JP5031734B2 - Method for producing extender pigment dispersion for oil-based printing, extender pigment dispersion for oil-based printing obtained by the method, and use thereof - Google Patents

Description

The present invention relates to a method for producing an oil-based printing extender dispersion used for fluidity adjustment and water width adjustment of an oil-based printing ink composition used in offset printing or the like. Moreover, it is related with the extender dispersion for oil-based printing obtained by this manufacturing method, and its use.

Ink compositions for oil-based printing used in offset printing (including newspaper printing) and the like often have extender pigments added for the purpose of fluidity adjustment, water width adjustment, etc. Reference 1).

As means for incorporating the extender pigment into the oil-based printing ink composition, means (1), (2) and the like are implemented.
(1) A powdery extender that has been surface-treated is added to an oil-based printing ink composition and dispersed.
(2) An oily varnish is added to a wet cake or press cake of an extender pigment containing 50 to 80% of water and stirred to disperse the pigment in the oily varnish. Then, the obtained oily extender pigment composition is added to and dispersed in the oily printing ink composition.

However, in the above means (1), powdery extender pigments are aggregated. For this reason, in order to make it disperse | distribute in the ink composition for oil-based printing, there exists a problem that a lot of energy and dispersion | distribution for a long time are needed. Further, in the above means (2), an extender wet cake or press cake containing 50 to 80% of water is used. For this reason, it has the problem that transportation cost increases.
Journal of Japan Society of Printing Science (Vol. 39, No. 1, 2002)

Therefore, the problem to be solved by the present invention is to provide a method for producing an extender dispersion for oil-based printing that can be moistened with a wetting agent containing water to improve dispersibility and greatly improve productivity over conventional means. Is to provide. In this case, the object is to obtain the above effect despite the use of extender pigments that are surface treated to give good wettability to the oil varnish and do not wet with water alone. . Another problem to be solved by the present invention is to provide an oil-based extender dispersion for oil-based printing obtained by the production method and its use.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a specific method in which an extender that has been surface-treated is wetted with water in a method for producing an extender dispersion for oil-based printing. It has been found that all of the above problems can be solved by using a compound in combination. As a result, the present invention has been completed.

That is, (1) at least one compound selected from the group consisting of water (A) and compounds represented by the following general formulas (1) to (4) (100 parts by mass of the surface-treated extender pigment ( B) and (A) / (B) = 99.9 / 0.1 to 80.0 / 20.0 in a mass ratio of wetting agent 19 to 190 parts by weight,
Dispersing the wet extender in oily varnish and then removing water (A);
The present invention relates to a method for producing an extender dispersion for oil-based printing.
R ¹ —OH General formula (1)
(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be linear or branched);
_{^{R 2 - (O-R 3}} ) n -OH Formula (2)
(In the formula, R ² is a monovalent hydrocarbon group having 1 to 18 carbon atoms and may be an aliphatic group or an aromatic group. R ³ is an ethylene group, a propylene group, or A butylene group, n is an integer from 1 to 10);
HO—R ⁴ —OH general formula (3)
(Wherein R ⁴ is a hydrocarbon group having 2 to 12 carbon atoms, and may be an aliphatic group or an aromatic group, and may be linear or branched);
R ^5- (OH) ₃ General formula (4)
(In the formula, R ⁵ is a trivalent hydrocarbon group having 3 to 6 carbon atoms, which may be linear or branched).

In addition, the present invention provides (2) a particle size of the extender pigment that has been subjected to a surface treatment with a roll mill or a bead mill after completion of the step of wetting and dispersing and then removing the water (A). The invention relates to a method for producing an extender dispersion for oil-based printing as described in the above item (1), which comprises a step of kneading until the particle size becomes 10 μm or less with a grind gauge.

In the present invention, (3) the compound (B) is at least one compound selected from the group consisting of compounds represented by the following general formulas (5) to (9) having a boiling point of 200 ° C. or higher. The method for producing an extender dispersion for oil-based printing according to claim 1.
R ¹ —OH General formula (5)
(Wherein R ¹ is a hydrocarbon group having 9 to 16 carbon atoms, which may be linear or branched);
_{^{R 2 - (O-R 3}} ) n -OH Formula (6)
(Wherein R ² is a monovalent aliphatic group having 2 to 8 carbon atoms, R ³ is an ethylene group, and n is an integer of 1 to 3);
_{^{R 2 - (O-R 3}} ) n -OH Formula (7)
(Wherein R ² is a monovalent hydrocarbon group having 14 to 15 carbon atoms containing an aromatic group, R ³ is an ethylene group, and n is an integer of 5 to 10);
HO—R ⁴ —OH general formula (8)
(In the formula, R ⁴ is a divalent hydrocarbon group having 6 to 12 carbon atoms, and may be an aliphatic group or an aromatic group. good.);
R ^5- (OH) ₃ General formula (9)
(In the formula, R ⁵ is a trivalent hydrocarbon group having 4 to 6 carbon atoms, which may be linear or branched.)

