JP3214094B2 - Waterborne gravure printing ink binder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an alkylene oxide
Rosin derivative and an emulsion or hydrosol
The present invention relates to a binder for an aqueous gravure printing ink containing a fixed ratio .

[0002]

2. Description of the Related Art Conventionally, as a binder used for gravure printing ink, an organic solvent system has been mainly used. For example, in oil-based gravure printing inks applied to magazines, weekly magazines, and other materials, a reaction between a rosin-based compound and a metal compound as the binder is considered in consideration of performance such as drying properties after printing and gloss of printed matter. Products (metal salts of resin acids) have been widely used.

However, in recent years, there has been a long-awaited demand for making gravure printing inks water-soluble from the viewpoints of air pollution control, regulations under the Fire Service Law, occupational safety and health, and the like. Demands for development are increasing. Already, as an aqueous binder in this application, acrylic resins and styrene-acrylic resins have mainly been proposed, and various attempts have been made to make them water-soluble or water-dispersible, but these have not necessarily produced satisfactory properties. There is no present.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances concerning a binder for a gravure printing ink, the present invention provides an aqueous gravure having gloss and drying properties comparable to those of a conventional solvent-type ink using a metal salt of a resin acid. An object is to obtain an excellent aqueous binder suitable for providing a printing ink.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a specific rosin derivative
And an emulsion or hydrosol in a prescribed ratio
Water-based gravure printing ink binder
Water-based gravure printing with excellent gloss and drying
Knowledge that it can provide The present invention has been completed based on such findings.

[0006] The present invention has the following general formula (1): X - [( Y-O) n-H] m (1) ( wherein, X is a rosin material residue, Y is -CH ₂ CH ₂
- or _-CH 2 CH _(CH 3) - the same or different groups represented, n represents the number of up to 5 to 100, m is a number from 1 to 4, respectively. An alkylene oxide-added rosin derivative represented by the formula
And a printing ink binder containing
Alkylene oxide addition to total binder solids
The present invention relates to a binder for aqueous gravure printing ink, wherein the content of the rosin derivative is 3 to 70% by weight .

In the present invention , the rosin substance as a raw material of the alkylene oxide-added rosin derivative includes natural rosins such as gum rosin, tall oil rosin and wood rosin, and purified products thereof; disproportionation, hydrogenation, dehydration, Various modified rosins obtained by quantification and sulfonation; acid addition rosins obtained by addition reaction of maleic acid, maleic anhydride, fumaric acid, acrylic acid, etc. to the rosins; partial esters or partial amides of such acid addition rosins And the like. These rosin substances can be used alone or in combination of two or more.

In the present invention , the alkylene oxide as another raw material of the alkylene oxide-added rosin derivative includes ethylene oxide and propylene oxide, and these can be used alone or in combination.

The number of moles of the alkylene oxide to be added is carefully determined in consideration of the performance of the resulting binder and ink, and is usually in the range of 5 to 100 moles, preferably 10 to 40 moles, and more preferably. Is 10 to 25 mol. If the added mole number is less than 5 moles, the water solubility of the binder is reduced and the gloss of the ink is poor. On the other hand, if it is 100 moles or more, the water resistance is deteriorated and the obtained ink penetrates into the paper. There is.

In the present invention, as described above, an emulsion or hydrosol is added to an alkylene oxide-added rosin derivative.
It is necessary to use them together at a predetermined ratio . As such a emulsion or hydrosol, Ru can be particularly selected and used those limited without the various known. Specifically, an emulsion of an acrylic polymer, an emulsion of an acryl-styrene polymer, an emulsion of a styrene polymer, an emulsion of a metal salt of a resin acid, an emulsion of an esterified product of a resin acid and a polyhydric alcohol, and a hydrosol corresponding thereto And these can be used alone or in appropriate combination. Among them, various emulsions of acrylic, acrylic-styrene and styrene polymers are preferable from the viewpoint of abrasion resistance.

