JPH09291244A - Resin composition for printing ink, its production and printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for printing ink, excellent in both of the drying property and the transparency of the film of the ink and capable of giving a print which is rapidly drying and vivid in color by reacting an amino compound in the presence of a rosin modified with a specific adding compound. SOLUTION: This resin composition is obtained by reacting (C) an amino compound with (D) a metallic compound in the presence of (B) a rosin modified by adding (A) α,β-monoethylene unsaturated carboxylic acid, and preferably further in the presence of an organic solvent and water. Furthermore, the component C is preferably a compound containing one or more OH groups in a molecule, and e.g. 100 pts.wt. of the component B is made to react preferably with 3-15 pts.wt. of the component A, 0.2-20 pts.wt. of the component C and 6-15 pts.wt. of the component D.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a printing ink resin composition which is useful as a binder for printing inks, particularly a binder for gravure printing inks, a method for producing the same, and an essential constitution of the printing ink resin composition. It relates to a printing ink contained as a component.

[0002]

2. Description of the Related Art A resin composition of this kind obtained from a rosin and / or its derivative and a metal compound is currently used for forming an ink film having a high softening point and excellent drying property.
It is widely used as a binder for gravure printing ink.

Conventionally, it has been proposed that these resin compositions be obtained by dissolving rosin and / or its derivative in an organic solvent and adding water and a metal compound to react them (JP-A-2-286749). Gazette). However,
Although these conventional resin compositions are excellent in dryness, they lack transparency of the ink film and do not satisfy the dryness and the transparency of the ink film.

[0004] That is, if the ink film lacks transparency, there is a disadvantage that the color of the printed matter is reduced, and the whole printed matter looks dull. In addition, when the drying property is reduced in order to obtain a highly transparent printed matter, the ink penetrates to the back surface of the paper, causing a problem of so-called “offset”.

Also, to provide improved printability on low grade paper stock and improved gloss on coated paper stock, gravure printing inks for publications using, for example, polyamide-modified metal resinates ( JP-A-61-25227
7) has been proposed. However, this method has a drawback in that the compatibility between the metal resinate and the polyamide is insufficient, and a highly transparent ink film cannot be obtained.

[0006]

The problem to be solved by the present invention is to provide a resin for printing ink, which is excellent in both the drying property of the ink and the transparency of the ink film, and which is quick-drying and can provide a colorful printed matter. It is intended to provide a composition, a method for producing the same, and a printing ink containing the resin composition for a printing ink as an essential constituent, particularly a printing gravure printing ink.

[0007]

Means for Solving the Problems As a result of intensive investigations, the present inventors have carried out a metal-added rosin having an α, β-monoethylenically unsaturated carboxylic acid (hereinafter referred to as an added rosin). It was found that the above problems can be solved by reacting not only with a known method but also with an amino compound, and the present invention has been completed.

That is, the present invention is a resin composition for a printing ink obtained by reacting an amino compound with a metal compound in the presence of a rosin to which an α, β-monoethylenically unsaturated carboxylic acid is added. .

The resin composition for printing ink of the present invention is obtained by reacting an amino compound with a metal compound in the presence of rosin and rosin to which α, β-monoethylenically unsaturated carboxylic acid is added. , A printing ink resin composition, and further obtained by reacting an amino compound and a metal compound in the presence of an organic solvent and water, and a printing ink resin composition, and this amino compound, especially one molecule It contains a resin composition for printing ink, which is a compound containing one or more hydroxyl groups.

The present invention is a method for producing a resin composition for a printing ink, which comprises reacting an amino compound with a metal compound in the presence of a rosin having an α, β-monoethylenically unsaturated carboxylic acid added thereto. Is the way.

The method for producing a resin composition for a printing ink of the present invention comprises reacting a rosin with a metal compound in the presence of a rosin having an α, β-monoethylenically unsaturated carboxylic acid added thereto. And a method for producing a resin composition for printing ink, wherein the amino compound and the metal compound are reacted in the presence of an organic solvent and water, a resin composition for printing ink. And a production method characterized in that the amino compound is a compound containing one or more hydroxyl groups in one molecule.

Further, the present invention also includes a printing ink containing the resin composition for printing ink obtained in the present invention as an essential component.