In addition, the present invention provides (4) an oil-based printing extender obtained by the method for producing an oil-based printing extender dispersion described in any one of (1) to (3) above. Concerning the dispersion.

The present invention also relates to (5) an offset printing ink composition comprising the oil-based printing extender dispersion described in the above item (4).

Hereinafter, the present invention will be described in more detail.

First, the constituent materials and the production method used in the production method of the extender dispersion for oil-based printing of the present invention (hereinafter also referred to as “extension pigment dispersion”) will be described.

As an extender used in the production method of the present invention, a surface-treated extender pigment that cannot be wetted with water alone can be exemplified. If it is conventionally used for the ink composition for oil-based printing, it can be used without being specifically limited. Examples of the extender pigment include calcium carbonate, silica, barium sulfate, barium carbonate, kaolinite, which are surface-treated with halogenated silanes, alkoxysilanes, silazanes, siloxanes, long-chain fatty acid salts, and the like. Examples include talc, organic bentonite, titanium oxide, magnesium carbonate, and alumina white. These can use what was surface-treated by a conventionally well-known method.

Therefore, in the present invention, in order to wet the extender pigment, a wetting agent containing at least one compound (B) selected from the group of water (A) and general formulas (1) to (4) is used. Use.

It does not specifically limit as water (A) to be used, A tap water, well water, ion-exchange water, distilled water, etc. can be used. From the viewpoint that the content of water-soluble ionic substances that adversely affect printing is small, it is preferable to use ion-exchanged water or the like.

Examples of the compound (B) used in combination with water (A) include at least one compound selected from the group consisting of the compounds represented by the general formulas (1) to (4).

Specific examples of the compound (B) include the following. For example, as the compound represented by the general formula (1), methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol 2-methyl-2-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-pentanol, 2- Pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl- 1-butanol, 3-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentane 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 1- Octanol, 2-octanol, 3-octanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 1-nonanol, 2-nonanol, 3,5,5-trimethyl- 1-hexanol, 1-decanol, 2-decanol, 4-decanol, 3,7-dimethyl 1-octanol, 3,7-dimethyl-3-octanol, 1-undecanol, 2-undecanol, 2-butyl-1-octanol 1-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 1-hexadecano Le, 2-hexadecanol, 2-hexyl-1-decanol, 1-heptadecanol, 1-octadecanol and the like.

Examples of the compound represented by the general formula (2) include 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, 2-ethylhexyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol. Hexyl diglycol, 2-ethylhexyl diglycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, octylphenol ethylene glycol 3 mol adduct, nonylphenol ethylene glycol 5 mol adduct, nonylphenol ethylene glycol 7.5 mol adduct, Examples include lauryl alcohol ethylene glycol 9 mol adduct, oleyl alcohol ethylene glycol 10 mol adduct, and the like.

Examples of the compound represented by the general formula (3) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 1,2-butanediol. 1,5-pentanediol, 1,4-pentanediol, 1,2-pentanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,5- Hexanediol, 1,2-hexanediol, 2,5-hexanediol, 3,3-dimethyl-1,2-butanediol, 2-methyl-2,4-pentanediol, 1,7-heptanediol, 2, 2-dimethyl-1,3-propanediol, 2,4-dimethyl-2,4-propanediol, 2-methyl-propyl-1,3-propanediol 1,8-octanediol, 1,2-octanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3- Pentanediol, 1,9-nonanediol, 2-butyl 2-ethyl-1,3-propanediol, 1,10-decanediol, 1,2-decanediol, 2,2-dibutyl-1,3-propanediol 1,12-dodecanediol, 1,2-dodecanediol and the like.

Examples of the compound represented by the general formula (4) include glycerin, 1,2,4-butanetriol, and 3-methyl-1,3,5-pentanetriol.

Among these, at least one compound selected from the group consisting of compounds represented by the above general formulas (5) to (9) having a boiling point of 200 ° C. or higher is preferable.

In addition, when using the ink composition for offset printing described below containing an extender pigment dispersion, 1-decanol, 2-decanol, 4-decanol having a boiling point of 200 ° C. or more from the viewpoint of printability, 3,7-dimethyl 1-octanol, 3,7-dimethyl-3-octanol, 1-undecanol, 2-undecanol, 1-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 1 -Hexadecanol, 2-hexadecanol, 2-hexyl-1-decanol, ethyl diglycol, butyl diglycol, hexyl diglycol, 2-ethylhexyl diglycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 3 mol of octylphenol ethylene glycol Adduct, nonylphenol ethylene glycol 5 mol adduct, nonylphenol ethylene glycol 7.5 mol adduct, lauryl alcohol ethylene glycol 9 mol adduct, oleyl alcohol ethylene glycol 10 mol adduct, 1,6-hexanediol, 1,5- Hexanediol, 1,2-hexanediol, 2,5-hexanediol, 3,3-dimethyl-1,2-butanediol, 1,7-heptanediol, 2,2-dimethyl-1,3-propanediol, 2,4-dimethyl-2,4-propanediol, 2-methyl-propyl-1,3-propanediol, 1,8-octanediol, 1,2-octanediol, 2,5-dimethyl-2,5- Hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-to Methyl-1,3-pentanediol, 1,9-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,10-decanediol, 1,2-decanediol, 2,2-dibutyl -1,3-propanediol, 1,12-dodecanediol, 1,2-dodecanediol, glycerin, 1,2,4-butanetriol, 3-methyl-1,3,5-pentanetriol, etc. (boiling point 200) It is particularly preferable to use a compound having a temperature equal to or higher than 0 ° C. and hereinafter referred to as “compound group 1”.

