obtain a uniform paste-like base ink. Note that the kneading and dispersing step for finely dividing the pigment particles is not necessary at all. Furthermore, the varnish used for producing the pigment concentrate can be the same as or different from the varnish used for flushing. Next, according to an example,
The present invention will be explained. In the examples, "parts" and "%" refer to parts by weight,
Indicates weight %.

[0014]

[Example] Production Example 1 (Production of easily dispersible pigment) 660 parts of water and phthalocyanine pigment (Toyo Ink Mfg. Co., Ltd.)
OnolBlue SM) 5 parts of a copper phthalocyanine derivative represented by the following formula were mixed and stirred into 330 parts of a wet cake with a pigment concentration of 30%. An aqueous rosin sodium solution was added to this aqueous suspension so that the copper phthalocyanine derivative and rosin were in equimolar numbers. CuPc-SO2NH(CH2)2
-N(CH3)2 (CuPc indicates a copper phthalocyanine residue.) To 100 parts of this aqueous suspension heated to 50°C in a beaker, add a rosin-modified phenolic resin/petroleum-based high boiling point solvent (Nippon Oil Co., Ltd. Flushing was carried out by adding 6 parts of an oil-based varnish of No. 0 Solvent H) manufactured by ), manufactured by Co., Ltd., in a weight ratio of 40/60, while stirring at a rotational speed of about 3000 rpm using a high-speed mixer. Flushing was completed in 10 to 20 minutes, and the easily dispersible pigment suspended on the water surface was separated by suction filtration. Since the primary particles of this easily dispersible pigment are weakly aggregated, filtration is quick, and after filtration, it is already in a powder form, and even residual moisture of about 30% can be dried in a few hours at room temperature. finished.

Next, the dispersibility of the obtained easily dispersible pigment was evaluated by an ink test. When the easily dispersible pigment and lithographic ink varnish were stirred using a high-speed mixer, mixing was completed in a few minutes. The dispersibility of this ink was measured using a grindmeter and was found to be 7.5 microns or less. Furthermore, when comparing the coloring power with conventional inks using white ink cut, the easily dispersible pigment of the present invention was superior.

Production Examples 2 to 4 (Production of easily dispersible pigment) Production Example 1 was carried out using the following pigments and pigment color derivatives under the conditions shown in Table 1.
An easily dispersible pigment was obtained in the same manner as above.

Pigment and dye derivative production example 2 LIONOL RED 6B 42
06 (Red pigment manufactured by Toyo Ink Manufacturing)

[Chemical formula 1]

Production Example 3 No. 1207 LIONO
L YELLOW (yellow pigment manufactured by Toyo Ink)

[Case 2]

Production Example 4 Carbon black

[Chemical formula 3]

[0020]

[Table 1]

[0021] Results close to those of Production Example 1 were obtained in all production examples.

Comparative Production Example 1 100 parts of an aqueous suspension of Lionol Blue SM with a pigment concentration of 10% was heated to 50°C, and while stirring with a high-speed mixer (3000 rpm), rosin-modified phenolic resin/Nippon Oil Co., Ltd. Oil-based varnish (for lithographic ink) with a weight ratio of 40/60 consisting of No. 0 Solvent H manufactured by Manufacturer Co., Ltd.
6 parts were added, and the pigment was separated from water by suction, filtration, and dried at room temperature. When the obtained pigment was mixed with the above-mentioned oil-based varnish using a high-speed mixer, small particles were observed in the ink, and when the dispersibility was measured using a grindmeter, it was found to be 20 microns.

Production Example 5 (Production of easily dispersible pigment) Production Example 1
An easily dispersible pigment was produced in the same manner as in Production Example 1, except that the oil-based varnish was replaced with rosin-modified alkyd resin/linseed oil/petroleum-based high-boiling solvent (weight ratio 30/20/50). Almost the same results as in Production Example 1 were obtained.

Production Example 6 (Production of easily dispersible pigment) Production Example 2
An easily dispersible pigment was produced in the same manner as in Production Example 2, except that the oil-based varnish was replaced with rosin-modified phenolic resin/No. 0 Solvent H (weight ratio 50/50). Almost the same results as Production Example 2 were obtained.

Production Example 7 (Production of easily dispersible pigment) Production Example 1
When flushing was carried out at room temperature, flushing was completed although it took about 1.5 hours. The easily dispersible pigment obtained showed almost the same results as Production Example 1. Examples using the easily dispersible pigment obtained as described above are shown below.

Example 1 (offset sheet-fed ink) 100 parts of each of the easily dispersible pigments obtained in Production Examples 1 to 7 were added with a let-down varnish for general sheet-fed paper ink (rosin-modified phenolic resin/linseed oil/petroleum oil). By adding 180 parts of high-boiling point solvent (weight ratio 40/20/40) and 20 parts of auxiliary agents such as dryers, drying inhibitors, compounds, etc., and simply mixing and homogenizing with a planetary mixer, each offset ink was created. The flow values (spread meter reading, SR) of each offset ink were all 16 to 18 mm/min and 25°C (radial value), and the tack values (incometer reading, IR) were all 10 to 12. . When offset sheet-fed printing was performed using the obtained offset ink, good printed matter was obtained with good gloss, blank residue, and plate residue. The printing is done by Mitsubishi Heavy Industries DAIYA-
I. A four-color printing press was used.

