DE1546771C - Arakawa Rinsan Kagaku Kogyo K.K., Osaka (Japan) - Google Patents

Description

The invention relates to intaglio printing inks ("gravure ink"), which act as a binding agent in certain Contains modified petroleum-based resin for printing on paper.

Gravure printing inks (hereinafter referred to as printing inks for short) not only have to be cheap, they also have to be cheap Print also have high gloss and dry quickly and are allowed due to the high speed have no tendency to stick when pressed. Furthermore, they must have excellent viscosity stability. Around To meet these requirements, printing inks have previously been made by mixing pigments with one Carrier made by dissolving a modified rosin in an organic solvent was made. However, these known printing inks have not necessarily been satisfactory in terms of their quality the stability of viscosity and gloss when printing. Be used in the manufacture of paints a wide variety of synthetic resins are used, but so far no binders have been used for printing inks needed that come close to the economic efficiency and suitability of modified rosin.

In an effort to produce printing inks using inexpensive petroleum-based resins, which are available in large quantities as are available, an attempt was initially made to disperse pigments in a binder that by directly dissolving a petroleum-based resin in an organic solvent. However, the resulting printing ink was found to be poor in printing glossiness Drying speed and viscosity stability, so that their later use was impossible. The invention relates to printing inks which do not have the disadvantages mentioned above, have a significantly higher gloss when printed than printing inks containing modified rosin than Binder used, dry quickly, no tendency to stick when printing at high speed and have stable viscosity. The printing inks according to the invention are characterized by that a modified petroleum-based resin is used as a binder, which by reaction of a petroleum-based resin in the molten state with an α, /? - unsaturated dicarboxylic acid and reaction of the adduct obtained with a reactive compound of a Group II metal of the Periodic table has been established.

The petroleum-based resin used as starting material for the purposes of the invention is an unsaturated hydrocarbon resin which is produced by polymerizing petroleum fractions which ^{boil between -20 and 280 °} C. in the presence of Friedel-Crafts catalysts. This unsaturated hydrocarbon resin is described in the following references: U.S. Patents 2698841, 2762851 and 2,933,468, "Sekiyu to Sekiyu Kagaku" (Petroleum and Petrochemicals, published by Kabushiki Kaisha Saiwai Shobo, Japan), 5, No. 8, p . 3 (1961), and No. 9, p. 32 (1961). These resins are cheap and can be supplied in large quantities.

The petroleum fractions used to make the resin are produced as the main product or by-product of the steam cracking of petroleum spirits. They can be polymerized in the presence of a Friedel-Crafts catalyst after having been fractionated as required. The normal polymerization temperature is below 100 "C. The resins produced contain one or more ethylenic double bonds in the molecule. Their properties vary depending on the fractions used and the polymerization conditions used, but they usually have a molecular weight of 300 to 2000, a softening point of 50 to 130 ⁰ C (ball and ring), a bromine number from 5 to 80, an acid number from 0 to 5 and a saponification number from 0 to 5.

For the purposes of the invention, not only are all petroleum resins with the stated physical properties suitable Properties, rather it. petroleum resins can also be used, whose properties are outside are within this range, but petroleum resins, their softening point and bromine number are particularly preferred lie within the stated ranges.

The expression "Λ, / J-unsaturated dicarboxylic acid" includes both the anhydrides and the acids. Representative examples of suitable acids are maleic acid, Fumaric acid, citraconic acid and maleic anhydride, citraconic anhydride, etc. are particularly preferred this becomes maleic anhydride.

According to the invention, the α, / 9-unsaturated Dicarboxylic acids reacted with the petroleum resins in the melt flow. The reaction temperature must be in the range lie between the melting point of the petroleum resin and the boiling point of the α, /? - unsaturated dicarboxylic acid. The optimal reaction temperature will depend on the type of petroleum resin and the one used «, / ^ - unsaturated dicarboxylic acid chosen. In general, a temperature of from 200 to 210.degree. C. is expedient.