[0013]

BEST MODE FOR CARRYING OUT 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. Particularly, only representative examples are polymerized rosins such as gum rosin, tole oil rosin, wood rosin and dimerized rosin. These may be used alone or as a mixture, and the mixing ratio is not particularly limited.

As the α, β-monoethylenically unsaturated carboxylic acid used for preparing the addition rosin of the present invention, any known and conventional one can be used. Particularly, only representative ones include 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 acid alone or in combination of two or more kinds.

As the metal compound used in the present invention, any of those generally used in this type of introduction reaction can be used. Particularly, only representative examples are oxides, hydroxides and organic acid salts of various metals such as calcium, magnesium, zinc, barium, manganese, tin or aluminum.

In order to introduce many metal compounds without gelation, it is particularly desirable to use such divalent or trivalent metal compounds. Above all, calcium,
The use of divalent metal oxides or hydroxides of magnesium or zinc is preferred. The amount of the metal compound used is 5 to the total amount of rosin and added rosin.
A range of 15% by weight is suitable.

Further, the organic solvent used is not particularly limited as long as it does not dissolve in water.
Particularly, only representative examples are aromatic hydrocarbon solvents such as toluene or xylene, ester solvents such as ethyl acetate or butyl acetate, and ketone solvents such as methyl (iso) butyl ketone. Further, toluene or xylene may be used alone or in combination of two or more kinds.

As the amino compound of the present invention, any of those commonly used can be used, but of these, only typical ones are exemplified by monoethanolamine, diethanolamine and triethanolamine. , Dimethylethanolamine, diethylethanolamine, di (iso) propylethanolamine, dibutylethanolamine, aminomethylethanolamine, aminoethylethanolamine, amino (iso) propylethanolamine, amino (iso) butylethanol -Lamine, methyldiethanolamine, ethyldiethanolamine,

(Iso) propyldiethanolamine,
(Iso, tertiary) butyldiethanolamine, aminomethyl (iso) propanolamine, aminoethyl (iso) propanolamine, amino (iso) propyl (iso) propylamine, morpholine, methylmorpholine, ethylmorpholine, piperazine, trimethylamine ,

Triethylamine, tributylamine, diethylamine, di (iso) propylamine, (iso) propylamine, (iso) butylamine, (iso) octylamine, ethylenediamine, propylenediamine and the like, and two or more of them may be used. All in all.

The introduction reaction of the addition rosin of the metal compound or the addition rosin and the rosin is carried out in the presence of water and an organic solvent. The reaction temperature is 100 ° C. or lower, preferably 50
A range of -80 ° C is suitable. When it is carried out at a temperature higher than 100 ° C., evaporation of water and other coexisting organic solvents is likely to occur inevitably in a state where the reaction does not proceed sufficiently. Then, the unreacted metal compound is likely to remain, and the introduction reaction of the metal compound is not sufficiently performed, which is not preferable.

The reaction time of the addition reaction of the metal compound or the addition rosin and the introduction reaction into the rosin is 0.5 to 10 hours,
It is preferably carried out for 2 to 7 hours. In the reaction of introducing such a metal compound into an addition rosin or an addition rosin and a rosin, it is necessary to pay attention to the problem of controlling the heat of reaction. The reaction of the addition rosin or the addition rosin with the metal compound in the presence of water is accompanied by severe heat generation, and therefore, it is necessary to pay sufficient attention to bumping of the reaction contents.

The reaction temperature for introducing the amino compound into the addition rosin or the addition rosin and the rosin is appropriately 100 ° C. or higher, preferably 120 to 220 ° C. 100 ℃
If it is carried out at a lower temperature, dehydration does not proceed sufficiently, which is not preferable. However,
When the amino compound is introduced by the neutralization reaction between the addition rosin or the addition rosin and the amino compound, the temperature is preferably less than 100 ° C, preferably 30 to 80 ° C.

The amount of the amino compound used is 0.2% by weight based on the total amount of the added rosin or the added rosin and the rosin.
The above range is preferably 1 to 10% by weight. When the amount of the amino compound used is 0.2% by weight or less, it is difficult to obtain a resin composition for printing ink which is excellent in both the drying property of the ink and the transparency of the ink film. Furthermore, as the acid value of the resin composition for printing ink of the present invention,
The solid equivalent acid value is preferably in the range of 40 to 150 KOH mg / g.