The amount of the water (A) and at least one compound (B) selected from the group consisting of the compounds represented by the general formulas (1) to (4) is 100 parts by mass of extender pigment, The total amount of the water (A) and the compound (B) is 19 to 190 parts by mass. Moreover, it uses so that the mass ratio of (A) / (B) may become 99.9 / 0.1-80.0 / 20.0 from the point of an environmental aspect or wettability.

When the total amount of (A) and (B) is less than 19 parts by mass, good dispersion cannot be obtained. On the other hand, when the amount is more than 190 parts by mass, the dehydration time becomes longer, and the productivity is lowered. In addition, there is a problem that the amount of dehydrated water increases and an extra treatment is required.

In addition, in the mass ratio of (A) / (B), when the mass ratio of (A) is larger than 99.9, good dispersion cannot be obtained. On the other hand, when the mass ratio of (A) is smaller than 80.0, there is a problem that printability is lowered when added to an oil-based printing ink composition. In addition, when a favorable dispersion is obtained, the one where the mass ratio of (A) is large is preferable from the surface of cost.

Next, as the varnish for oil-based printing ink (oil-based varnish) used in the production method of the present invention, one containing a binder resin and an oily liquid can be used.

As the binder resin, rosin-modified phenolic resin, rosin-modified maleic acid resin, petroleum resin-modified phenolic resin, polyester resin not containing phenol, alkyd resin, petroleum resin, etc. used in ink compositions for offset printing are used. be able to.

The amount of the binder resin used in the varnish for oil-based printing ink is usually in the range of 20 to 60% by mass with respect to 100% by mass of the varnish for oil-based printing ink. Preferably it is 30-50 mass%, More preferably, it is the range of 35-45 mass%.

As the oily liquid, vegetable oil components, mineral oil components and the like can be used.

Examples of the vegetable oil component include vegetable oils and fatty acid ester compounds derived from vegetable oils.

Examples of the vegetable oil include dry oil or semi-dry oil suitable for offset printing such as soybean oil, cottonseed oil, linseed oil, safflower oil, tung oil, tall oil, dehydrated castor oil, and canola oil. These may be used alone or in combination of two or more.

Examples of the fatty acid ester compound derived from the vegetable oil include monoalkyl ester compounds of fatty acids derived from the drying oil or semi-drying oil. As the fatty acid constituting the fatty acid monoalkyl ester, a saturated or unsaturated fatty acid having 16 to 20 carbon atoms is preferable. Specific examples include stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid. The alcohol-derived alkyl group constituting the fatty acid monoalkyl ester preferably has 1 to 10 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and 2-ethylhexyl alkyl groups. These fatty acid ester compounds may be used alone or in combination of two or more.

Examples of the mineral oil component include those that are not compatible with water and have a boiling point of 180 ° C. or higher, preferably 200 ° C. or higher. Specifically, petroleum solvents such as n-paraffin solvents, isoparaffin solvents, naphthene solvents, aromatic solvents, α-olefin solvents, etc., conventionally used as ink solvents for offset printing, Examples include spindle oil, machine oil, cylinder oil, turpentine oil, and mineral split.

In the varnish for oil-based printing ink, the vegetable oil component and the mineral oil component may be a vegetable oil component alone or a mineral oil component alone. Moreover, you may use together and use a vegetable oil component and a mineral oil component.

Furthermore, additives such as a gelling agent, a drier (drying agent), a drying retarder, and an antioxidant may be appropriately used in the varnish for oil-based printing ink as necessary.

<Method for producing extender pigment dispersion>
Next, the manufacturing method of the extender dispersion of this invention is demonstrated.
In the production method of the present invention, 100 parts by mass of the extender pigment is used, and the water (A) and the compound (B) are mixed in a mass ratio of (A) / (B) = 99.9 / 0.1-80 / 20. A step of wetting with 19 to 190 parts by weight of a wetting agent contained in Also included is a step of dispersing the wet extender pigment in an oil varnish and then removing water.

In the step of removing water, it is preferable that the low-boiling-point wetting agent component other than water, that is, the low-boiling-point compound (B) is removed at the same time when water is removed. On the other hand, it is preferable to leave a high-boiling component such as the above compound group 1 having a boiling point of 200 ° C. or higher in the composition.

