JPH0680918A - Binder for water-base gravure printing ink - Google Patents

Abstract

PURPOSE:To provide the title binder satisfactory in the gloss and driability of print. CONSTITUTION:An alkylene oxide/rosin derivative adduct of the general formula: X-[(Y-O)n-H]m (wherein X is a residue of a rosin substance, n is a number of 5-100, and m is a number of 1-4) is used in an amount of 3-70wt.% based on the total weight of the solid of a printing ink binder.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a binder for an aqueous gravure printing ink containing a specific amount of an alkylene oxide-added rosin derivative.

[0002]

2. Description of the Related Art Conventionally, organic solvents have been the mainstream as binders used in gravure printing inks. For example, in oil-based gravure printing inks applied to magazines, weekly magazines, and other materials, in consideration of performances such as dryness after printing and gloss of printed matter, reaction between a rosin compound and a metal compound as the binder The product (metal salt of resin acid) has been widely used.

However, in recent years, water-based gravure printing inks have been earnestly demanded from the viewpoints of prevention of air pollution, regulations under the Fire Service Law, occupational safety and health, etc. Therefore, a water-based binder having performance comparable to that of the organic solvent-based binder is desired. The demand for development is increasing. Already, acrylic resins and styrene-acrylic resins have been mainly proposed as water-based binders for such applications, and various attempts have been made to make them water-soluble or water-dispersed, but these have not necessarily led to satisfactory properties. The current situation is not.

[0004]

DISCLOSURE OF THE INVENTION In view of the above-mentioned circumstances regarding the binder for gravure printing inks, the present invention is an aqueous gravure having gloss and drying properties comparable to those of solvent-based inks using conventional resinous acid metal salts. It is intended to obtain an excellent aqueous binder suitable for providing a printing ink.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, by using a specific rosin derivative as an essential component of a binder, the pigment dispersibility and gloss are excellent. It was found that a water-based gravure printing ink can be obtained. It was also found that by using an emulsion or hydrosol in combination with the rosin derivative, an aqueous gravure printing ink excellent in not only pigment dispersibility and gloss but also drying property can be obtained. 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 (3) is contained in an amount of 3 to 70% by weight based on the total solid content of the printing ink binder.

Examples of the rosin substance which is a raw material of the alkylene oxide-added rosin derivative of the present invention include natural rosins such as gum rosin, tall oil rosin and wood rosin and purified products thereof; disproportionation, hydrogenation, dehydration and dimerization of the rosin. , Various modified rosins obtained by sulfonation; acid addition rosins obtained by addition reaction of maleic acid, maleic anhydride, fumaric acid, acrylic acid, etc. with the rosins; partial ester or partial amidation products of such acid addition rosins Can be exemplified. Each of these rosin substances is used alone or 2
A combination of two or more species can be used.

As the alkylene oxide which is another raw material of the alkylene oxide-added rosin derivative of the present invention, ethylene oxide and propylene oxide are applicable, and these can be used alone or in combination.

The number of moles of the alkylene oxide added is carefully determined in consideration of the performance of the binder or ink to be obtained, 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 number of added moles is less than 5 moles, the water solubility of the binder is lowered 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 resulting ink is permeated into the paper. There is.

In the present invention, as described above, it is preferable to appropriately use an emulsion or a hydrosol together with the alkylene oxide-added rosin derivative. Such emulsions and hydrosols are not particularly limited and various known ones can be selected and used. Specifically, acrylic polymer emulsion, acrylic-styrene polymer emulsion, styrene polymer emulsion, resin acid metal salt emulsion. Examples thereof include emulsions of esterified products of resin acids and polyhydric alcohols, and hydrosols corresponding to these, and these can be used alone or in an appropriate combination. Of these, 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 constituent of the binder of the present invention, is not particularly limited, and various conventionally known methods can be adopted as they are. For example, (1) while heating and melting the rosin substance, ethylene oxide and / or propylene oxide is press-fitted in an inert gas atmosphere such as nitrogen in the presence of an acidic or basic catalyst at 150 to 200 ° C. for 1 to 5 hours. (2) The rosin derivative and at least one of polyethylene glycol, polypropylene glycol, poly (ethylene-propylene) glycol, etc., without catalyst or under a known catalyst such as Lewis acid. Examples thereof include a method of esterification at 200 to 300 ° C. for about 10 to 20 hours.

The specific alkylene oxide-added rosin derivative thus obtained has good solubility in water and good pigment dispersibility, so that an aqueous gravure ink having a high solid content can be prepared.