The method for producing the alkylene oxide-added rosin derivative, which is an essential component of the binder of the present invention, is not particularly limited, and various conventionally known methods can be employed as they are. For example, (1) while heating and melting the rosin substance, press-fit ethylene oxide and / or propylene oxide under an inert gas atmosphere such as nitrogen in the presence of an acidic or basic catalyst and at 150 to 200 ° C. for 1 to 5 hours. (2) the rosin derivative and at least one kind of polyethylene glycol, polypropylene glycol, poly (ethylene-propylene) glycol or the like in the absence of a catalyst or a known catalyst such as a Lewis acid; A method of esterifying at 200 to 300 ° C. for about 10 to 20 hours is exemplified.

[0012] The specific alkylene oxide-added rosin derivative thus obtained has good solubility in water and good pigment dispersibility, so that it is possible to prepare a high solids aqueous gravure printing ink.

In the present invention, it is essential to use the emulsion or hydrosol as described above in combination with the alkylene oxide-added rosin derivative in order to further improve the drying property of the obtained aqueous gravure printing ink. By appropriately selecting the type of the emulsion or hydrosol and the combination ratio thereof, various aqueous gravure printing ink binders having desired performance can be prepared. Usually, it is good to use an emulsion or a hydrosol together so that the alkylene oxide-added rosin derivative is in the range of 3 to 70% by weight, preferably 10 to 60% by weight, based on the total solid content of the binder.

The binder for an aqueous gravure printing ink of the present invention is prepared by kneading a known pigment together with various known pigments, if necessary, a hydrophilic solvent such as alcohol or glycol ether, and other additives, and kneading the mixture by a known method. The intended aqueous gravure printing ink can be easily prepared. The binder content in the ink composition is not particularly limited, but is usually appropriately determined in consideration of various properties and viscosity of the obtained ink, and is preferably about 10 to 60% by weight of the ink composition. Is preferably 25 to 50% by weight.

[0015]

By using the binder for aqueous gravure printing ink of the present invention, it is possible to provide a binder for aqueous gravure printing ink which satisfies both the gloss and the drying property of the printed matter.

[0016]

EXAMPLES The present invention will be described in detail below with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples.

Production Example 1 300 g of rosin and 2.0 g of anhydrous potassium carbonate were charged in an autoclave, heated and melted while replacing with nitrogen, and then 660 g of ethylene oxide was injected with nitrogen. After the injection was completed, the reaction was carried out at 100 to 200 ° C. for 2 hours with stirring to obtain a polyethylene glycol ester of rosin (addition product of 15 mol of ethylene oxide).

Production Example 2 A reaction was carried out in the same manner as in Production Example 1 except that 220 g of ethylene oxide was used to obtain a polyethylene glycol ester of rosin (addition product of 5 mol of ethylene oxide).

Preparation Example 3 The same reaction as in Preparation Example 1 was carried out except that 880 g of ethylene oxide was used, and a polyethylene glycol ester of rosin (addition product of 20 mol of ethylene oxide)
I got

Production Example 4 In Production Example 1, hydrogenated rosin 300 was used in place of rosin.
The reaction was carried out in the same manner except that g was used, and a polyethylene glycol ester of hydrogenated rosin (ethylene oxide 15
Mol addition product).

Production Example 5 A reaction was carried out in the same manner as in Production Example 4 except that 440 g of ethylene oxide was used to obtain a polyethylene glycol ester of hydrogenated rosin (addition product of 10 mol of ethylene oxide).

Production Example 6 A reaction was carried out in the same manner as in Production Example 4 except that 880 g of ethylene oxide was used to obtain a polyethylene glycol ester of hydrogenated rosin (addition product of 20 mol of ethylene oxide).

Production Example 7 The reaction was carried out in the same manner as in Production Example 4 except that 1320 g of ethylene oxide was used, to obtain a polyethylene glycol ester of hydrogenated rosin (addition product of 30 mol of ethylene oxide).

Production Example 8 To 100 g of rosin, 219 g of polyethylene glycol (average molecular weight: 600) was added.
Esterification was performed for 13 hours to obtain polyethylene glycol ester of rosin (addition product of ethylene oxide 14 mol).

Table 1 shows the properties of the various alkylene oxide-added rosin derivatives obtained in Production Examples 1 to 8.