It is preferable to heat at 80-150 degreeC as conditions under pressure reduction, and it is especially preferable to heat at 90-120 degreeC. Moreover, it is preferable that pressure reduction conditions are 50-300 (Torr) (= 6.7-40 kPa), and it is especially preferable to reduce pressure at 60-150 (Torr) (= 8.0-20 kPa).
In addition, the process of removing the water includes not only a process of removing only water but also a process of removing components other than water and water. Specifically, a step of removing water and a low-boiling-point wetting agent component (boiling point less than 200 ° C.) may be mentioned. In particular, when a high-boiling humectant component (boiling point 200 ° C. or higher) is contained, a step of removing water and the high-boiling humectant component may be mentioned. Furthermore, the process of removing water, a low boiling point wetting agent component, and a high boiling point wetting agent component is also mentioned.

In the step of wetting the pigment with the wetting agent, water (A) and compound (B) may be mixed in advance to prepare the wetting agent, and then the pigment may be moistened. Further, water (A) and compound (B) may be separately added to the pigment and stirred to be wetted.

In the production method of the present invention, the apparatus for wetting the extender pigment is not particularly limited. Among them, it is preferable to use either a disper or a flasher (kneader).

In the production method of the present invention, an apparatus used for dispersing the above extender pigment wetted in the oil-based printing varnish is not particularly limited. For example, a stirrer having a flasher (kneader) or a dewatering mechanism can be used.

In the production method of the present invention, it is preferable to perform a dehydration step until the water content in the composition after dispersing the pigment in the oil varnish is preferably 2% by mass or less. Moreover, it is preferable to perform the process of kneading after that. The apparatus for kneading is not particularly limited, and for example, a roll mill or a bead mill can be used. In this step, it is preferable that the extender is kneaded until the particle diameter of the extender is 10 μm or less with a grind gauge. The water content can be measured by a Karl Fischer moisture meter or the like.

In addition, a suitable amount of gelling agent (about 15 mass% or less with respect to binder resin) can be used for oil-based printing varnish as needed, and binder resin can be bridge | crosslinked. Examples of the gelling agent used in such a case include aluminum alcoholates and an ariminium chelate compound. Preferred examples include aluminum triisopropoxide, mono-sec-butoxyaluminum diisopropoxide, aluminum tri-sec-butoxide, ethyl acetoacetate aluminum diisopropoxide, aluminum trisethyl acetoacetate and the like.

Although it does not specifically limit as a specific example of these series of processes, For example, an extender pigment dispersion can be manufactured with the following procedures.
First, the extender pigment and wetting agent are added to a disper or flasher (kneader) and stirred to wet the extender pigment. Thereafter, the varnish for oil-based printing ink is added and stirred with a flasher (kneader) or a stirrer having a dehydrating mechanism, and the extender pigment is dispersed in the varnish for oil-based printing ink. Subsequently, it removes until the content of the water in a composition becomes 2 mass% or less. Further, after that, if necessary, varnish for oil-based printing ink and an oily liquid are added, and the mixture is kneaded with a bead mill or a three-roll mill until the particle size of the extender pigment becomes 10 μm or less.

<External pigment dispersion>
The pigment dispersion obtained by the above production method is also one aspect of the present invention. In the extender pigment dispersion of the present invention, the extender pigment is sufficiently dispersed in the varnish for oil-based printing ink. Moreover, by adding to the ink composition for offset printing mentioned later, it is advantageous at the point which can adjust fluidity | liquidity, a water width, etc. effectively.

<Ink composition for offset printing>
In the offset printing ink composition, the amount of the extender pigment dispersion of the present invention is not particularly limited. In order to adjust the fluidity and the water width of the ink composition for offset printing, for example, it can be used by adding an amount such that the total amount of extender used is 30% by mass or less. Although not particularly limited, an offset printing ink composition can be obtained by adding an extender pigment dispersion as described above to an offset printing ink composition containing a colorant, a binder resin, a vegetable oil component and / or a mineral oil component. Obtainable. The ink composition for offset printing obtained in this way is also one aspect of the present invention. When used for printing, the ink composition for offset printing of the present invention has an advantageous effect of suppressing smearing during printing.

The ink composition for offset printing is effective as an ink composition that can be used for non-heat-type printing such as newspaper printing and telephone book printing, and further for offset printing in general, such as heat-set printing, sheet-fed printing, and waterless printing. . Thus, an ink composition for offset printing containing the extender pigment dispersion is also a preferred embodiment of the present invention.

The extender pigment dispersion used in the ink composition for offset printing uses a wetting agent containing water and at least one compound group 1 as a solvent for wetting the extender pigment in the production method. It is preferable to use what was obtained.

The compound group 1 does not adversely affect printability even if it remains in the offset printing ink composition. Moreover, in the case of the ink composition for offset printing used for printing using a dampening water, if the said compound group 1 is used, since water-width suitability becomes favorable, it is preferable.

