DE2812899A1 - PRINT INK COMPOSITION - Google Patents

Description

⁰ ATEhJTATJWALTE A. GRÜNECKER

DIPL-ING

H. KINKELDEY

T DR-ING

W. STOCKMAIR

O O 1 OQQQ OR-INGAeE (CALTtOl)

^{L ö} ' ^{l Ö ya} K. SCHUMANN

DR RER NAT. ■ DIPL-PHYS

P. H. JAKOB

DlPL-ING

G.BEZOLD

DRRERNAT-DIPL-CHEM.

MUNICH

NIPPON OIL CO. , LTD. Lindau

3-12, 1-chome, Nishi Shimbashi, Miaato-ku

Tokyo, Japan''s Munich 22

________ ^ ____________________ MAXIMILIANSTRASSE 43

March 23, 1978 P 12 568

Print color composition

The invention relates to aqueous and alcoholic printing compositions, which contain a resin as a carrier or vehicle, which is produced by reacting cyclopentadiene, dicyclopentadiene or one of its alkyl derivatives with an unsaturated carboxylic acid such as maleic acid to form an acid-modified one Resin and then reaction of the resin thus obtained with a phenolic resin of the resol type is obtained. According to a Embodiment, the invention relates to a method for producing the resin which is suitable as a carrier or vehicle.

The invention relates to alcoholic or aqueous printing ink compositions or printing ink compositions (for the sake of simplicity in the present application the "Ink compositions used). It relates particularly to those printing ink compositions which contain a resin varnish as the main component, which is obtained by reacting Cyclopentadiene, dicyclopentadiene or one of their alkylsubsti-

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tuted products is obtained with an unsaturated carboxylic acid to form a resin, which then with a phenolic resin of the resol type is reacted and dissolved in an alcohol and / or water.

Known gravure or rubber printing inks contain flammable solvents in almost all cases, and they give therefore, when they are used, they cause pollution of the work environment, the risk of ignition and deliver exhaust gases, that pollute the air. Because printing inks that contain an alcohol or water as a solvent are easy to handle and are advantageous and quick to set because of pollution, there has been a long-felt need for such Paints containing various aqueous resins. However, when printed, they show insufficient printability and are obtained no satisfactory printing results, such as, in particular, insufficient gloss and water resistance. They were therefore only used for special applications, such as printing wallpaper. Aqueous printing inks later became brought onto the market, made from colophony or maleic acid resin reacted with maleic acid or maleic acid derivatives as the main binder and casein or shellac as an additive. You are now in considerable Extensively used in rubber inks for kraft paper, corrugated board, etc., but they are considered to be printable are not satisfactory and do not give prints with satisfactory scuff resistance and scuff resistance after printing on a substrate. In addition, the resources for the rosin, which is one of the Materials for the rosin reacted with maleic acid, and its price fluctuates and a price increase is expected. Rosin, which occurs naturally, also varies widely in quality or properties, and it is very much today difficult to get consistently high quality compared to synthetic resins. There is therefore a

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great need for the development of new resins which can be used instead of rosin in the cases described above can be.

The applicant has surprisingly found that a specific resin which, instead of the aqueous resins, such as of the rosin reacted with maleic acid or with maleic acid derivatives, can be used, obtained from dicyclopentadiene which is a by-product in the petroleum industry. According to the invention it is possible to use alcoholic and aqueous Manufacture printing inks using the specific resin.

It is known that resins formed by thermal reaction of cyclopentadiene o.a. with an unsaturated carboxylic acid are useful carriers for aqueous or alcoholic inks or printing inks (JA-OSen 62208/74 and 104906/76). After printing, however, the aqueous or alcoholic inks that use these known resins as a carrier do not necessarily give prints with completely satisfactory water resistance and gloss.

The present invention is based on the object of eliminating the disadvantages of the known printing inks. According to the invention becomes cyclopentadiene or a similar compound with an unsaturated carboxylic acid at elevated temperature reacted, and the resulting resin is then reacted with a resol-type phenolic resin to form a final resin product, which was surprisingly found to be Carrier for aqueous or alcoholic printing inks has very good properties. After printing on a substrate, aqueous or alcoholic inks give this final resin as Contain carrier, prints with significantly improved water resistance, improved drying properties (short ab = setting time) and improved gloss.

