JP3740737B2 - Method for producing resin composition for printing ink, and method for producing printing ink - Google Patents

Description

【００５０】
【発明の効果】
本発明は、インキの乾燥性とインキ皮膜の透明性のいずれにも優れ、速乾性でしかも彩やかな印刷物が得られる印刷インキ用樹脂組成物、その製造方法、及び該印刷インキ用樹脂組成物を必須の成分とする印刷インキを提供することができる。[0001]
BACKGROUND OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention provides a printing ink resin composition useful as a binder for printing ink, especially a gravure printing ink binder, and a printing ink resin composition obtained by this manufacturing method as an essential component. The present invention relates to a method for producing a printing ink to be contained.
[0002]
[Prior art]
This type of resin composition obtained from rosin and / or a derivative thereof and a metal compound is used in a large amount as a binder for gravure printing inks and the like since it forms an ink film having a high softening point and excellent drying properties. It is used.
[0003]
Conventionally, it has been proposed that these resin compositions are obtained by dissolving rosin and / or a derivative thereof in an organic solvent and adding water and a metal compound to cause a reaction (JP-A-2-286749). However, these conventional resin compositions are excellent in drying properties, but lack transparency of the ink film and do not satisfy drying properties and transparency of the ink film.
[0004]
That is, if the ink film lacks transparency, the color of the printed material is reduced in color, and the entire printed material looks dull. Further, when the drying property is lowered in order to obtain a printed matter with high transparency, the ink penetrates to the back side of the paper, so that a problem of so-called “set-off” occurs.
[0005]
Also, in order to provide improved printability on the lower paper surface and improved gloss on the coated paper material, for example, a gravure printing ink for publications using a polyamide-modified metal resinate (JP-A 61-252277) has been proposed. However, this method has a drawback that the compatibility between the metal resinate and the polyamide is insufficient, and an ink film having high transparency cannot be obtained.
[0006]
[Problems to be solved by the invention]
The problem to be solved by the present invention is a method for producing a resin composition for printing ink, which is excellent in both ink drying properties and ink film transparency, can be quickly dried, and provides a colorful printed material. An object of the present invention is to provide a method for producing a printing ink containing the resin composition for printing ink obtained by the production method as an essential constituent, particularly a method for producing an ink for publishing gravure printing.
[0007]
[Means for Solving the Problems]
As a result of extensive studies, the present inventors have simply reacted α, β-monoethylenically unsaturated carboxylic acid-added rosin (hereinafter referred to as “added rosin”) with a metal compound by a known method. However, it was found that the above problem can be solved by reacting with an amino compound having a hydroxyl group, and the present invention has been completed.
[0008]
That is, the present invention comprises a rosin added with α, β-monoethylenically unsaturated carboxylic acid, an amino compound having a hydroxyl group, and an oxide, hydroxide and organic acid salt of a divalent or trivalent metal. It is a manufacturing method of the resin composition for printing inks characterized by making 1 or more types of metal compounds chosen from the group which consists of react.
[0009]
Moreover, the manufacturing method of the resin composition for printing ink of this invention is the manufacturing method using (alpha), (beta) -monoethylenically unsaturated dicarboxylic acid as (alpha), (beta) -monoethylenically unsaturated carboxylic acid, and the amino compound which has a hydroxyl group. Including a production method using an amino compound having 1 to 3 hydroxyl groups, and a production method using an oxide and / or hydroxide of one or more metals selected from the group consisting of calcium, magnesium and zinc as a metal compound. It is a waste.
[0010]
In the production method of the present invention, the present invention comprises reacting a rosin added with an α, β-monoethylenically unsaturated carboxylic acid with an amino compound having a hydroxyl group, and then divalent to trivalent in the presence of an organic solvent. And a production method in which at least one metal compound selected from the group consisting of metal oxides, hydroxides and organic acid salts is reacted.
[0011]
Moreover, this invention includes the manufacturing method which uses a rosin together with the rosin which added (beta) -monoethylenically unsaturated carboxylic acid in the manufacturing method of the said invention.
[0012]
Furthermore, the present invention includes a method for producing a printing ink characterized in that the resin composition for printing ink obtained by the production method of the present invention is contained as an essential component.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail. As the rosin referred to in the present invention, any of those usually used can be used. In particular, only representative ones are exemplified by polymerized rosins such as gum rosin, tall oil rosin, wood rosin or dimerized rosin. These are used alone or in combination, and the mixing ratio is not particularly limited.