When the compound group 1 is used, the content in the offset printing ink composition is preferably 0.01 to 2% by mass with respect to 100% by mass of the offset printing ink composition.

According to the method for producing an extender dispersion for oil-based printing of the present invention, the following effects can be obtained.
That is, even if an extender that is surface treated to give good wettability to the oil varnish and does not wet with water alone is used, it can be wetted with a wetting agent containing water. To increase dispersibility. As a result, productivity can be greatly improved as compared with the conventional means.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” means “mass%”. In the following examples, “flushing” means mixing and stirring an extender pigment moistened with a wetting agent containing water and the above compound (B) and an oily varnish, and removing the extender pigment from the aqueous phase to the oily phase. The process of phase inversion. Moreover, the calcium carbonate white gloss flower CC (product made from calcium Shiroishi) used is the calcium carbonate by which the surface treatment of the fatty acid was performed.

<Production Example 1>
<Colored pigment dispersion>
The mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 (manufactured by Nippon Oil Co., Ltd., petroleum-based hydrocarbon) is 40/25 in a tabletop flasher (manufactured by Inoue Machinery). 320 parts of binder resin oil varnish 1 which is / 35 was added. Next, 100 parts of a yellow pigment press cake (23% pure pigment content) was added thereto and flushed at 50 ° C. for 60 minutes. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure for 60 minutes until the amount of remaining water was 2% or less. To the obtained dispersion, a rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) in a mass ratio of 40/30/29/1. 60 parts of binder resin oil varnish 2 and then 150 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded meat dispersion was performed to obtain a colored pigment dispersion.

<Example 1>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of nonylphenol ethylene glycol 5 mol adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to form a slurry. By these operations, 53.0 parts of a wetting agent composed of ion-exchanged water and a nonylphenol ethylene glycol 5 mol adduct (water / nonylphenol ethylene glycol 5 mol adduct = 94.3 / 5.7) and carbon dioxide as an extender pigment. Calcium white glaze CC was moistened. Thereafter, a binder resin oil varnish in which the mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 (manufactured by Nippon Oil Co., Ltd., petroleum hydrocarbon) is 40/25/35 25 parts of 1 was added and flushed at 50 ° C. for 60 minutes. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 1 for sex printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain ink composition 1 for offset printing.

<Example 2>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 0.09 part of nonylphenol ethylene glycol 5-mole adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to form a slurry. By these operations, 50.09 parts of a wetting agent (water / nonylphenol ethylene glycol 5 mol adduct = 99.8 / 0.2) composed of ion-exchanged water and nonylphenol ethylene glycol 5 mol adduct was added to the carbonic acid as an extender. Calcium white glaze CC was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 2 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 2 for offset printing.

<Example 3>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 11.5 parts of nonylphenol ethylene glycol 5-mole adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to form a slurry. By these operations, 61.5 parts of a wetting agent (water / nonylphenol ethylene glycol 5 mol adduct = 81.3 / 18.7) composed of ion-exchanged water and nonylphenol ethylene glycol 5 mol adduct was added to carbonic acid as an extender. Calcium white glaze CC was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the liberated wetting agent was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily extender pigment dispersion 3 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain ink composition 3 for offset printing.

<Example 4>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 20 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 0.02 part of nonylphenol ethylene glycol 5-mole adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to form a slurry. By these operations, 20.02 parts of wetting agent composed of ion-exchanged water and nonylphenol ethylene glycol 5 mol adduct (water / nonylphenol ethylene glycol 5 mol adduct = 99.9 / 0.1) was added to the carbonic acid as an extender. Calcium white glaze CC was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily extender pigment dispersion 4 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 4 for offset printing.

<Example 5>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 150 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 36 parts of nonylphenol ethylene glycol 5 mol adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to form a slurry. By these operations, 186 parts of a wetting agent (water / nonylphenol ethylene glycol 5 mol adduct = 80.0 / 20.0) composed of ion-exchanged water and nonylphenol ethylene glycol 5 mol adduct was added to calcium carbonate white luster as an extender pigment. CC was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of remaining water was 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily extender pigment dispersion 5 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 5 for offset printing.

<Example 6>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of ethanol was added and stirred and mixed to form a slurry. By these operations, 53.0 parts of a wetting agent composed of ion-exchanged water and ethanol (water / ethanol = 94.3 / 5.7) was used to wet the extender calcium carbonate white glossy CC. Thereafter, 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 6 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 6 for offset printing.

<Example 7>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 1-decanol was added and stirred and mixed to form a slurry. By these operations, calcium carbonate white luster CC as an extender was wetted with 53.0 parts of a wetting agent (water / 1-decanol = 94.3 / 5.7) composed of ion-exchanged water and 1-decanol. Thereafter, 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily extender pigment dispersion 7 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 7 for offset printing.