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Those used in the printing inks of the invention Resins are made as follows.

Cyclopentadiene, dicyclopentadiene or one of their alkyl-substituted products (A) is reacted with heat with an unsaturated carboxylic acid (B) to form an acid-modified resin (I). In this reaction, it is necessary to use materials (A) and (B) in weight ratios of 80/20 'to 50/50. If materials (A) and (B) are used in weight ratios above 80/20, the resulting resin has a deteriorated solubility in alcohol or water, while if (A) and (B) are used in weight ratios below 50/50 the resulting resin will be significantly discolored. The reaction is conducted at 160 to 300 ° C, preferably 200, for 30 minutes carried out to 250 C ⁰ to 15 hours. If a reaction temperature below 160 ° C is used, insoluble material will be formed in the resulting resin, while if a reaction temperature above 300 ° C is used, the resulting resin will be markedly discolored.

The acid-modified resin (I) thus obtained is then reacted with a resol type phenol resin under heat. at this reaction is the phenolic resin (C) from. Resole type in amounts of 5 to 50 parts by weight / 100 parts by weight of acid-modified Resin (I) used. If the material (C) is used in an amount less than 5 parts by weight, the resin (I) becomes insufficient modified, while when used in amounts over 50 parts by weight, no final resin with satisfactory solubility is obtained in water or alcohol. The reaction is carried out at 150 to 250 ° C for 30 minutes to 10 hours, the final resin according to the invention for printing inks or printing ink is obtained.

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The resin according to the invention can also be obtained by mixing cyclopentadiene or the like. (A), the unsaturated carboxylic acid (B) and the phenolic resin (C) of the resol type with each other, and reacting the resulting mixture at 160 are made to 300 ⁰ C for 0.5 to 15 hours _o

Cyclopentadiene, dicyclopentadiene or any of their alkyl-substituted products (A) used as one of the materials for the end resin need not necessarily be pure. However, it is preferred that the material (A) contain 80% by weight or more of cyclopentadiene, dicyclopentadiene or one of their alkyl-substituted products. contains in terms of reactivity, reaction rate and the like property in the material (A). The material (A) can advantageously be a concentrated fraction _s the resultant by thermal codimerization of cyclopentadiene or methylcyclopentadiene with formation of dicyclopentadiene Cyclopentadiene-Methylcyclopentadiene-Codimer ₀ Cyclopentadiene = · Isoprene-Codimer, Cyclopentadiene-Piperylen-Codimer among others in the mixture and then distilling the Reaction mixture for removing the greater part of the Cc constituents, such as Cc-01efins and C ^ -paraffins, with formation of the concentrated fraction. The material (A) can optionally contain polymerizable vinylic compounds in amounts below 50% by weight, based on the material (A).

The unsaturated carboxylic acids (B) used in the present application include acrylic acid, methacrylic acid, Maleic acid, maleic anhydride, tetrahydrophthalic acid and their anhydride, fumaric acid, citraconic acid and itaconic acid.

The resol type phenolic resin (C) used as the third material in the present invention can be by reacting a phenolic compound with formaldehyde

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be prepared in the presence of an alkali catalyst. The phenolic used in the present application Compounds include phenol and alkyl substituted phenols such as cresol, p-tertiary butylphenol, p-tertiary octylphenol, and Nonylphenol.

In the manufacture of printing inks using of the final resin according to the invention, it is good to use this resin together with a conventional, water-soluble or alcohol-soluble Resin, such as rosin reacted with maleic acid or maleic anhydride, or rosin, modified with fumaric acid Rosin or rosin, to be used with maleic acid resin, alkyd resin, shellac or acrylic resin.

