JPS63230776A - Manufacture of particulate coloring agent - Google Patents

Abstract

PURPOSE:To obtain a particulate coloring agent having excellent handleability and capability of being diluted, by the flushing of a mixture of an aqueous suspension of an organic pigment, an oil varnish, and a specified higher alcohol. CONSTITUTION:An aqueous suspension (A) of an organic pigment, having a pigment concentration of 30wt.% or less, is mixed with an oil varnish (B) comprising a mixture of a resin (e.g., a polyester resin), an oil (e.g., linseed oil), and a solvent having a boiling point of 200 deg.C or higher (e.g., n-paraffin) in the weight proportions of 10-50/0-60/10-75, having a viscosity of 1-50PS (25 deg.C); and 10wt.% or less, based on the organic pigment, 10C or higher alcohol (C) which is liquid at ordinary temperature (e.g., decanol). The mixture is flushed at 20-80 deg.C for phase inversion from O/W to W/O and then rapidly cooled to near ordinary temperature, and water is removed therefrom to give a particulate coloring agent.

Description

[Detailed description of the invention] "Purpose of invention" (Industrial application field) The present invention relates to organic pigments, resins and higher alcohols.

Furthermore, if necessary, it contains a high boiling point solvent, etc., and the pigment concentration is 3.
0 to 70% by weight of a granular colorant for lithographic ink, etc., which is obtained by a flushing method from a mixture of an aqueous suspension of pigment and an oil-based varnish containing a higher alcohol. Normal pigment concentration 30-7
The present invention relates to a method for producing a granular colorant with excellent dispersibility of 0% by weight.

(Prior Art) Conventionally, in order to manufacture printing inks and the like, it is required to enhance the coloring effect of the R material by sufficiently dispersing the pigment in an organic medium such as varnish or resin. Methods for dispersing the R material include kneading the dry pigment in an organic medium, and removing a portion of water from an aqueous suspension of the R material to obtain an R'l14 concentration of 25.
A flashing method is known in which an aqueous paste and an oil-based varnish containing up to 45% by weight are charged into a flasher, the R material is phase inverted from the aqueous phase to the oily phase, and then water is removed by decantation.

In the method using dried pigments, the pigments undergo strong agglomeration during the drying process, and it is difficult to make 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 a pigment drying process, so! The pigment particles of the 1-component dispersion are uniform and fine, and a product with excellent coloring effects such as 2, coloring power, 1, 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 1U suspension of the synthesized pigment using a filter press or the like.

Furthermore, pigment dispersions (liquid or semi-liquid) obtained by conventional flushing methods have a high pigment concentration.
Moreover, the handling property becomes worse as the pigment concentration increases.

In the conventional flushing method, a pigment dispersion is obtained without a drying process, so there is no problem of pigment aggregation. In general, any type of printing ink cannot be used, depending on the combination with 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.

Also, Special Publication No. 49-8495, Special Publication No. 60-3537
No. 5, JP-A-53-134032 discloses a method in which additives are added in advance and then flushed, or a method in which a high-speed stirrer is used. Adding additives such as surfactants may have an advantageous effect on the flushing process, but the resulting colorants generally contain a large amount of additives2, for example in offset inks. When used, there is a problem with offset suitability and there is no versatility.

In the case of lithographic ink, a paste-like base ink having a relatively high pigment concentration is prepared, and the base ink is mixed with a press and diluted to produce the final lithographic ink. However, since it is paste-like, it is difficult to handle and it is difficult to obtain a high-concentration base ink with good printability. It is difficult to obtain a high ratio. Furthermore, there is no base ink that is versatile and can be used for multiple purposes.

(Problems to be solved by the invention) A highly versatile coloring agent with less pigment aggregation,
Moreover, the colorant has a simplified manufacturing process.
In other words, there has been a desire for a colorant that can be manufactured at room temperature and that not only shortens the manufacturing time, but also improves the dispersibility of the resulting colorant.

Also desirable are colorants that can be manufactured continuously. Furthermore, in terms of versatility, it is desirable that the colorant can be applied to various lithographic inks and the like as a colorant, and that it has a high pigment concentration and can be diluted to two different concentrations as a colorant.