The general composition of the resin composition for printing inks of the present invention is, by weight, α, β with respect to 100 parts of rosin.
-It is obtained by reacting 1 to 30 parts of monoethylenically unsaturated carboxylic acid, 5 to 19.5 parts of metal compound, and 0.2 to 20 parts of amino compound, and a more preferable composition is: 3 to 15 parts of α, β-monoethylenically unsaturated carboxylic acid and 6 to 100 parts of rosin and metal compound
15 parts and 0.2 to 20 parts of the amino compound.

The general composition of the printing ink of the present invention is 10 to 50 parts by weight of the resin composition (solid content) for the printing ink of the present invention, 3 to 35 parts of the colorant, and 0 parts by weight of the filler. ~ 20
Part, the solvent is 40 to 75 parts, and a more preferable composition of the ink is that the resin composition for printing ink (solid) is 15 parts.
~ 35 parts, 5-20 parts colorant, 5-15 parts filler,
The solvent is 45 to 60 parts.

As the colorant used in the printing ink of the present invention, known or commonly used colorants such as inorganic or organic pigments and dyes are used, but pigments are used from the viewpoint of water resistance. Preferably.

Specific examples of organic pigments include carmine 6
B, 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 red, indanthrone blue, pyrimidine yellow , Thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow,
Examples include aniline black and daylight fluorescent pigments.

Specific examples of the inorganic pigments include carbon black, aluminum powder, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, dark blue, red iron oxide, yellow iron oxide, iron black and titanium oxide.
Examples thereof include zinc oxide.

Specific examples of the dyes include tartrazine lake, Rhodan 6G lake, Victoria pure blue lake, alkali blue G toner, brilliant green lake, and the like, and coal tar can also be used.

As the filler, those used in ordinary ink may be used alone or in admixture 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 the additive, wax, pigment dispersant, defoaming agent and other known additives can be used.

[0032]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
This will be described more specifically. In the following, “parts” means “parts by weight” unless otherwise specified.

(Example 1) A 2 L four-necked flask equipped with a stirrer, a thermometer and a decanter was charged with 500 parts of tole oil rosin and 40 parts of fumaric acid to prepare 250 parts.
The reaction was carried out by holding at ℃ for 1 hour to obtain a mixture of rosin and fumaric acid-added rosin. Then, the temperature was lowered to 140 ° C., 16 parts of triethanolamine was charged, and the reaction was carried out at the same temperature for 2 hours to obtain a reaction product of rosin, fumaric acid-added rosin and triethanolamine.

Subsequently, 540 parts of toluene was added to this reaction product, and the temperature was maintained at 70 ° C. to obtain 80 parts of ion-exchanged water.
, 10 parts of calcium hydroxide and 15 parts of magnesium oxide were added over 3 hours to carry out the reaction. Subsequently, 35 parts of zinc oxide was added at the same temperature, and the reaction was carried out for 3 hours. Then, the temperature was maintained at 110 ° C. for 3 hours, and water was removed by a decanter.

The appearance of the obtained resin composition is transparent,
The characteristic values of this resin composition were as follows. Acid value (acid value in terms of solid content, same as below): 89KOH mg / g Viscosity (25 ° C, viscosity measured by B-type viscometer, same below): 1050 cps Weight average molecular weight (GPC, polystyrene equivalent; same below): 600 nonvolatile Min: 51%

Next, 45 parts of the resin composition obtained, 7 parts of a red pigment (Carmine 6B), calcium carbonate, toluene 30
Parts were dispersed with a pigment disperser (paint shaker) for 1 hour. Then, the viscosity was adjusted to 12 seconds with a viscometer (Zahn cup No. 3) using toluene to obtain a red ink composition.

Example 2 A reaction vessel similar to that used in Example 1 was charged with 450 parts of gum rosin, 50 parts of dimer-rosin (manufactured by Hercules, polymerized rosin) and 30 parts of fumaric acid. The reaction was carried out at 0 ° C for 1 hour to obtain a mixture of rosin and fumaric acid-added rosin. Subsequently, the temperature was lowered to 120 ° C., and the dimethylethanolamine 13
A part was charged and the temperature was raised to 135 ° C. over 0.5 hour. The reaction was carried out at the same temperature for 2 hours to obtain a reaction product of rosin and fumaric acid adduct and dimethylethanolamine.