The alcohols used in the aqueous or alcoholic printing inks according to the invention include monohydric ones Alcohols such as butanol, isopropanol, ethanol and methanol; polyhydric Alcohols such as ethylene glycol, propylene glycol, diethylene glycol and glycerin; Mixtures of these alcohols; and mixtures these alcohols and water. In the production of aqueous printing inks using the invention End resins, the end resin can be modified to the amine salt or alkali metal salt to increase its solubility in water will. The final resin or finished resin dissolves more easily in a solvent when the solvent is a solvent mixture is made up of water and an alcohol, thereby decreasing the amount of amine or alkali that is used can. The amines and alkalis that can be used include alkanolamines, such as monoethanolamine, diethanolamine, Triethanolamine; Alkylamines, such as ethylamine and diethylamine, as well as Ν, Ν-dimethylaminopropylamine, morpholine, piperidine, Ammonia, KOH, NaOH etc.

When producing a printing ink using the alcoholic or aqueous lacquer according to the invention, it is

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It is necessary that the pigments used are stable when they are present together with the water, alcohol and alkali which are contained as components in the printing ink, since it is important that the pigments are compatible or wettable with the printing ink binder varnish is further preferred that a wax compound (such as polyethylene wax) is in the printing ink incorporated to improve the frictional resistance of the film-like printing produced with the ink, and further that other additives, according to need, such as antifoaming agents and dispersing agents _s are present.

Using the final resin of the invention is it is possible to produce printing inks with satisfactory water resistance and gloss, such as printing inks for the aqueous gravure printing and flexographic printing inks or printing inks for rubber printing.

The following examples and reference examples illustrate the invention. All percentages and parts are _s unless otherwise indicated, expressed by the weight

Reference example

60 parts of dicyclopentadiene with a purity of 95% and 40 parts of maleic acid are placed in an autoclave equipped with a stirrer The mixture is reacted at 220 ° C. for 5 h. The autoclave is then cooled and the reaction product is used for removal unreacted material and the low polymer distilled to produce resin (I) =

To 100 parts of the resin (I) is added per 3 '5? 15 "30 50 _P and 55 parts of a phenolic resin commercially available resol-type (manufactured under the trademark HITANOL 2501 by Hitachi Kasei Kogyo Co _{0 9} Ltdo) to form a mixture _s

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which is then melted and ^{reacted for 2 hours at 220 °} C. to form a resin. The resins (II) -1 to (II) -6 thus obtained show the solubility in water and an alcohol shown in the following table and have the phenolic resin modification degree also shown in the following table.

Resin Resin Resin Resin Resin (H) -I (II-2) (l $ -3 (H) -4 (II) -5 (H) -6

Amount of phenolic resin
iro 100 parts resin
I) (parts) 3 5 15 30 50 55

Solubility in water , * \

and in alcohol ζ ^ 'ζ ζ ζ ζ

Degree of modification ngz ζ ζ ζ ζ ζ

(1) ζ = satisfactory

(2) ngz = not entirely satisfactory

From the results of the table above, it can be seen that the preferred amount of resol type phenolic resin that is per 100 parts of resin (I) is used, ranges from 5 to 50 parts.

example 1

60 parts of dicyclopentadiene with a purity of 95% and 40 parts of maleic acid are placed in an autoclave equipped with a stirrer. The resulting mixture is reacted at 220 ° C. for 5 h. Thereafter, the autoclave is cooled and the reaction product is unreacted for removal Material and lower polymers are distilled therefrom to form resin (I).

100 parts of the resin thus obtained are prepared with 12 parts of a commercially available resol type phenolic resin ( under the trademark HITANOL 2501 from Hitachi Kasei Kogyo Co., Ltd.) and the resulting mixture is

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melted and 2 h at 220 ° C to form the resin (II) reacted with a softening point of 141 ° C and an acid number of 105.