In the reaction, a peroxide catalyst, e.g. B. p-tert-butyl peroxide, tert-butyl perbenzoate or benzoyl peroxide, used as needed. The amount of dicarboxylic acid used depends on the Petroleum resin and the reaction conditions used. It is usually 1 to 30 percent by weight, in particular 3 to 15 percent by weight, calculated as maleic anhydride and based on the Weight of the petroleum resin used. An organic solvent for the reaction system may be added Petroleum resin can be added to reduce its melt viscosity. The mechanism of this The reaction has not yet been clearly established, but the reaction can be viewed as an addition reaction as disclosed in U.S. Patent 2,933,468. Due to the Λ, / 9-unsaturated dicarboxylic acid a carboxyl group has been introduced into the product. The reaction is easier when using petroleum resins with a higher bromine number can be used.

The addition product into which a carboxyl group has been introduced is then reactive with a Compound of a metal of group II of the periodic table implemented. Examples of this reactive compounds are the oxides, halides and hydroxides of the metals mentioned, e.g. B. of magnesium, calcium, zinc, barium, strontium, cadmium etc. The most suitable of these are those Oxides or hydroxides of calcium or zinc. There are two methods for this reaction, namely implementation of the adduct in molten form with the reaction compound of the divalent metal and a common double decomposition process in which the adduct is first converted into an alkali salt in the presence or absence converted to a solvent and the alkali salt then with the reactive compound of the divalent metal is implemented. the

the first method is more economical and consists of a melting process in which the reaction temperature depends on the type of adduct and the reactive compound. In general, temperatures from 200 to 280 ^° C. are suitable. The reaction only takes place by heating. The reaction rate can be increased by using a metal salt of an aliphatic monocarboxylic acid as a catalyst. Calcium acetate is preferred as the catalyst. The reactive compound is expediently used in the amount equivalent to the reaction (based on the adduct) or in a smaller amount. In general, an amount of from 2 to 8 percent by weight, in particular from 4 to 7 percent by weight (calculated as calcium), based on the adduct, is suitable.

In the above-described reaction, all or part of those introduced into the petroleum resin form Carboxyl groups a salt with the metal of Group II of the Periodic Table, reducing the polarity that Molecular weight and the softening point of the petroleum resin can be increased.

In the method for producing the modified petroleum resin according to the invention, various are Changes possible. For example, the reaction in the first stage, i.e. H. in the implementation of the Petroleum resin with the Λ, / 9-dicarboxylic acid, in the presence to be completed by rosin. Natural resin, wood resin (from the Extract of stumps and other parts of the tree obtained rosin) or tall oil resin or their esters or metal salts in question, the metal belonging to group II of the periodic table. In this case, too, the reaction takes place in the melt flow, with the α, / ί-dicarboxylic acid not only in the petroleum resin, but also is introduced into the rosin through addition reaction. This method has the advantages of an increased softening point of the resin mixture obtained and an improved one Drying of the printing ink produced with this resin mixture. Another benefit is there in the fact that the dicarboxylic acid which has not reacted with the petroleum resin is caused by reaction with the rosin is consumed, a cumbersome process to remove the unreacted acid becomes superfluous. The time at which the rosin is added will depend on the Nature of the petroleum resins and «, ^ - dicarboxylic acids used as starting materials and of those used Chosen reaction conditions. For example, if a petroleum resin with low reactivity and a bromine number of 5 to 20 is used, the rosin can be used in the course of the reaction of the petroleum resin with the Λ, / 3-dicarboxylic acid are added. When using a petroleum resin of higher reactivity with a bromine number greater than 20 the rosin can be added in the initial phase or during this reaction, with the «, / Ϊ -dicarboxylic acid in the petroleum resin and in the rosin introduced and a resin mixture of higher softening point obtained in an advantageous manner will.

In each of the cases described above, even if a predominant amount of the added Rosin remains in the unreacted state, this rosin does not have any detrimental effects Influence on the product. Accordingly, the amount of rosin to be added may differ from the theoretical one Amount, based on the acid, that does not react with the petroleum resin, up to any greater Amount can be varied, generally less than twice the amount by weight of rosin, based on petroleum resin used, is preferred.