[0014]
As the α, β-monoethylenically unsaturated carboxylic acid used for preparing the addition rosin used in the present invention, any known and conventional ones can be used. In particular, only representative ones are exemplified by unsaturated dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid or itaconic acid. In order to introduce as many kinds of metal compounds as possible without gelation, it is desirable to use such unsaturated dicarboxylic acids alone or in combination of two or more.
[0015]
In addition, the metal compound used in the present invention may be an oxide, hydroxide or organic acid salt of a divalent or trivalent metal. Zinc, barium, manganese, tin or aluminum, and various metal oxides, hydroxides or organic acid salts.
[0016]
In order to introduce many metal compounds without gelation, it is particularly preferable to use an oxide or hydroxide of a divalent metal such as calcium, magnesium or zinc. The amount of the metal compound used is suitably in the range of 5 to 15% by weight based on the total amount of rosin and added rosin.
[0017]
Furthermore, the organic solvent to be used is not particularly limited as long as it does not dissolve in water. In particular, only representative ones are exemplified by aromatic hydrocarbons such as toluene or xylene, ester solvents such as ethyl acetate or butyl acetate, or ketone solvents such as methyl (iso) butyl ketone. Also, toluene or xylene alone or in combination of two or more may be used.
[0018]
As the amino compound having a hydroxyl group used in the present invention, any of the commonly used amino compounds can be used, but among them, monoethanolamine, diethanolamine, triethanol- can be used only to exemplify typical ones. Ruamine, dimethylethanolamine, diethylethanolamine, di (iso) propylethanolamine, dibutylethanolamine, aminomethylethanolamine, aminoethylethanolamine, amino (iso) propylethanolamine, amino (iso) Butylethanolamine, methyldiethanolamine, ethyldiethanolamine, (iso) propyldiethanolamine, (iso, tert-) butyldiethanolamine, aminomethyl (iso) propanolamine, aminoethyl (iso) propanol Hydroxyl amino compound having 1 to 3 such as triethanolamine and the like.
[0019]
The introduction reaction of the metal compound into the addition rosin or the introduction reaction of the metal compound into the addition rosin and rosin is performed in the presence of water and an organic solvent. The reaction temperature is 100 ° C. or lower, preferably 50 to 80 ° C. When the reaction is performed at a temperature higher than 100 ° C., evaporation of water and other organic solvents coexisting easily occurs in a state where the reaction does not proceed sufficiently. And an unreacted metal compound tends to remain, and the introduction reaction of the metal compound is not sufficiently performed, which is not preferable.
[0020]
The reaction time of the introduction reaction of the metal compound into the addition rosin or the introduction reaction of the addition of the metal compound into the rosin and rosin is 0.5 to 10 hours, preferably 2 to 7 hours. What should be noted in the introduction reaction of such a metal compound is a problem of control of reaction heat. The reaction between a metal compound and an addition rosin or rosin in the presence of water is accompanied by a violent exotherm. Therefore, it is necessary to pay sufficient attention to bumping of the reaction contents.
[0021]
The reaction temperature for introducing the amino compound into the addition rosin, or the reaction temperature for introducing the amino compound into the addition rosin and rosin is 100 ° C. or higher, preferably 120 to 220 ° C. When it is performed at a temperature lower than 100 ° C., it is not preferable because dehydration does not proceed sufficiently.
[0022]
The amount of the amino compound used is in the range of 0.2 parts by weight or more, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the added rosin or the total amount of the added rosin and rosin. When the amount of the amino compound used is 0.2 parts by weight or less, it is difficult to obtain a resin composition for printing ink that is excellent in both ink drying properties and ink film transparency. Furthermore, the acid value of the resin composition for printing ink obtained by the production method of the present invention is preferably in the range of 40 to 150 KOH mg / g in terms of solid acid value.
[0023]
In the method for producing a resin composition for printing ink of the present invention, generally, 1 to 30 parts by weight of an α, β-monoethylenically unsaturated carboxylic acid and 5 to 19 parts of a metal compound with respect to 100 parts by weight of rosin. 0.5 parts by weight and 0.2 to 20 parts by weight of the amino compound are used, and more preferably, 3 parts by weight of α, β-monoethylenically unsaturated carboxylic acid is 3 to 100 parts by weight of rosin. 15 parts by weight, 6 to 15 parts by weight of a metal compound, and 0.2 to 20 parts by weight of an amino compound are used.