In the present invention, it is essential to use the above-mentioned emulsion or hydrosol together with the alkylene oxide-added rosin derivative in order to further improve the drying property of the obtained aqueous gravure printing ink. By properly selecting the type of the emulsion or hydrosol and the combination ratio thereof, various binders for aqueous gravure printing ink having desired performance can be prepared. Usually, it is preferable to use the emulsion or hydrosol in combination 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 the aqueous gravure printing ink of the present invention is prepared by using various conventionally known pigments, if necessary, a hydrophilic solvent such as alcohol or glycol ether, and other additives in combination, and kneading by a known method. The desired water-based gravure ink can be easily prepared. The binder content in the ink composition is not particularly limited, but it is usually appropriately determined in consideration of various properties and viscosity of the obtained ink, and is preferably about 10 to 60% by weight in the ink composition, preferably 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 is satisfactory in terms of glossiness and dryness of 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 placed in an autoclave, heated and melted while substituting with nitrogen, and then 660 g of ethylene oxide was injected with nitrogen. After completion of the press-fitting, 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 ethylene oxide 15 mol).

Production Example 2 A reaction was performed 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 (5 mol ethylene oxide addition product).

Production Example 3 The same reaction as in Production Example 1 was conducted except that 880 g of ethylene oxide was used, and polyethylene glycol ester of rosin (addition product of 20 mol of ethylene oxide) was used.
Got

Production Example 4 In Production Example 1, hydrogenated rosin 300 was used instead of rosin.
The same reaction was performed except that g was used, and polyethylene glycol ester of hydrogenated rosin (ethylene oxide 15
A molar addition product) was obtained.

Production Example 5 A reaction was conducted 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 ethylene oxide 10 mol).

Production Example 6 The same reaction as in Production Example 4 was carried out 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 same reaction as in Production Example 4 was conducted 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 8 219 g of polyethylene glycol (average molecular weight 600) was added to 100 g of rosin, and the mixture was heated at 200 ° C. to 300 ° C. for 10 to 10.
Esterification was carried out for 13 hours to obtain polyethylene glycol ester of rosin (addition product of ethylene oxide 14 mol).

Properties of various alkylene oxide-added rosin derivatives obtained in Production Examples 1 to 8 are shown in Table 1.

[0026]

[Table 1]

Example 1 Alkylene oxide-added rosin derivative 1 obtained in Production Example 1
Acrylic emulsion (manufactured by Johnson,
Product name "Joncryl 775", solid content 45, 5
%) 44.0 g, and then 1 indigo pigment (manufactured by Toyo Ink Mfg. Co., Ltd., trade name "Rionol Blue KLH")
0.0g and 35.7g of water were added, respectively. Kneading was performed using a sand mill to obtain indigo ink. The content of the added rosin derivative is 33.3% by weight (based on the solid content of the ink binder). Each of the obtained indigo inks was spread on a coated paper using a bar coater # 10, and the gloss was visually evaluated according to the following criteria. The dryness was evaluated according to the following criteria by touching with fingers. 5: Very good 4: Good 3: Somewhat good 2: Inferior 1: Very inferior

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.

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.

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.

Example 5 In Example 1, 4.0 g of the addition product obtained in Production Example 4 was used.
, 64.0 g of the acrylic emulsion and 21.
The ingredients were compounded and evaluated in the same manner as in Example 1 except that 0 g was added. The content of the added rosin derivative is 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.

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.

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.

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.

COMPARATIVE EXAMPLE 1 71.0 g of the acrylic emulsion, 10.0 g of lionol blue, 3.3 g of isopropanol, and 1 part of water
5.6 g was added and kneaded with a sand mill for evaluation.

Comparative Example 2 Toluene varnish of resin acid metal salt (trade name "Lime Resin No. 12" manufactured by Arakawa Chemical Industry Co., Ltd.) (nonvolatile content 5)
5.0 wt%) 68.2 g of lionol blue KLH1
0.0 g and 21.8 g of toluene were added, and the mixture was kneaded with a sand mill and evaluated.

Comparative Example 3 70.0 g of a varnish for neutralizing maleated rosin with aqueous ammonia (nonvolatile content: 50% by weight) was added to Rionol Blue KLH1.
0.0 g and 20.0 g of water were added, and the mixture was kneaded with a sand mill and evaluated.

Table 2 shows the performance of the various water-based inks obtained in Examples 1 to 9 and Comparative Examples 1 to 3.

[0040]

[Table 2]

Claims (2)

[Claims] 1. A 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 (3) is contained in an amount of 3 to 70% by weight based on the total solid content of the printing ink binder. 2. The printing ink binder according to claim 1, which contains an emulsion or a hydrosol.