[0026]

[Table 1]

Example 1 Alkylene oxide-added rosin derivative 1 obtained in Production Example 1
0.0 g of an acrylic emulsion (manufactured by Johnson,
Brand name "Joncryl 775", solid content 45,5
%) And then 1 part of a blue pigment (manufactured by Toyo Ink Mfg. Co., Ltd., trade name "Lionol Blue KLH").
0.0 g and 35.7 g of water were added. The mixture was kneaded using a sand mill to obtain an indigo ink. The content of the additional rosin derivative was 33.3% by weight (based on the solid content of the ink binder). Each of the obtained indigo inks was spread on coated paper using a bar coater # 10, and the gloss was visually evaluated according to the following criteria. In addition, the drying property was evaluated by finger touch according to the following criteria. 5: Very good 4: Good 3: Somewhat good 2: Poor 1: Very poor

Example 2 Example 1 was repeated except that 10.0 g of the alkylene oxide-added rosin derivative obtained in Production Example 2 was used.
An ink was prepared and evaluated in the same manner as in the above.

Example 3 Example 1 was repeated except that 10.0 g of the alkylene oxide-added rosin derivative obtained in Production Example 3 was used.
An ink was prepared and evaluated in the same manner as in the above.

Example 4 Example 1 was repeated except that 10.0 g of the alkylene oxide-added rosin derivative obtained in Production Example 4 was used.
An ink was prepared and evaluated in the same manner as in the above.

Example 5 In Example 1, 4.0 g of the addition product obtained in Production Example 4
And 64.0 g of the acrylic emulsion and 21.
Except that 0 g was added, it was blended and evaluated in the same manner as in Example 1. The content of the added rosin derivative was 12.1% by weight.
(Solid content of ink binder).

Example 6 Example 1 was repeated except that 10.0 g of the alkylene oxide-added rosin derivative obtained in Production Example 5 was used.
An ink was prepared and evaluated in the same manner as in the above.

Example 7 Example 1 was repeated except that 10.0 g of the alkylene oxide-added rosin derivative obtained in Production Example 6 was used.
An ink was prepared and evaluated in the same manner as in the above.

Example 8 Example 1 was repeated except that 10.0 g of the alkylene oxide-added rosin derivative obtained in Production Example 7 was used.
An ink was prepared and evaluated in the same manner as in the above.

Example 9 Example 1 was repeated except that 10.0 g of the alkylene oxide-added rosin derivative obtained in Production Example 8 was used.
An ink was prepared and evaluated in the same manner as in the above.

Comparative Example 1 10.0 g of lionol blue, 3.3 g of isopropanol, and 1 part of water were added to 71.0 g of the acrylic emulsion.
5.6 g was added, kneaded with a sand mill and evaluated.

Comparative Example 2 Toluene varnish (metallic resin No. 12 of Arakawa Chemical Industries, Ltd., trade name: Lime Resin No. 12) with a resin content of 5
5.0 wt%) 68.2 g of Lionol Blue KLH1
0.0 g and 21.8 g of toluene were added, kneaded with a sand mill, and evaluated.

Comparative Example 3 Lionol Blue KLH1 was added to 70.0 g of a varnish (50% by weight of non-volatile content) neutralized with aqueous ammonia of maleated rosin.
0.0 g and 20.0 g of water were added, kneaded with a sand mill, and evaluated.

Table 2 shows the performance of the aqueous inks obtained in Examples 1 to 9 and Comparative Examples 1 to 3.

[0040]

[Table 2]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (1)

(57) [Claims] 1. The following general formula (1): X-[(YO) n-H] m (1) (wherein X represents a rosin substance residue, and Y represents —CH ₂ CH ₂₎
- or _-CH 2 CH _(CH 3) - the same or different groups represented, n represents the number of up to 5 to 100, m is a number from 1 to 4, respectively. An alkylene oxide-added rosin derivative represented by the formula
And a printing ink binder containing
Alkylene oxide addition to total binder solids
A binder for an aqueous gravure printing ink, wherein the content of the rosin derivative is 3 to 70% by weight .