Further, in order to prevent deterioration in water resistance by introducing a large amount of To prevent carboxyl groups, there is a possibility of those in the petroleum resin and / or rosin introduced and unreacted carboxyl groups which are not a salt with the metal of group II des Forming the periodic table, using aliphatic polyhydric alcohols such as ethylene glycol, Glycerine, pentaerythritol, diethylene glycol, propylene glycol, trimethylolalkane and neopentyl glycol, to esterify. These aliphatic polyhydric alcohols can be added to the reaction system at any stage will. The addition is preferably made at the end of the second stage; H. the implementation of the First .Stufe obtained adduct with the reactive compound of the metal of group II. The The amount added varies within wide limits. Preferably, however, the number based of the unreacted carboxyl groups required theoretical amount or a smaller amount Amount used.

The measure of adding rosin and polyhydric alcohol can be beneficial but not absolutely necessary.

The printing inks for paper of the present invention can be easily prepared by dispersing pigments in a binder obtained by dissolving each modified petroleum resin in an organic solvent. A reinforcing filler, e.g. B. ethyl cellulose, can be added to improve the flexibility and abrasion resistance of printed surfaces, as is customary in the art. This ethyl cellulose is usually mixed with the binder in the form of a solution in an aromatic hydrocarbon. The viscosity of the binder can be within a wide range and depends on the pigment to be admixed and the mixer used. In general, a viscosity of 30 to 150 cP at 25 ° C. is expedient. For example, when used as a pigment Carmine 6 B and mixed in a sand mill, a binder, a viscosity of 4OcP at 25 ⁰ C is suitable. The concentration of the resin can be chosen so that the viscosity of the binder is kept in the above-mentioned range. Usually a concentration of 30 to 50 percent by weight is used. As a solvent for the resin, aromatic hydrocarbons, e.g. B. xylene, benzene, toluene, etc. can be used.

In general, the following proportions between binder, pigment and reinforcing filler are used applied:

binder
Pigment ...

General area | Preferred range parts by weight

60 to 97
3 to 40

80 to 90
10 to 20

The amount of reinforcing filler, if any, used is less than 12 percent by weight, preferably less than 10 percent by weight,

based on the end product. The proportions of the components depend on the intended use the printing ink, d. that is, it is not intended to be limited to the above ranges.

In the production of the printing ink according to the invention the modified petroleum resin can be used alone or in a mixture with other resins, z. B. with coumarone-indene resin, lime-modified Rosin, hydrogenated rosin, disproportionated Rosin, ester resin, rosin-modified phenolic resin, phenol-formaldehyde condensate, Alkylphenol-formaldehyde condensate, with rosin-modified maleic acid resin, etc.

»5 Example 1

100 kg of a brownish, transparent petroleum resin, which had a softening point of 65 ° C. (sphere ao and ring), a bromine number of 43.9 and a molecular weight of 600, 15 kg of maleic anhydride and Given 1 kg of p-tert-butyl peroxide. The system was slowly heated to melt with stirring until the temperature reached 145 ° C. This temperature was maintained for 1 hour then raised within another 30 minutes at 200 ^c C and maintained for further 30 minutes followed by melt reaction further. 8 kg of calcium hydroxide and 0.5 kg of calcium acetate were added and heated to 260 ° C. over the course of one hour. The mixture was left to react for 3 hours. The pressure in the reactor was then slightly reduced, whereby a small amount of volatile substances was removed 115 kg of modified petroleum resin, which had an acid number of 59.2 and a softening point of 114 ° C., were poured from the kettle.

The modified petroleum resin obtained was dissolved in the same amount of toluene. By adding more cream Toluene, the solution was diluted to a viscosity of 40 cP at 25 ° C. to form the binder. To 88 parts by weight of this binder were added 12 parts by weight of the pigment Carmine 6B. The printing ink was obtained by mixing in a sand mill. .