"Structure of the Invention" (Means for Solving the Problems) The present invention contains an organic pigment, a resin, a higher alcohol, and if necessary, a high boiling point solvent, and the pigment concentration is 30 to 30.
70% by weight of a granular colorant for lithographic ink, etc., which is a method for producing a granular colorant for use in lithographic inks, etc., in which an aqueous suspension of pigment (preferably without substantially any additives added in advance) having a pigment concentration of 30% by weight or less; In a method for producing a granular colorant by mixing with an oil-based press, flashing, and isolating, a normal temperature liquid higher alcohol having a carbon number of 10 or more is added to the oil-based press in advance, or an aqueous suspension of pigment, This is a method for producing a granular colorant by mixing an oil press and a higher alcohol and flashing.

The granular colorant of the present invention contains a resin and a higher alcohol, and if necessary, a high boiling point solvent.

Contains (non-)drying oil, water, etc. However, the water content is about 20% by weight or less, and the final lithographic ink is used. Alternatively, when preparing a pigment concentrate, the water content is usually 2% by weight or less.

In addition, the above granular colorant is added to a varnish with a pigment concentration of 15 to 50.
This invention relates to a pigment concentrate that is added to a pigment concentration of 1% by weight and used for coloring printing inks such as lithographic inks, paints, etc.

The inventors of the present invention have two grains and are easy to handle.

In order to obtain a granular colorant that has high dilution ability, is versatile, and can be developed into a pigment concentrate commonly referred to as a conch base, the following conditions were investigated.

(1) Pigment concentration of the aqueous suspension of pigment (2) Composition and physical properties of the oil-based varnish (type, composition ratio, viscosity of resin, drying oil, solvent, etc.) (3) Pigment bone of the aqueous suspension of the pigment Ratio to oil-based varnish (4) Conditions for flushing The present invention is mainly related to the above (2) and (4), but the ratio of higher alcohol having a carbon number of 10 or more and liquid at room temperature to the pigment is 10% by weight. Below, preferably 1 to 8
By mixing it with an oil-based varnish or the like in a proportion of % by weight and flashing it, it is possible to shorten the production time and make it easier to disperse.

The higher alcohol is an alcohol having a carbon number of 10 or more and is liquid at room temperature, such as one or more of decanol, trimethylnonyl alcohol, dodecanol, tridecanol, and heptadecanol.

Regarding the pigment concentration of the aqueous pigment suspension in (1) above, 9 If the aqueous pigment suspension as synthesized can be used as it is, it is used as it is, but the aqueous paste does not require any dehydration. However, it is not more than 30% by weight, preferably between 5 and 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 from the viewpoint of the manufacturing process;
It is superior to water-based pastes in terms of hydrophilic process. Note that if the pigment concentration of the aqueous pigment suspension is too low or too high, the effort or time required for the flushing process will increase, which is not preferable. Therefore, the pigment concentration of the as-synthesized pigment aqueous suspension is too low.

Or when it is large, the pigment concentration can be adjusted as necessary.

Depending on the type of pigment, the pigment concentration in the aqueous pigment suspension will vary. For organic pigments, it is 5 to 25i% by weight. To obtain the preferred pigment concentration in the pigment aqueous suspension, it can be dehydrated.

In addition, in the present invention, preferably substantially no additives such as surfactants are added to the pigment aqueous suspension.

Note that additives already included during 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.

Regarding the composition of the oil-based varnish in (2) above, it is preferable to use a resin etc. that will make the obtained granular colorant for lithographic ink versatile. That is, it is preferable to use a coloring agent that can be mixed with two types of varnishes such as lithographic inks when further obtaining a pigment concentrate from two particulate colorants. In addition, it is desirable that the pigment can be mixed with various varnishes and vehicles when preparing the final lithographic ink or paint, rather than forming a pigment concentrate.

Resins for oil-based varnishes used for flushing include polyester resins (also alkyd resins), petroleum resins, phenolic resins, rosin-modified phenolic resins, epoxy resins, ketone resins, rosins, rosin derivatives, rosin-modified maleic acid resins, etc. . Drying oils include soybean oil, tung oil, linseed oil, etc., and drying oils obtained by denaturing these oils may also be used. Of course, semi-drying or non-drying oils can also be used. Solvents include normal paraffin, isoparaffin,
Organic solvents such as naphthenes (cycloparaffins), α-olefins, and other aliphatic hydrocarbons. As the solvent, a high boiling point solvent having a boiling point of 200° C. or higher is preferable. The higher alcohol is a higher alcohol having a carbon number of 10 or more and is liquid at room temperature. The composition of the oil-based varnish is 2 weight ratios of resin/oil/solvent of 10-5010-60/10-70 or a higher alcohol is added to the oil-based varnish (if
10-5010 as resin/oil/solvent/higher alcohol
~60/10~7010.5~5.