Example 2 (offset rotary ink) 100 parts of the easily dispersible pigments obtained in Production Examples 1 to 7 were mixed with a let-down varnish for offset rotary coated paper ink (rosin-modified phenolic resin/linseed oil/petroleum-based high boiling point By simply adding 180 parts of solvent (weight ratio 45/10/45) and 20 parts of auxiliary agents such as dryers, drying inhibitors, compounds, etc., and mixing them uniformly with a planetary mixer, each offset ink can be made. It was created. The flow value (SR) of each offset ink is 19 to 20 m.
m/min・25° C. (radial value), and the tack value (IR) was 5 to 6 in all cases. When offset rotary printing was performed using the obtained offset ink, good printed matter was obtained. For printing, an L-500 four-color printing machine manufactured by Mitsubishi Heavy Industries and a TEC dryer device manufactured by Inoue Metals were used.

Comparative Example 1 Using the pigment obtained in Comparative Production Example 1, 180 parts of the same letdown varnish as in Example 1 and 20 parts of auxiliary agent were added, and the mixture was passed through three rolls twice without kneading. mixed with. The flow value was 17 mm/min and the tack value was 11. When this ink was used for printing in the same manner as in Example 1, the printed matter was inferior in coloring strength and gloss compared to Example 1.

Production Examples 8 to 10 and Example 3 Easily dispersible pigments were obtained according to Production Example 1 under the conditions shown in Table 2. The obtained easily dispersible pigments were mixed with amino alkyd resin varnish for baking paints (solid content 46%) using a high-speed mixer so that the pigment content was 6%, and the dispersibility was measured using a grind meter. When evaluated, all of them were 1
It was less than 0 micrometer.

[0030]

[Table 2]

Comparative Production Example 2 and Comparative Example 2 Lionol
Blue SM aqueous suspension 1 with a pigment concentration of 10%
Heat 00 parts to 50℃ and mix it with a high speed mixer (30
While stirring at 00 rpm), 6 parts of an oil-based varnish of amino alkyd resin varnish for baking paints was added, and the pigment was separated from water by suction and filtration, and dried at room temperature. When the obtained pigment was mixed with the above-mentioned oil-based varnish using a high-speed mixer, small particles were observed in the paint, and when the dispersibility was measured using a grindmeter, it was found to be 50 microns.

Production Example 11 660 parts of water and a phthalocyanine pigment (LionolBlue SM manufactured by Toyo Ink Mfg. Co., Ltd.) at a pigment concentration of 30
% wet cake were mixed and stirred with 10 parts of a copper phthalocyanine derivative represented by the following formula. To this aqueous suspension, an alkaline aqueous solution of fumaric acid-modified rosin was added so that the copper phthalocyanine derivative and rosin were in equimolar proportions, stirred at 50°C for 30 minutes, adjusted to pH 7, filtered, and washed with water. , drying, and pulverization to obtain 113 parts of a pigment composition. CuPc-CONH(CH2)3-N(C2H5
)2 (CuPc indicates copper phthalocyanine residue.)

Comparative Production Example 3 The same treatment as in Production Example 11 was carried out except that no fumaric acid-modified rosin was added, to obtain 108 parts of a pigment composition.

Production Example 12 In Production Example 11, azo lake pigment (Toyo Ink Mfg. Co., Ltd. Lionol Red 6B 42) was used as the pigment.
06) to the dye derivative,

The same treatment was carried out except that 114 parts of a pigment composition was obtained except that 114 parts of a pigment composition was obtained.

Comparative Production Example 4 The same treatment as in Production Example 12 was carried out except that no fumaric acid-modified rosin was added, to obtain 108 parts of a pigment composition.

Production Example 13 In Production Example 11, disazo pigment (Toyo Ink Mfg. Co., Ltd. No. 1207 Lionol Yel) was used as the pigment.
low) to the dye derivative,

The same treatment was carried out except that 115 parts of a pigment composition was obtained.

Comparative Production Example 5 The same treatment as in Production Example 13 was carried out except that no fumaric acid-modified rosin was added, to obtain 109 parts of a pigment composition. Examples 4-6 and Comparative Examples 3-5

Production Examples 11 to 13 and Comparative Production Examples 3 to 5
To 100 parts of each of the pigment compositions obtained, let-down varnish for general sheet paper ink (rosin-modified phenolic resin/linseed oil/petroleum-based high-boiling solvent, weight ratio 40/2) was added.
0/40) and 20 parts of auxiliary agents such as a dryer, a drying inhibitor, and compounds were added and kneaded with three rolls to prepare each offset ink. The flow values (SR) of each offset ink are shown in Table 3. All examples have better fluidity than the corresponding comparative examples. After adjusting the flow value and tack value of the obtained offset ink to 16 to 18 mm/min and 10 to 12 mm/min by adding letdown varnish or a petroleum-based high boiling point solvent, offset sheet-fed printing was performed. However,
In each of the examples, printed matter with better gloss than the corresponding comparative example was obtained. The printing is done by Mitsubishi Heavy Industries DAIYA-I.
, a four-color printing press was used.

[0038]

[Table 3]

Claims (1)

[Claims] 1. A printing ink or coating composition comprising an organic pigment, an organic acid salt of a dye derivative represented by the following general formula (1), and an oil-based varnish. D-[X-(CH2)n-N(R1,R2
)]m (1) (wherein D is at least one organic dye residue selected from azo, phthalocyanine, phthalocyanine green, quinacridone, anthraquinone, dioxazine, perylene, perinone, and X is -O-
, -NR3 -, -S-, -CO-, -SO2 -, -
CR3 R4 −, −SO2 NR3 −, −CONR
3 - (wherein R3 is a hydrogen atom, an alkyl group or an aryl group, and R4 is an alkyl group or an aryl group); R1 and R2 are hydrogen atoms and have a substituent; m is an integer of 1 to 4, and n is an integer of 1 to 4. )