Next, 530 parts of toluene was added to this mixture, and the mixture was kept at a temperature of 80 ° C. to obtain 8 parts of deionized water.
0 part and 12.5 parts of calcium hydroxide and 16 parts of zinc oxide
The mixture consisting of 1 part and 2 parts was added over 2 hours and reacted at the same temperature. Then, 30 parts of magnesium oxide was added over 1 hour, and the mixture was 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 characteristics of this resin composition were as follows.

Acid value: 78 KOH mg / g Viscosity: 1,030 cps Weight average molecular weight: 530 Nonvolatile content: 51% Next, by the same operation as in Example 1, a red ink having a viscosity of 12.5 seconds was obtained.

(Example 3) In a reaction vessel similar to that of Example 1, 500 parts of tole oil rosin and 3 parts of maleic anhydride were added.
4 parts were charged and the reaction was carried out at 170 ° C. for 1 hour to obtain a mixture of rosin and maleic anhydride-added rosin. Then, the temperature was lowered to 120 ° C., 10 parts of dimethylethanolamine was charged, and the reaction was carried out at a temperature of 135 ° C. for 2 hours to obtain a reaction product of rosin, fumaric acid-added rosin and dimethylethanolamine.

Next, 540 parts of toluene was added to this reaction product, and the temperature was maintained at 70 ° C. to obtain 80 parts of ion-exchanged water.
Parts, 10 parts of zinc oxide and 15 parts of calcium hydroxide were added over 3 hours to carry out the reaction. Next, 25 parts of magnesium oxide was added over 1 hour, and the reaction was carried out for 2 hours. Then, the temperature was maintained at 110 ° C. for 3 hours, and water was removed by a decanter. The appearance of the obtained resin composition was transparent, and the characteristics of this resin composition were as follows.

Acid value: 85 KOH mg / g Viscosity: 600 cps Weight average molecular weight: 500 Nonvolatile matter: 50.5% By the same operation as in Example 1, a red ink having a viscosity of 12 seconds was obtained.

(Comparative Example 1) Using the same reaction vessel as in Example 1, 500 parts of tole oil rosin and 40 parts of fumaric acid were used.
A portion was charged and the mixture was kept at 250 ° C. for 1 hour to carry out a reaction to obtain a mixture of rosin and fumaric acid-added rosin. Subsequently, 540 parts of toluene are added to this mixture and 70
Maintaining the temperature of ℃, 80 parts of ion-exchanged water, 10 parts of calcium hydroxide and 15 parts of magnesium oxide are added to 3 parts.
The reaction was carried out by adding over time. Subsequently, 35 parts of zinc oxide was added, and the reaction was carried out for 3 hours. Then, the temperature was maintained at 110 ° C. for 3 hours, and water was removed by a decanter.

The appearance of the obtained resin composition is transparent,
The characteristic values of this resin composition were as follows. Acid value: 100 KOH mg / g Viscosity: 600 cps Weight average molecular weight: 480 Nonvolatile matter: 51% Next, the same operation as in Example 1 was carried out to obtain a target red ink having a viscosity of 12 seconds.

(Comparative Example 2) In the same reaction vessel as in Example 1, 450 parts of gum rosin, 50 parts of polymerized rosin (dimer-rosin) manufactured by Hercules and 30 parts of fumaric acid were used.
A portion was charged and the reaction was carried out at 240 ° C. for 1 hour to obtain a mixture of rosin and fumaric acid-added rosin. continue,
To this mixture was added 530 parts of toluene and a further 80
While maintaining the temperature of ° C, a mixture of 80 parts of ion-exchanged water, 12.5 parts of calcium hydroxide and 16 parts of zinc oxide was added over 2 hours and the reaction was carried out at the same temperature.

Then, 30 parts of magnesium oxide was added over 1 hour to carry out the reaction, and then the mixture was kept at 110 ° C. for 3 hours to remove water by a decanter. The appearance of the obtained resin composition was transparent, and various characteristic values of this resin composition were as follows. Acid value: 90 KOH mg / g Viscosity: 1030 cps Weight average molecular weight: 530 Nonvolatile matter: 51% Next, by the same operation as in Example 1, a target red ink having a viscosity of 12 seconds was obtained.