An example of the composition of an oil-based varnish for lithographic ink is rosin-modified phenolic resin/linseed oil/petroleum-based high boiling point solvent, with a weight ratio of 40/10150. Note 9
The granular colorant of the present invention does not contain drying oil, and contains resin,
It may also be a granular colorant for lithographic ink obtained from a higher alcohol and a solvent. It may also be obtained from resins, higher alcohols and drying oils, resins, higher alcohols and high boiling point solvents. For example, rosin modified phenolic resin/linseed oil (weight ratio 20/80), rosin modified phenolic resin/petroleum-based high boiling point solvent (weight ratio 3
0/70) or rosin-modified phenolic resin/linseed oil/higher alcohol (weight ratio 20/7015) or rosin-modified phenolic resin/petroleum-based high boiling point solvent/higher alcohol (weight ratio 30/6515).

The viscosity of oil-based varnish is at room temperature (25"C).

It ranges from 1 to 50 PS, preferably from 3 to 20 PS.

By adjusting the viscosity of the oil-based varnish to 1 to 50 PS (25°C), flushing can be performed at room temperature (25°C), and the production time can be further shortened. Further, it is possible to impart even more easily dispersible properties to the granular colorant that has been flushed and isolated.

The ratio of the pigment content of the pigment aqueous suspension in (3) above to the oil-based varnish is such that the pigment concentration as a flashed and isolated granular colorant is usually 30 to 70% by weight. Flushing. In other words, the higher the pigment concentration as a particulate colorant, which is determined by the pigment content of the pigment aqueous suspension and the solid content of the oil-based varnish, the better in terms of dilution ability, but if it is too high, the lithographic plate Mixability with varnishes such as inks is poor. Also, if it is too low,
Poor dilution ability.

2. Mixing of the granular colorant for lithographic ink of the present invention and varnish such as lithographic ink does not require grinding of R material particles, and the granular colorant and varnish such as lithographic ink of the present invention are simply mixed uniformly with a mixer. , can be made into final inks and paints.

The temperature for flushing in (4) above is 20 to 8
Although the process is carried out at 0°C, since the present invention contains a higher alcohol, flushing can be carried out even at temperatures around room temperature, which is advantageous in terms of production. However, it can also be heated if necessary.

For flushing, it is possible to use a flasher, but it is also possible to use the reaction vessel (tank) used for the synthesis of the R material as it is, or to prepare an aqueous suspension of the synthesized pigment at a pigment concentration of 5 to 30. An oil-based varnish is added to a tank containing an aqueous pigment suspension that has been dehydrated to a concentration of % by weight, and is mixed with stirring to undergo a phase transformation from 0/W to Wlo.
After dehydration (suction, vacuum dehydration, etc.), a granular coloring agent is produced.

Since the flushing of the present invention uses a low viscosity varnish, it is possible to make the production continuous, and the continuous convection stirring device allows for
Continuous flushing is possible.

In flushing, #I is in an ice-water suspension.

Narube (adds varnish using highly versatile resin,
Immediately after converting from 0/W to Wlo, it is preferable to rapidly cool it to around room temperature and take it out after water to obtain a granular colorant.The particle size of the granular colorant can be adjusted by adjusting the amount of varnish, temperature, etc. .

To add higher alcohol, etc., higher alcohol and oil-based varnish are simultaneously added to an aqueous suspension of organic pigment and flushed. Alternatively, it is possible to add an oil-based varnish containing higher alcohol in advance and perform flashing. Furthermore, it can also be added to an aqueous suspension of an organic pigment.

By adding 10% by weight or less of higher alcohol to the pigment, it is possible to further shorten the production time, and it is also possible to impart even more easy dispersibility to the granular colorant isolated by flashing. can.

Next, two embodiments of the present invention will be explained with reference to examples. In the examples, "part", "
%" means 1 part by weight and 2% by weight.

Example 1 Azo pigment (t'h 1207Lio manufactured by Toyo Ink Manufacturing Co., Ltd.)
90 parts of an aqueous pigment suspension with a pigment concentration of 10% (No. 10 parts of an oil-based varnish with a certain weight ratio of 3B15715 and a viscosity of 10PS (25°C) was charged into a disper (manufactured by Tokushu Kika Kogyo, 2 rotations approximately 200 Orpm) at room temperature (25°C), and after raising the temperature to 60°C, Flushing at that temperature for 10 minutes under normal pressure (
A phase transformation from oil-in-water type 0/W to water-in-oil type W10 was performed.