<Example 8>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 35 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 1-tridecanol was added and stirred and mixed to form a slurry. By these operations, calcium carbonate white luster CC as an extender was moistened with 53.0 parts (water / 1-tridecanol = 94.3 / 5.7) of a wetting agent composed of ion-exchanged water and 1-tridecanol. Thereafter, 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the liberated wetting agent was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily extender pigment dispersion 8 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain ink composition 8 for offset printing.

<Example 9>
In a tabletop flasher (manufactured by Inoue Kikai), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 60 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 1-hexadecanol was added and stirred and mixed to form a slurry. By these operations, 53.0 parts of a wetting agent composed of ion-exchanged water and 1-hexadecanol (water / 1-hexadecanol = 94.3 / 5.7) was added to the extender calcium carbonate white luster CC. Moistened. Thereafter, 25 parts of binder resin oil varnish having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added and flushed at 50 ° C. for 60 minutes. Went. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 9 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 9 for offset printing.

<Example 10>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of ethylene diglycol was added and stirred and mixed to form a slurry. By these operations, calcium carbonate white luster CC as an extender was moistened with 53.0 parts of a wetting agent composed of ion-exchanged water and ethylene diglycol (water / ethylene diglycol = 94.3 / 5.7). Thereafter, 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 10 for oil-based printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 10 for offset printing.

<Example 11>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of hexyl diglycol was added and stirred and mixed to form a slurry. By these operations, 53.0 parts of a wetting agent composed of ion-exchanged water and hexyl diglycol (water / hexyl diglycol = 94.3 / 5.7) was used to wet the extender calcium carbonate white glaze CC. Thereafter, 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion was 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of the binder resin oil varnish which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 11 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 11 for offset printing.

<Example 12>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of lauryl alcohol ethylene glycol 9 mol adduct (manufactured by Nikko Chemicals) was added and stirred and mixed to form a slurry. By these operations, 53.0 parts of wetting agent (water / lauryl alcohol ethylene glycol 9 mol adduct = 94.3 / 5.7) consisting of ion-exchanged water and lauryl alcohol ethylene glycol 9 mol adduct, Some calcium carbonate white glaze CC was moistened. Thereafter, 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 12 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 12 for offset printing.

<Example 13>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Subsequently, 3.0 parts of octylphenol ethylene glycol 3 mol adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to form a slurry. By these operations, 53.0 parts of a wetting agent composed of ion-exchanged water and octylphenol ethylene glycol (water / octylphenol ethylene glycol = 94.3 / 5.7) was used to wet the extender calcium carbonate white glaze CC. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 13 for oil-based printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 13 for offset printing.

<Example 14>
In a tabletop flasher (manufactured by Inoue Kikai), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 45 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 1,2-hexanediol was added and stirred and mixed to form a slurry. By these operations, 53.0 parts of a wetting agent composed of ion-exchanged water and 1,2-hexanediol (water / 1,2-hexanediol = 94.3 / 5.7) was used as an extender, and calcium carbonate white luster. CC was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 14 for oil-based printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 14 for offset printing.

<Example 15>
In a tabletop flasher (manufactured by Inoue Kikai), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 45 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 2-ethyl-1,3-hexanediol was added and stirred and mixed to form a slurry. By these operations, with 53.0 parts of a wetting agent composed of ion-exchanged water and 2-ethyl-1,3-hexanediol (water / 2-ethyl-1,3-hexanediol = 94.3 / 5.7) The body pigment, calcium carbonate white glaze CC, was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 15 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 15 for offset printing.

<Example 16>
In a tabletop flasher (manufactured by Inoue Kikai), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 45 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 1,2-octanediol was added and stirred and mixed to form a slurry. By these operations, 53.0 parts (water / 1,2-octanediol = 94.3 / 5.7) of a wetting agent composed of ion-exchanged water and 1,2-octanediol was used as an extender, such as calcium carbonate white luster. CC was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, a weight ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 16 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 16 for offset printing.

<Example 17>
In a tabletop flasher (manufactured by Inoue Kikai), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 45 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 2-butyl-2-ethyl-1,3-propanediol was added and stirred and mixed to form a slurry. By these operations, 53.0 parts of a wetting agent composed of ion-exchanged water and 2-butyl-2-ethyl-1,3-propanediol (water / 2-butyl-2-ethyl-1,3-propanediol = 94 3 / 5.7), the extender pigment calcium carbonate white luster CC was moistened. Thereafter, 30 parts of a binder resin oil varnish 1 having a weight ratio of 40/25/35 of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent 6 was added and flushed at 50 ° C. for 60 minutes. Went. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, a weight ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily printing extender pigment dispersion 17 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 17 for offset printing.

<Example 18>
In a tabletop flasher (manufactured by Inoue Kikai), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 45 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 3.0 parts of 1,2,4-butanetriol was added and stirred and mixed to form a slurry. By these operations, 53.0 parts of wetting agent composed of ion-exchanged water and 1,2,4-butanetriol (water / 1,2,4-butanetriol = 94.3 / 5.7) Some calcium carbonate white glaze CC was moistened. Thereafter, 30 parts of a binder resin oily varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, a weight ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 22 for oil-based printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 22 for offset printing.