E xample 1 2

Into a 300-1 stainless steel reactor, 100 kg of a brown transparent oil resin had a softening point of 65 ⁰ C, so a bromine number of 43.9 and a molecular weight of 600, and added 20 kg of maleic anhydride. The mixture was rapidly heated to 200 ° C. with stirring to melt and held in the melt at 200 to 210 ° C. for 3 hours to continue the reaction. Then 9 kg of calcium hydroxide and 0.5 kg of calcium acetate were added, whereupon ^{the mixture was heated to 260 °} C. over the course of one hour with stirring and the mixture was left to react for 3 hours. A small amount of volatile substances was removed by lowering the pressure in the reactor. The product obtained was 120 kg of the desired modified Mrdölliarzes with an acid number of 47.8 and a softening point of 117 ° C.

The one prepared in the same manner as in Example 1 Solution of the modified petroleum resin formed in toluene became the desired with the pigment Carmine 6B Mixed printing ink.

B e i s ρ i e 1 3

In a 300 l stainless steel reactor, 500 kg of petroleum resin having a softening point was charged of 65 ° C, a bromine number of 43.9 and a molecular weight of 600 and 600 kg maleic anhydride given. The mixture became melting

Held for 2 hours with stirring at 200 ° to 210 ⁰ C, was added followed by 50 kg Pfianzenharz having a softening point of 8I ⁰ C and an acid number of 165th The mixture was then kept ^{at 200 ° C. for 1 hour and then heated to 260 °} C. over the course of one hour. During this time, 7 kg of calcium hydroxide and 0.5 kg of calcium acetate were added in ten successive portions, whereupon

Was held ^{at 255 to 265 0} C with stirring for 3 hours. A small amount of volatile substances was removed by reducing the pressure in the reactor. 110 kg of resin with an acid number of 39.5 and a softening point of 160 ° C. were taken as the product.

The printing ink for paper was prepared by adding the modified petroleum resin obtained to that in Example 1 was processed.

B e i s ρ i e 1 4

Into a 300-1 stainless steel reactor 50 kg petroleum resin was added with a softening point of 65 ⁰ C, a bromine number of 43.9 and a molecular weight of 600, 50 kg tall oil rosin and 10 kg of fumaric acid. The mixture was heated in one hour to melt at 200 to 21O ⁰ C, followed by 7 kg calcium hydroxide and 0.5 kg of calcium acetate were added and the temperature was raised to 260 ⁰ C einer_ hour. The mixture was then stirred for a further 3 hours, after which the pressure in the reactor was reduced and a small amount of volatile substances was removed. 110 kg modified petroleum resin having an acid number of 53.9 and a softening point of 181 ^C C were removed from the reactor.

The obtained resin was made into a printing ink for paper in the manner described in Example 1 processed.

Example 5

50 kg of petroleum resin with a softening point of 65 ° C., a bromine number of 43.9 and a molecular weight of 600, 10 kg of maleic anhydride and 0.5 kg of di-tert-butyl peroxide were placed in a 300 l stainless steel reactor. The mixture was heated to melting with stirring to 145 ° C, held for 1 hour at this temperature and then heated within 30 minutes to 200 ³ C and held for 30 minutes at this temperature. Then 50 kg of vegetable resin with a softening point of 81 ^° C. and an acid number of 165 were added. The mixture was ^{kept at 200 °} C. for 1 hour. The temperature was then raised within one hour to 26O ⁰ C. During this time, 8 kg of calcium hydroxide, 0.5 kg of calcium acetate and 1 kg of zinc oxide were added in six successive portions through the inlet opening, whereupon the mixture was kept at 255 to 265 ° C. for 3 hours with stirring. The pressure in the reactor was reduced which removed a small amount of volatiles. The product became 112 kg of the modified petroleum resin

7 8

with an acid number of 45.1 and a softening,. _. . .

point of 190 ° C obtained. b) Dry.property

The resin obtained was in Example 1 Ig of the printing ink to be tested in a

described manner given to a printing ink for paper Petri dish of 60 mm diameter. To

processed. 5 an hour this was due to evaporation of the original existing solvent decreased weight

, Example 6 determined.