[0024]
In the printing ink production method of the present invention, generally, the printing ink resin composition (solid content) obtained by the production method of the present invention is 10 to 50 parts by weight, the colorant is 3 to 35 parts by weight, and the filler. 0 to 20 parts by weight, and the solvent is used in a range of 40 to 75 parts by weight. More preferably, the resin composition for printing ink (solid) is 15 to 35 parts by weight, and the colorant is 5 to 5 parts by weight. 20 parts by weight, 5 to 15 parts by weight of filler, and 45 to 60 parts by weight of solvent are used.
[0025]
As the colorant used in the method for producing a printing ink of the present invention, known and conventional ones used in ordinary inks such as inorganic or organic pigments and dyes are used, but pigments are used from the viewpoint of water resistance. It is preferable.
[0026]
Specific examples of organic pigments include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthal yellow, chromophthal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone Examples thereof include red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, and daylight fluorescent pigment.
[0027]
Specific examples of inorganic pigments include carbon black, aluminum powder, bronze powder, chrome vermillion, chrome lead, cadmium yellow, cadmium red, ultramarine, bitumen, bengara, yellow iron oxide, iron black, titanium oxide, and zinc oxide. Can be mentioned.
[0028]
Specific examples of the dye include tartrazine lake, rhodan 6G lake, Victoria pure blue lake, alkali blue G toner, brilliant green lake and the like, and in addition, coal tar can also be used.
[0029]
Further, the filler used in ordinary ink is used alone or in combination of two or more. Specific examples include carbonates such as calcium carbonate and magnesium carbonate, sulfates such as precipitated barium sulfate, and silicates such as silica and talc. Further, as additives, waxes, pigment dispersants, antifoaming agents, and other known ones can be used.
[0030]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “part” means “part by weight” unless otherwise specified.
[0031]
Example 1
A 2 L four-necked flask equipped with a stirrer, a thermometer and a decanter was charged with 500 parts of tall oil rosin and 40 parts of fumaric acid and held at 250 ° C. for 1 hour to carry out the reaction. And a fumaric acid-added rosin was obtained. Subsequently, the temperature was lowered to 140 ° C., 16 parts of triethanolamine was added, and a reaction was performed at the same temperature for 2 hours to obtain a reaction product of rosin, fumaric acid-added rosin and triethanolamine.
[0032]
Subsequently, 540 parts of toluene was added to the reaction product, and maintained at a temperature of 70 ° C., and 80 parts of ion-exchanged water, 10 parts of calcium hydroxide and 15 parts of magnesium oxide were added over 3 hours. Was done. Subsequently, 35 parts of zinc oxide was added at the same temperature, and the reaction was performed for 3 hours. Then, the temperature was maintained at 110 ° C. for 3 hours, and water was removed with a decanter.
[0033]
The appearance of the obtained resin composition was transparent, and various characteristic values of this resin composition were as follows.
Acid value (acid value in terms of solid content, the same applies hereinafter): 89 KOH mg / g
Viscosity (25 ° C., viscosity measured with a B-type viscometer, the same applies hereinafter): 1050 cps
Weight average molecular weight (GPC, polystyrene conversion; the same applies hereinafter): 600
Nonvolatile content: 51%
[0034]
Next, 45 parts of the obtained resin composition, 7 parts of red pigment (carmine 6B), 30 parts of calcium carbonate and toluene were dispersed for 1 hour with a pigment disperser (paint shaker). Subsequently, the viscosity was adjusted to 12 seconds with a viscometer (Zahn Cup No. 3) using toluene to obtain a red ink composition.
[0035]
(Example 2)
In a reaction vessel similar to that of Example 1, 450 parts of gum rosin, 50 parts of dimer rosin (polymerized rosin, manufactured by Hercules Co.) and 30 parts of fumaric acid were charged and reacted at 240 ° C. for 1 hour. A mixture of rosin and fumaric acid-added rosin was obtained. Subsequently, the temperature was lowered to 120 ° C., 13 parts of dimethylethanolamine was charged, and the temperature was raised to 135 ° C. in 0.5 hours. The reaction was carried out at the same temperature for 2 hours to obtain a reaction product of rosin, fumaric acid adduct and dimethylethanolamine.