After decanting and removing the separated and precipitated free water, 4
It took 30 minutes at 0°C under reduced pressure to almost completely remove the remaining moisture. As a result, a granular colorant with a pigment concentration of 47% was obtained.

The average particle diameter of this granular colorant was 1.0 mm, and the kneaded dust (grind meter reading, OR) of the R material itself was 1.0 (2.5 μm). In addition, GR
In the measurement, the pigment concentrate was diluted with a petroleum solvent.

Auxiliary agents such as lithographic ink varnish and compound were added to the obtained granular colorant, and the mixture was heated in a planetary mixer (50 rpm).
pm) for 10 minutes to prepare a lithographic ink.

Examples 2 to 7 Table 1 shows examples in which the higher alcohol concentration (relative to pigment) and flushing time were changed in Example 1.

(Hereinafter, blank space) Table 1 The average particle diameter of the granular colorant measured in the same manner as in Example 1 was 0.
．． 1 to 1.0, and the GR of the pigment particles themselves were all 1.0 (2.5 μm) or less.

On the other hand, the average particle size of the granular colorant in Comparative Example 1 was 2.0 mm, and in Comparative Example 2, the colorant formed into large lumps.

Example 8 Phthalocyanine pigment (Lionol manufactured by Toyo Ink Manufacturing Co., Ltd.)
Blue SM-A) 95 parts of a pigment aqueous suspension with a pigment concentration of 10% and M amount ratio of rosin modified phenol resin/petroleum high boiling point solvent/heptadecanol 4015515
and 5 parts of oil-based varnish with a viscosity of 10PS (25℃) at room temperature (
25℃) into a disper, and at that temperature under normal pressure 15℃.
Flushing was performed for a minute.

After decanting and removing the separated and precipitated free water, 6
It took 30 minutes at 0°C under reduced pressure to almost completely remove the remaining moisture. As a result, a granular colorant with a pigment concentration of 65.5% was obtained.

Using this granular colorant for lithographic ink, the average particle diameter measured in the same manner as in Example 1 was 1.2 m, and the GR of the 2B material particles themselves was 1.0 (2.5 μm).

Examples 9 to 11 In Example 8, granular colorants were prepared with different higher alcohol concentrations, and the OR of the pigment particles themselves measured in the same manner as in Example 1 was compared and shown in Table 1-2.

Table 2 In Examples 9, 10 and 11, the flushing time was the same as in Example 8.

On the other hand, in Comparative Example 3, flushing took longer than in Example 8.

Example 12 Azo pigment (Lionol Red manufactured by Toyo Ink Manufacturing Co., Ltd.)
6B 4206) with a pigment concentration of 20% 8
0 parts and 20 parts of the oil-based varnish of Example 1 were put into a Nigu at room temperature, heated to 40°C, and then heated at that temperature for 15 minutes under normal pressure.
Flushing was performed for a minute.

After decanting and removing the separated and precipitated free water, 5
It took 40 minutes at 0°C under reduced pressure to almost completely remove the remaining moisture. As a result, a granular colorant with a pigment concentration of 44.5% was obtained.

Using this granular colorant, the average particle diameter of the granular colorant measured in the same manner as in Example 1 was 1.0 mm, and the GR of the pigment particles themselves was 2.0 < 5 μm).

Example 13 In Example 1, the oil-based varnish was replaced with a rosin-modified alkyd resin with a viscosity of 20PS/Amaniura/petroleum-based high boiling point solvent/n-
Change to dodecanol (weight ratio 25/2015015),
A granular colorant was produced in the same manner as in Example 1 except for the above. Almost the same results as in Example 1 were obtained.

Example 14 In Example 8, the oil-based varnish was changed to a rosin-modified phenolic resin with a viscosity of 20PS/linseed oil/petroleum-based high boiling point melt/heptadecanol (weight ratio 35/1015015),
A granular colorant was produced in the same manner as in Example 8 except for the above. Almost the same results as in Example 8 were obtained.

Example 15 A granular colorant was produced in the same manner as in Example 13 except that the oil-based varnish in Example 12 was changed to rosin-modified phenolic resin/linseed oil/Diadol 13 (weight ratio 20/7515) having a viscosity of 18 PS. Almost the same results as in Example 13 were obtained.