Example 2

65 parts of dicyclopentadiene with a purity of 92% _s 35 parts of maleic anhydride and 40 parts of xylene are placed in an autoclave equipped with a stirrer. The resulting mixture is reacted for 2 hours at 260 ° C., then the reaction product is distilled! the resin (III) is obtained «,

Then 100 parts of the resin (III) thus obtained with 15 parts of a commercially available phenolic resin from Resole type (manufactured under the trademark HITANOL 2180 by Hitachi Kasei Kogyo Co., Ltd ») mixed to form a mixture, which melted and formed at 230 ° C for 1 hour of the resin (IV) with a softening point of and an acid number of 180 is reacted.

Comparative example 1

In a flask equipped with a .Rührvorrichtung autoclave charged 60 parts of dicyclopentadiene having a purity of 95% and 40 parts of maleic acid to form a mixture containing 6 h reacted at 230 ⁰ C is "The reaction product is to remove unreacted material and low polymers destilliert5 one This gives the resin (V] with a softening point of 151 ^° C. and an acid number of 120.

Comparative example 2

65 parts of dicyclopentadiene with a purity of 95% » 35 parts of maleic anhydride and 40 parts of xylene are placed in an autoclave equipped with a stirrer

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given. The resulting mixture is ^{reacted at 270 °} C. for 2.5 hours. The reaction product is then distilled; . the resin (VI) with a softening point of 155 ° C. and an acid number of 210 is obtained.

Example 3

30 parts of the resin (II) obtained in Example 1 are mixed with 50 parts of isopropyl alcohol (IPA) and 18 parts of water and 7 parts 28 & Lgem ammonia water mixed; you get a solution called "Varnish A".

Using the varnish A thus obtained, a gravure printing ink is produced according to the following recipe:

Color a

Lacquer A 74 parts

Phthalocyanine Blue 15 parts

Antifoam Agent (manufactured under the

Trademark SHIN-STSU SILICONE KF-96 of

Shin-etsu Kagaku Co., Ltd.) 1 part

Water 10 parts

Comparative example 3

35 parts of the resin (V) obtained according to Comparative Example 1 are mixed with 43 parts of IPA, 15 parts of water and 7 parts 28 #! Ammonia water mixed to produce a solution, which is referred to as "paint B".

Using the varnish B obtained in this way, a gravure printing ink is produced according to the following recipe:

Color B

Lacquer B 75 parts

Phthalocyanine Blue 15 parts

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• A-

■ IS

Anti-foaming agent (manufactured under the

Trademark SHIN-ETSU SILICONE KF-96 by

Shin-etsu Kagaku Co., Ltd.) 1 part

Water 9 parts

The above-described intaglio inks A and B are printed on art paper using an intaglio printing machine printed and their properties are checked. The results are shown in the following table-

Tabel

Shine of the water-resistant-blocking print speed

Color A satisfactory - satisfactory none

(Example 1)

Color B (not quite closed = not satisfied = none same example 1) pacifying

The experiment is carried out as follows

Gloss of prints - determined visually by observing the dried prints;

Water resistance (more precisely, friction resistance when wet) - determined by performing a friction resistance test using a Southerland friction tester impregnated with one with water Cloth is wrapped;

Blocking - it occurs when the pressure used · = paint has unsatisfactory drying properties (low drying speed) »

It can be seen from the table above that the printing ink A containing the resin according to the invention _{9 has} better properties than the ink B ₉ . which was produced according to comparative example = · game 3 o It can be seen that the printing ink A is a very good ₉ aqueous gravure printing ink «

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Example 4

40 parts of the resin (IV) obtained according to Example 2 are dissolved in 55 parts of diethylene glycol at 180 ⁰ C. After cooling, the resulting solution is mixed with 5 parts of monoethanolamine to form varnish C. Using the lacquer C, a glycol printing ink is produced according to the following recipe.

Printing ink C

Lacquer C ⁱ 74 parts

Piness Red 2B (red pigment, manufactured

by Toyo Ink Mfg.Co., Ltd.) 15 parts

Wax compound 5 parts

Diethylene glycol 6 parts

Comparative example 4

45 parts of the resin (VI) obtained according to Comparative Example 2 are dissolved in 50 parts of diethylene glycol at 180.degree solved. After cooling, the resulting solution is mixed with 5 parts of monoethanolamine to produce the varnish D. Using the varnish D, a glycol printing ink is produced according to the following recipe.