[0036]
Next, 530 parts of toluene is added to the mixture, and the mixture is further maintained at a temperature of 80 ° C. and comprises 80 parts of ion-exchanged water, 12.5 parts of calcium hydroxide, and 16 parts of zinc oxide. It was added over 2 hours and reacted at the same temperature. Next, 30 parts of magnesium oxide was added over 1 hour, and then kept at 110 ° C. for 3 hours, and water was removed by a decanter. The appearance of the obtained resin composition was transparent, and various properties of this resin composition were as follows.
[0037]
Acid value: 78KOH mg / g
Viscosity: 1,030 cps
Weight average molecular weight: 530
Nonvolatile content: 51%
Next, a red ink having a viscosity of 12.5 seconds was obtained in the same manner as in Example 1.
[0038]
Example 3
In the same reaction vessel as in Example 1, 500 parts of tall oil rosin and 34 parts of maleic anhydride were charged and kept at 170 ° C. for 1 hour to carry out the reaction, and rosin and maleic anhydride-added rosin were mixed. A mixture was obtained. Subsequently, the temperature was lowered to 120 ° C., 10 parts of dimethylethanolamine was added, and the reaction was conducted at 135 ° C. for 2 hours to obtain a reaction product of rosin, fumaric acid-added rosin and dimethylethanolamine.
[0039]
Then, 540 parts of toluene is added to the reaction and maintained at a temperature of 70 ° C., 80 parts of ion exchange water, 10 parts of zinc oxide and 15 parts of calcium hydroxide are added over 3 hours. Reaction was performed. Next, 25 parts of magnesium oxide was added over 1 hour and reacted for 2 hours, then held at 110 ° C. for 3 hours, and water was removed with a decanter. The appearance of the obtained resin composition was transparent, and the characteristics of this resin composition were as follows.
[0040]
Acid value: 85KOH mg / g
Viscosity: 600 cps
Weight average molecular weight: 500
Nonvolatile content: 50.5%
Next, a red ink having a viscosity of 12 seconds was obtained in the same manner as in Example 1.
[0041]
(Comparative Example 1)
Using the same reaction vessel as in Example 1, 500 parts of tall oil rosin and 40 parts of fumaric acid were charged, and the reaction was carried out by maintaining at 250 ° C. for 1 hour to obtain a rosin and fumaric acid-added rosin. A mixture was obtained. Subsequently, 540 parts of toluene is added to the mixture and maintained at a temperature of 70 ° C., and 80 parts of ion-exchanged water, 10 parts of calcium hydroxide and 15 parts of magnesium oxide are added over 3 hours to react. Was done. Subsequently, 35 parts of zinc oxide was added and the reaction was carried out for 3 hours, and then kept at 110 ° C. for 3 hours, and water was removed with a decanter.
[0042]
The appearance of the obtained resin composition was transparent, and various characteristic values of this resin composition were as follows.
Acid value: 100KOH mg / g
Viscosity: 600 cps
Weight average molecular weight: 480
Nonvolatile content: 51%
Next, a target red ink having a viscosity of 12 seconds was obtained in the same manner as in Example 1.
[0043]
(Comparative Example 2)
In a reaction vessel similar to that in Example 1, 450 parts of gum rosin, 50 parts of polymerized rosin (dimer-rosin) and 30 parts of fumaric acid, manufactured by Hercules Co., Ltd., were reacted at 240 ° C. for 1 hour. Thus, a mixture of rosin and fumaric acid-added rosin was obtained. Subsequently, 530 parts of toluene was added to this mixture, and the mixture was further maintained at a temperature of 80 ° C. to prepare a mixture of 80 parts of ion-exchanged water, 12.5 parts of calcium hydroxide, and 16 parts of zinc oxide. The reaction was carried out at the same temperature for 2 hours.
[0044]
Subsequently, 30 parts of magnesium oxide was added over 1 hour to carry out the reaction, and then kept at 110 ° C. for 3 hours to remove water with a decanter. The appearance of the obtained resin composition was transparent, and various characteristic values of this resin composition were as follows. Acid value: 90KOH mg / g
Viscosity: 1030 cps
Weight average molecular weight: 530
Nonvolatile content: 51%
Next, a target red ink having a viscosity of 12 seconds was obtained in the same manner as in Example 1.