Example 16 In Example 1, 9.5 parts of an oil-based varnish containing rosin-modified phenolic resin/petroleum-based high boiling point solvent (40/60) and having a viscosity of 10 PS and 130.5 parts of Diadol were added at the same time for flushing, and the rest was as follows. A granular colorant was produced in the same manner as in Example 1. Almost the same results as in Example 1 were obtained.

Coloring examples (application examples) using the granular colorant obtained as described above are shown below.

Application example 1 (offset sheet-fed ink) Example 1~
100 parts of each of the granular colorants obtained in step 16 Letdown varnish for general sheet-fed tissue paper ink (rosin-modified phenolic resin/linseed oil/petroleum-based high boiling point solvent 2 weight ratio 40/
20/40) 180 copies.

Auxiliary agents for dryers, drying inhibitors, compounds, etc. 2
Add 0 parts and simply mix with a planetary mixer,
I created each offset ink by just making it uniform. The flow values (Sblendmeter Reading, SR) of the offset inks obtained using the respective particulate colorants or pigment concentrates are all 17-19 mm.
/min・25℃ (radius value), tank value (income value)
tar reading.

IR) were all 9-11.

When offset sheet-fed printing was carried out using the obtained offset ink, good printed matter was obtained, with good gloss and 7 remaining plates remaining on the plan. In addition.

For printing, a DAIYA-1.4 color printing machine manufactured by Mitsubishi Heavy Industries was used.

Application example 2 (offset rotary ink) Example 1~
To 100 parts of the granular colorant obtained in step 17, let-down varnish of off-cent rotary coated paper ink (rosin-modified phenolic resin/linseed oil/petroleum-based high-boiling solvent 2 weight ratio 45
/10/45) 180 parts, a dryer, a drying inhibitor,
Each offset ink was prepared by simply adding 20 parts of auxiliary agents such as compounds, and mixing and homogenizing with a planetary mixer. The flow values (SR) of the offset inks obtained using each granular colorant or pigment concentrate are all 19-21 mm/min at 25°C (radial value), and the tack values (IR) are It was also 5-6.

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 Benjo Metal were used.

Comparative Application Example 1 In Example 1, the flushing time was changed to 3 hours to obtain a granular colorant with an average particle size of 4 mm.

When 100 parts of the obtained granular colorant was mixed with a lithographic ink varnish, mixing with a planetary mixer resulted in:
There was a tendency that uniform mixing could not be achieved and particles with a particle diameter of 2 mm or more remained as they were.

Comparative Application Example 2 In Example 8, the oil-based varnish was mixed with rosin-modified phenolic resin/petroleum-based high boiling point solvent (weight ratio 60/40), viscosity L
ops High alcohol is not added.

One granular colorant was obtained by changing the flushing time to 20 minutes.

100 parts of a lithographic ink varnish and 20 parts of an auxiliary agent were added to 50 parts of this granular colorant, and the mixture was stirred and mixed using a planetary mixer to prepare an offset ink. When printed in the same manner as in Application Example 1, the printed matter was inferior in coloring strength and gloss compared to Application Example 1.

Comparative Application Example 3 In Example 1, the oil-based varnish was mixed with rosin-modified phenolic resin/petroleum-based high boiling point solvent (weight ratio 60/40), viscosity 1
0PS higher alcohol was not added, and the flushing time was changed to 15 minutes to obtain one granular colorant.

Adding 100 parts of lithographic ink varnish and 20 parts of auxiliary agent to 50 parts of this granular colorant, stirring and mixing with a planetary mixer to make the mixture uniform took 30 minutes, whereas it took 10 minutes in Application Example 1. It took. When the prepared offset ink was printed in the same manner as Application Example 2, the printed matter was inferior in coloring power and gloss compared to Application Example 2.

Claims (1)

[Scope of Claims] 1. A method for producing a granular colorant in which an aqueous suspension of an organic pigment having a pigment concentration of 30% by weight or less and an oil-based varnish are mixed, flushed, and isolated.
A method for producing a granular colorant, which comprises flushing a mixture containing 0% by weight or less of a higher alcohol having a carbon number of 10 or more that is liquid at room temperature. 2. 1 to 8% by weight of the above higher alcohol based on the organic pigment
2. A method for producing a granular colorant according to claim 1, which comprises flushing a mixture containing a granular colorant. 3. A method for producing a granular colorant according to claim 1 or 2, which uses an aqueous suspension of an organic pigment having a pigment concentration of 5 to 25% by weight. 4. A method for producing a granular colorant according to any one of claims 1 to 3, which comprises flushing at 20°C to 80°C.