Printing color D

Paint D 72 parts

Fineness Red 2B 15 parts

Wax compound 5 parts

Diethylene glycol 8 parts

The above glycol inks C and D are made on Kraft paper using a KORD printing machine (manufactured by Heidelberger Druckmaschinen AG) and then printed checked their properties. The results are shown in the table below.

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Tabel

Printing time until the prints are glossy water resistance color setting (sec)

C 15 satisfactory satisfactory D 20 not satisfied not entirely satisfied «

The experiment is carried out as follows?

Time to set - determined by touching the prints with human fingersj

Gloss of prints - determined visually by observation of the dried prints j

Water resistance (more precisely friction resistance when wet) - determined by the friction resistance » ability test using a Southerland friction test » Räts carry out ^ this with a cloth impregnated with water is wrapped.

From the above table it can be seen 'that the printing ink C containing resin of the invention, better properties than in Comparative Example 4 is prepared ink D and a very good ink glycol.

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Claims (5)

PATENT ADVOCATES A. GRÜNECKER Dl PL-ING H. KINKELDEY DA ING W. STOCKMAIR DR-ING ■ AeE (CALTECHl K. SCHUMANN DR RER NAT. - DIPL-PHYS P. H. JAKOB DJPL-INa G. BEZOLD DR RER NAT. - DPL-CHHM. MUNICH E. K. WEIL DA RHR OEC ING 8 MUNICH 22 MAXIMILIANSTRASSE 43 LINDAU Claims (1. Aqueous and alcoholic printing ink composition, characterized in that it contains, as a carrier, an end resin which is prepared by reacting (A) one Compound from the group of cyclopentadiene, dicyclopentadiene or one of their alkyl-substituted products with (B) a unsaturated carboxylic acid or its anhydride in weight ratios of 80/20 to 50/50 to form an acid-modified one Resin and then reacting the resin thus obtained with (C) a resol type phenolic resin in an amount of 5 to 50 parts by weight / 100 parts by weight of acid-modified resin forming the final resin. 2. Aqueous and alcoholic printing ink composition according to claim 1, characterized in that the unsaturated Carboxylic acid (B) in the production of the final resin acrylic acid, methacrylic acid, maleic acid, maleic anhydride, Tetrahydrophthalic acid or its anhydride, fumaric acid, Citraconic acid or itaconic acid is used, and that the resol type phenolic resin (C) used in the manufacture of the final resin is used by reacting cresol, p-tert-butyl- 809840/0908 TELEPHONE (089) 22 28 62 TELEX O5-29 380 TELEGRAMS MONAP phenol, p-tert.-octylenephenol or nonylphenol with formaldehyde has been obtained in the presence of an alkali catalyst. 3. Aqueous and alcoholic printing ink composition according to claim 1, characterized in that the reaction of the compound (A) with the acid or its anhydride (B) at 160 to 300 ⁰ C for 30 minutes to 15 hours and the reaction of the acid-modified resin with the Phenolic resin (C) can be carried out at 150 to 250 ^° C. for 30 minutes to 10 hours. 4. Process for the preparation of a final resin which is used as a carrier for aqueous and alcoholic printing ink compositions is suitable, characterized in that (A) a compound from the group consisting of cyclopentadiene, dicyclopentadiene and their alkyl-substituted products with (B) an unsaturated carboxylic acid or its anhydride in weight ratios from 80/20 to 50/50 to form an acid-modified resin and then the resin thus obtained with (C) a resol type phenolic resin in an amount of 5 to 50 parts by weight / 100 Parts by weight of acid-modified resin reacted to form the final resin. 5. The method according to claim 4, characterized in that that the reaction of the compound (A) with the acid or its anhydride (B) is carried out at 160 to 30O ⁰ C for 30 minutes to 15 hours and that the reaction of the acid-modified resin with the phenolic resin (C) at 150 to 250 ⁰ C takes place over 30 minutes to 10 hours. 809840/0906