[0045]
(Comparative Example 3)
In a reaction vessel similar to that in Example 1, 500 parts of tall oil rosin and 34 parts of maleic anhydride were charged, and the reaction was carried out by maintaining at 170 ° C. for 1 hour to obtain rosin and maleic anhydride-added rosin. A mixture was obtained. Subsequently, 540 parts of toluene is added to the mixture and maintained at a temperature of 70 ° C., 80 parts of ion exchange water, 10 parts of zinc oxide and 15 parts of calcium hydroxide are added over 3 hours. The reaction was performed. Subsequently, 25 parts of magnesium oxide was added over 1 hour, reacted for 2 hours, held at 110 ° C. for 3 hours, and water was removed with a decanter.
[0046]
The appearance of the obtained resin composition was transparent, and various characteristic values of this resin composition were as follows.
Acid value: 100KOH mg / g
Viscosity: 350 cps
Weight average molecular weight: 430
Nonvolatile content: 50.5%
Next, a red ink having a viscosity of 12 seconds was obtained in the same manner as in Example 1.
[0047]
(Application evaluation example)
The ink compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were printed on a vinyl chloride film and printing paper using a baby-printing machine manufactured by Higashitani Iron Works Co., Ltd. The dryness of the paper and the gloss of the printed material were comparatively measured. The transparency of the ink film was determined by drying a printed matter using a vinyl chloride film at 20 ° C. for 24 hours, and measuring the turbidity with a haze meter manufactured by Tokyo Denshoku Co., Ltd. The smaller the turbidity value, the better the transparency.
[0048]
Drying of the ink tester - Industrial Co., Ltd. heat - tosylate - Rutesuta - crimp superimposed printing paper and printed matter of the print paper at a pressure of 4 kg / cm ² using a time until the ink is not deposited on the print paper Was the drying time. The gloss was measured by drying a printed matter printed on printing paper at 20 ° C. for 24 hours and using a gloss meter with a reflective interface of 60 degrees. The evaluation results are shown in Table 1.
[0049]
[Table 1]

[0050]
【The invention's effect】
The present invention provides a resin composition for printing ink that is excellent in both drying properties of ink and transparency of an ink film, and provides a quick-drying and colorful printed material, a method for producing the same, and the resin composition for printing ink Can be provided as an essential component.

Claims (8)

1 selected from the group consisting of rosin to which an α, β-monoethylenically unsaturated carboxylic acid is added , an amino compound having a hydroxyl group, and an oxide, hydroxide and organic acid salt of a divalent or trivalent metal. The manufacturing method of the resin composition for printing inks characterized by making a metal compound of a seed | species or more react. The method for producing a resin composition for printing ink according to claim 1, wherein the α, β-monoethylenically unsaturated carboxylic acid is α, β-monoethylenically unsaturated dicarboxylic acid. The method for producing a resin composition for printing ink according to claim 2, wherein the amino compound having a hydroxyl group is an amino compound having 1 to 3 hydroxyl groups. One or more metal oxides selected from the group consisting of calcium, magnesium and zinc, wherein one or more metal compounds selected from the group consisting of divalent or trivalent metal oxides, hydroxides and organic acid salts 4. The method for producing a resin composition for printing ink according to claim 3, wherein the resin composition is a hydroxide. After reacting a rosin to which an α, β-monoethylenically unsaturated carboxylic acid has been added with an amino compound having a hydroxyl group, an oxide, hydroxide or organic acid of a divalent or trivalent metal in the presence of an organic solvent The manufacturing method of the resin composition for printing ink of any one of Claims 1-4 with which 1 or more types of metal compounds chosen from the group which consists of salts are made to react. The manufacturing method of the resin composition for printing inks of any one of Claims 1-4 which uses a rosin together with the rosin which added the (alpha), (beta) -monoethylenically unsaturated carboxylic acid. The manufacturing method of the resin composition for printing inks of Claim 5 which uses a rosin together with the rosin which added the (alpha), (beta) -monoethylenically unsaturated carboxylic acid. A printing ink comprising, as an essential component, a resin composition for printing ink obtained by the production method according to claim 1. Manufacturing method of ki.