<Comparative Example 1>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of a wetting agent consisting only of ion-exchanged water was added thereto, and the mixture was stirred and mixed with a kneader. However, calcium carbonate and water were separated and a slurry state was not formed.

<Comparative example 2>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Subsequently, 0.03 part of nonylphenol ethylene glycol 5-mol adduct (manufactured by Nikko Chemicals) was added and stirred and mixed. However, calcium carbonate and water were separated and a slurry state was not formed. In this Comparative Example 2, the total amount of the wetting agent (ion exchange water + nonylphenol ethylene glycol 5 mol adduct) was 50.03 parts, and the composition was water / nonylphenol ethylene glycol 5 mol adduct = 99.94 / 0. 06.

<Comparative Example 3>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 50 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 15.0 parts of nonylphenol ethylene glycol 5 mol adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to obtain a slurry. By these operations, 65 parts of a wetting agent (water / nonylphenol ethylene glycol 5 mol adduct = 77.0 / 23.0) composed of ion-exchanged water and nonylphenol ethylene glycol 5 mol adduct was added to calcium carbonate white gloss as an extender pigment. CC was moistened. Thereafter, 25 parts of a binder resin oily varnish 1 having a weight ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 minutes. Flushing was performed. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, a weight ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 18 for oil-based printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 18 for offset printing.

<Comparative example 4>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 10 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Next, 0.6 parts of nonylphenol ethylene glycol 5 mol adduct (manufactured by Nikko Chemicals) was added and stirred and mixed. However, calcium carbonate and water were separated and a slurry state was not formed. In this Comparative Example 4, the total amount of the wetting agent (ion exchange water + nonylphenol ethylene glycol 5 mol adduct) was 10.6 parts, and the composition was water / nonylphenol ethylene glycol 5 mol adduct = 94.3 / 5. 7.

<Comparative Example 5>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 200 parts of ion exchange water was added thereto, and the mixture was stirred and mixed by a kneader. Subsequently, 12.0 parts of nonylphenol ethylene glycol 5-mole adduct (manufactured by Nikko Chemicals) was added, stirred and mixed to form a slurry. By these operations, 212 parts of a wetting agent (water / nonylphenol ethylene glycol 5 mol adduct = 94.3 / 5.7) composed of ion-exchanged water and nonylphenol ethylene glycol 5 mol adduct was added to the body pigment calcium carbonate white luster. CC was moistened. Thereafter, 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent No. 6 of 40/25/35 was added, and the mixture was heated at 50 ° C. for 60 parts. Flushing was performed for a minute. By this flushing, the extender calcium carbonate white luster CC was dispersed in the oil varnish. Thereafter, the released water was removed. Thereafter, water was removed at 100 ° C. under reduced pressure (150 Torr (= 20 kPa)) for 60 minutes until the amount of water remaining in the extender pigment dispersion became 2% or less. In the obtained dispersion, the mass ratio of rosin-modified phenol resin (weight average molecular weight 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) was 40/30/29 / 42 parts of binder resin oil varnish 2 which is 1, and then 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 19 for oil-based printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 19 for offset printing.

<Reference Example 1>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 25 parts of binder resin oily varnish 1 having a mass ratio of rosin modified phenolic resin (weight average molecular weight 10,000) / soybean oil / AF solvent 6 of 40/25/35, and rosin modified phenolic resin (weight) 42 parts of binder resin oil varnish 2 having an average molecular weight of 80,000) / soybean oil / AF solvent No. 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide) having a mass ratio of 40/30/29/1, 28 parts of soybean oil were added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an extender dispersion 20 for oil-based printing was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain an ink composition 20 for offset printing.

<Reference Example 2>
In a tabletop flasher (Inoue Machine Co., Ltd.), 100 parts of calcium carbonate white glaze CC (manufactured by Shiraishi calcium) was charged at 25 ° C. Next, 3.0 parts of nonylphenol ethylene glycol 5 mol adduct (manufactured by Nikko Chemicals) was added and stirred and mixed. 25 parts of binder resin oil varnish 1 having a mass ratio of rosin-modified phenol resin (weight average molecular weight 10,000) / soybean oil / AF solvent 6 of 40/25/35, and rosin-modified phenol resin (weight average molecular weight 80 , 000) / soybean oil / AF solvent 6 / ALCH (ethyl acetoacetate aluminum diisopropoxide), 42 parts of binder resin oil varnish 2 having a mass ratio of 40/30/29/1, and then soybean oil 28 parts of was added and mixed. Thereafter, using a three-roll mill (manufactured by Inoue Kikai Co., Ltd.) at 45 ° C., kneaded dispersion was carried out until the particle diameter of the extender pigment that had been surface-treated by particle diameter measurement with a grindometer was 5 μm or less. As a result, an oily extender pigment dispersion 21 was obtained. 35 parts of this extender pigment dispersion, 50 parts of the color pigment dispersion of Production Example 1 and 15 parts of soybean oil were mixed and stirred to obtain ink composition 21 for offset printing.