■ '· .. evaluation

In a 300-1 stainless steel reactor Excellent

were 50 kg petroleum resin with a softening point ίο. '

of 65 ° C, a bromine number of 43.9 and a mole weight loss through evaporation over 80 · /.,

Weight of 600, 50 kg tall oil resin with one good:

Softening point of 75 ° C and an acid number weight loss through evaporation 50 to 80%,

given by 168. The mixture was melted ..

heated with stirring to 200 ⁰ C, with 7 kg 15 ⁵ ^ maleic ^Lech

acid anhydride and 7 kg of the following weight loss by evaporation below 50%.
described way produced phenol-formaldehyde

Precondensate (resin content 70%) were added. , ^{c) ΟΙί1ηζί (:! 5ί}

The mixture was stirred for 1 hour at The test ink was applied with a doctor blade

200 ^° C. and then applied ao to intaglio printing paper within 30 minutes. The shine of

brought to 230 ° C. Then 7 kg of calcium were printed on the surface at angles of 60 ° -60 °

hydroxide, 0.5 kg calcium acetate and 2 kg zinc oxide measured as a percentage of the reflectivity. To the

added. The temperature was set in 30 minutes for comparison, the results for comparison are in the table

26O ⁰ C increased and 3 hours at this value indicated printing inks for printing on paper,

keep. Then the pressure in the reactor as which were produced by the methods described in

decreased, with a small amount of volatile the following Comparative Examples 1 to 3 described

Substances has been removed. The received modi- are,

Comparative Example 1 had the fused petroleum resin in an amount of 115 kg

an acid number of 47.0 and a softening point ... ",,. -, ._. ",. .

from 179 ° C 30 Calcium modified rosin

The modified petroleum resin obtained was processed in a 300 l stainless steel reactor in the manner described in Example 1 to print 100 kg of vegetable resin with a softening ink for paper. point of 8I ⁰ C and an acid number of 165.4 kg

The aforementioned phenol-formaldehyde-calcium hydroxide and 0.2 kg calcium acetate are added.

Precondensate was prepared as follows: 17 kg of 35 D £ siJemiscfi was slowly added with stirring

Phenol, 22 kg of a 37% formalin solution and heated to 220 ° Ö for 3 hours at this temperature

0.3 kg of calcium hydroxide were used for 30 minutes at geiiaiieff. After lowering the pressure in the reactor

8O ⁰ C implemented. The system was filled with acetic acid and volatiles were removed

neutralized, washed with water, dehydrated 102 g calcium-modified rosin obtained,

and condensed to a resin content of 70%. 40 has an acid number of 95.0 and a softening point of 115 ° C.

B e i s ρ i e 1 7 The calcium-modified rosin obtained was based on that described in Example 1

During the production of the modified petroleum ■ manner processed into a printing ink,

resin in the same way as in Example 1 was 45

after the reaction of the resin with the calcium comparative example 2

connection and before lowering the pressure. ■ ■■■ ....>. r-j-n.

added kg of glycerol in the reactor 1, whereupon 2 STUN ^non-modified petroleum resin

the at the same temperature, ie 26O ⁰ C, stirred A brown, transparent, solid petroleum resin, the

would. By further work-up to the 50 softening point of 65 ° C, a bromine number

Game 1 described would have a printing ink of 43.9 and a molecular weight of 600,

for paper received. was dissolved in the same amount of toluene. Through

To better understand the advantages of the invention, further addition of toluene as a diluent

The following are the results of the test - the viscosity was adjusted to 40cP at 25 ° C,

Tests on viscosity stability, drying properties 55 whereby a binder for printing inks is obtained

and gloss as in the previous examples. In a sand mill, 88 parts of this were made

obtained printing inks in the following table with binder and 12 parts of the pigment carrrin 6 B

the values of printing inks from comparative to printing ink mixed,
looking compared. These exams were after

The following methods were carried out: 60 Comparative example 3

λ w, ~ t to i_ ·, '· - ■ -j ¹ ,, -, ■■■■■■ ···· Unmodified petroleum resin

a) Test for stability of the viscosity. .

Using a brown, see-through.