(Comparative Example 3) To a reaction vessel similar to that of Example 1, was charged 500 parts of tole oil rosin and 34 parts of maleic anhydride, and the reaction was carried out at 170 ° C for 1 hour to carry out the reaction. A mixture of rosin with maleic anhydride was obtained. Subsequently, 540 parts of toluene was added to this mixture, and the mixture was maintained at a temperature of 70 ° C to obtain 80% of ion-exchanged water.
Parts, 10 parts of zinc oxide and 15 parts of calcium hydroxide were added and reacted for 3 hours. continue,
Add 25 parts of magnesium oxide over 1 hour,
The reaction was carried out for 2 hours, the temperature was kept at 110 ° C. for 3 hours, and water was removed by a decanter.

The appearance of the obtained resin composition is transparent,
The characteristic values of this resin composition were as follows. Acid value: 100 KOH mg / g Viscosity: 350 cps Weight average molecular weight: 430 Nonvolatile matter: 50.5% Next, in the same manner as in Example 1, a red ink having a viscosity of 12 seconds was obtained.

(Application Evaluation Example) Examples 1 to 3 and Comparative Examples 1 to 1
The ink composition obtained in 3 was printed on a vinyl chloride film and printing paper using a Baby printing machine manufactured by Higashiya Iron Works Co., Ltd., and the transparency of the ink film, the drying property of the ink, and the gloss of the printed matter were compared. It was measured. For the transparency of the ink film, the printed matter using the vinyl chloride film is dried at 20 ° C. for 24 hours,
The turbidity was measured with a haze meter manufactured by Tokyo Denshoku Co., Ltd. The smaller the turbidity value, the better the transparency.

As for the drying property of the ink, the printed matter of the printing paper and the printing paper are overlapped and pressure-bonded by using a heat seal tester manufactured by Tester Sangyo Co., Ltd. at a pressure of 4 kg / cm ² , and the ink does not adhere to the printing paper. The time until was defined as the drying time. The gloss was measured by drying the printed matter printed on printing paper at 20 ° C. for 24 hours,
The degree of reflection was measured using a gloss meter. Table 1 shows the evaluation results.

[0051]

[Table 1]

[0052]

INDUSTRIAL APPLICABILITY The present invention provides a resin composition for a printing ink, which is excellent in both the drying property of an ink and the transparency of an ink film, and which is quick-drying, and can provide a colorful printed material, a method for producing the same, and the printing method. It is possible to provide a printing ink containing an ink resin composition as an essential component.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Katayama 2-7-24 Nishikicho, Warabi-shi, Saitama Prefecture (72) Tomoo Satake 477-11 Imabacho, Omiya-shi, Saitama Prefecture

Claims (9)

[Claims] 1. A resin composition for printing ink, which is obtained by reacting an amino compound with a metal compound in the presence of a rosin to which an α, β-monoethylenically unsaturated carboxylic acid is added. 2. A resin composition for printing ink, which is obtained by reacting an amino compound with a metal compound in the presence of rosin and rosin to which α, β-monoethylenically unsaturated carboxylic acid is added. 3. The printing ink resin composition according to claim 1, which is obtained by reacting an amino compound and a metal compound in the presence of an organic solvent and water. 4. The resin composition for printing ink according to claim 1, wherein the amino compound is a compound containing one or more hydroxyl groups in one molecule. 5. A method for producing a resin composition for a printing ink, which comprises reacting an amino compound with a metal compound in the presence of a rosin to which an α, β-monoethylenically unsaturated carboxylic acid has been added. 6. A resin composition for printing ink, which comprises reacting an amino compound with a metal compound in the presence of rosin and rosin to which α, β-monoethylenically unsaturated carboxylic acid is added. Production method. 7. The method for producing a printing ink resin composition according to claim 6, wherein the amino compound and the metal compound are reacted in the presence of an organic solvent and water. 8. The resin composition for a printing ink according to claim 5, wherein the amino compound is a compound having one or more hydroxyl groups in one molecule. Production method. 9. A printing ink containing the resin composition for printing ink according to claim 1 as an essential component.