<Evaluation>
(Printability)
Using a DAIYA printer manufactured by Mitsubishi Heavy Industries, printing was performed on the reprinted paper at 3000 to 8000 parts / hour, and the degree of stain on the paper surface was evaluated. Tables 1, 3 and 5 show the formulations of the oil-based printing extender pigment dispersion compositions of Examples, Comparative Examples, and Reference Examples. The composition of the ink composition for offset printing is shown in Tables 2, 4 and 6. The evaluation results are shown in Tables 7 to 9. In the table, the evaluation of slurrying was evaluated as “◯” when the slurry was prepared. Moreover, what was not able to produce a slurry was set as x.

[Evaluation criteria for stains during printing]
○: Ink adherence to non-image area and density unevenness ×: Ink adhesion to non-image area, density unevenness, etc.

(Evaluation of productivity of extender dispersion for oil-based printing)
By evaluating each item shown in Tables 7 to 9, the productivity of the extender dispersion for oil-based printing was evaluated.

As shown in Tables 7 to 9, in Examples 1 to 18, the slurry can be prepared without any particular problem. Compared to Comparative Example 5, the dehydration time and the meat grinding time can be shortened. As a result, the total time required for production can be shortened.
In Comparative Example 3, smear occurred during printing using the offset printing ink composition. On the other hand, dirt was not seen in Examples 1-18.

Thus, the manufacturing method of the extender dispersion for oil-based printing of this invention is excellent in productivity. Moreover, the composition for offset printing inks obtained is excellent also in the stain suppression effect at the time of printing.

The oil-based printing ink composition containing the oil-based printing extender pigment dispersion of the present invention includes non-heat-type printing such as newspaper printing and telephone book printing, and offset printing such as heat-set printing, sheet-fed printing, and waterless printing. It is effective as an ink composition that can be used throughout.

Claims (5)

100 parts by mass of the surface-treated extender pigment, water (A) and at least one compound (B) selected from the group consisting of compounds represented by the following general formulas (1) to (4) ( A step of wetting with 19 to 190 parts by weight of a wetting agent contained at a mass ratio of A) / (B) = 99.9 / 0.1 to 80.0 / 20.0;
Dispersing the wet extender in oily varnish and then removing water (A);
A process for producing an extender pigment dispersion for oil-based printing.
R ¹ —OH General formula (1)
(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be linear or branched);
_{^{R 2 - (O-R 3}} ) n -OH Formula (2)
(In the formula, R ² is a monovalent hydrocarbon group having 1 to 18 carbon atoms and may be an aliphatic group or an aromatic group. R ³ is an ethylene group, a propylene group, or A butylene group, n is an integer from 1 to 10);
HO—R ⁴ —OH general formula (3)
(Wherein R ⁴ is a hydrocarbon group having 2 to 12 carbon atoms, and may be an aliphatic group or an aromatic group, and may be linear or branched);
R ^5- (OH) ₃ General formula (4)
(In the formula, R ⁵ is a trivalent hydrocarbon group having 3 to 6 carbon atoms, which may be linear or branched). After completion of the step of wetting and dispersing, and then the step of removing water (A), the particle size of the extender pigment that has been surface-treated by a roll mill or a bead mill is 10 μm or less with a grind gauge. The method for producing an extender dispersion for oil-based printing according to claim 1, comprising a step of kneading. The compound (B) is at least one compound selected from the group consisting of compounds represented by the following general formulas (5) to (9) having a boiling point of 200 ° C or higher. A method for producing an extender dispersion for oil-based printing.
R ¹ —OH General formula (5)
(Wherein R ¹ is a hydrocarbon group having 9 to 16 carbon atoms, which may be linear or branched);
_{^{R 2 - (O-R 3}} ) n -OH Formula (6)
(Wherein R ² is a monovalent aliphatic group having 2 to 8 carbon atoms, R ³ is an ethylene group, and n is an integer of 1 to 3);
_{^{R 2 - (O-R 3}} ) n -OH Formula (7)
(Wherein R ² is a monovalent hydrocarbon group having 14 to 15 carbon atoms containing an aromatic group, R ³ is an ethylene group, and n is an integer of 5 to 10);
HO—R ⁴ —OH general formula (8)
(In the formula, R ⁴ is a divalent hydrocarbon group having 6 to 12 carbon atoms, and may be an aliphatic group or an aromatic group. good.);
R ^5- (OH) ₃ General formula (9)
(In the formula, R ⁵ is a trivalent hydrocarbon group having 4 to 6 carbon atoms, which may be linear or branched.) An extender dispersion for oil-based printing, which is obtained by the method for producing an extender dispersion for oil-based printing according to any one of claims 1 to 3. An ink composition for offset printing comprising the extender dispersion for oil-based printing according to claim 4.