The viscosity of the printing ink immediately after solid oil resin, which has a softening point of

the production and after 7 days with the 65 120 ~ (\ a bromine number of 21.5 and a molecular

Brookficld viscometer measured. The lighter the weight of the S50, the more printing ink was used for

Difference between these two values, so as to paper on the one described in Comparative Example 2

the sl; ibililat of the viscosity is better. Way made.

Comparative example 4

100 kg of a petroleum resin with a softening point of 65 ° C, an iodine number of 43.9 and a molecular weight of 600, 15 kg maleic anhydride and 1 kg di-tert-butyl peroxide melted by heating and after reaching a temperature of 145 ° C for 1 hour at stirred this temperature, then heated in half an hour to 200 ° C and below

Leave stirring at this temperature for 3 hours. The pressure in the reactor was then reduced and the volatile substances removed. There were kg of a modified resin with an acid number of 73.8 and a softening point of 96 ° C.

According to the manner described in Example 1, using the so modified Resin printing inks made for paper.

Tested printing ink

Viscosity stability

viscosity

immediately after manufacture cP

viscosity

Days after manufacture
cP

Dry property

shine

Example 1 ....

Example 2 Example 3 Example 4 Example 5 Example 6 Example 7

Comparative example 1,
Comparative example 2
Comparative example 3
Comparative example 4

92 90 88 98 90 85 90

95 96 94 98

96

95

120

100

80

86

98

2700
2800
3100
4200

Well

Well

excellent
excellent
excellent
excellent

Well

Well

bad
bad
bad

45.4
41.6
23.7
24.1
19.0
16.3
44.2

8.5
8.5
8.7
8.5

Of the inks tested in the tests described above, those with gloss values above 12% had excellent visible gloss on the printed areas. In the case of Examples 5 and 6, in which much smaller amounts of the
were turned, showed »·
colors impeccable .__ u ^

Dry properties. .rch Verwenau quantities the modified petroleum resin is used to give printing inks increased gloss.

Claims (1)

Patent claims: 1. Gravure printing ink for paper, containing a binder and pigment dispersed therein, thereby characterized in that a substantial part of the binder consists of a modified Petroleum resin is made by reacting a petroleum resin in the molten state with a ^ -unsaturated dicarboxylic acid and reaction of the adduct obtained with a reactive one Compound of a metal of Group II of the Periodic Table alone or. is made in a mixture with other resins. 2. Printing ink according to claim 1, characterized in that the modified resin from a steam-cracked by Friedel-Crafts Polyinerisation of between about -20 and 280 ⁰ C. . Ethylenically unsaturated hydrocarbon polymers obtained from boiling petroleum fractions with a bromine number from 5 to 80 and a softening point, measured according to the ball and Ring method, made from 50 to 130 ° C. 3. Printing ink according to claim 1, characterized in that for modifying the resin Maleic acid, fumaric acid, citraconic acid, maleic anhydride and citraconic anhydride are used will. 4. Printing ink according to claim 1, characterized in that the reactive compounds of metals in group II of the periodic table, calcium hydroxide or zinc oxide is used will. 5. Printing ink according to claim 1, characterized in that Young that the «, ^ - unsaturated dicarbon -te in amounts of 1 to 30 percent by weight, ^ gen on the weight of the initial resin, ^ is turned. . Printing ink according to claim 1, characterized in that that the reactive compound of each metal in amounts of 2 to 8 percent by weight, based on the weight of the resulting adduct. 7. Printing ink according to claim 1, characterized in that the implementation of the petroleum resin and the - «, ^ - unsaturated dicarboxylic acid in the presence of rosin is carried out, with the amount of rosin between the theoretical Up to double the amount based on the acid that does not react with the petroleum resin the amount, based on the petroleum resin, can be varied. . 8. Printing ink according to claim 1, 'characterized ^ that the adduct of x, /? - unsaturated dicarboxylic acid and petroleum resin and the reactive metal compound reacted in the presence of an aliphatic, polyhydric alcohol will. 9. Printing ink according to claim 1, characterized by a viscosity of the binder of 30 up to 15OcP at 25 ° C. 10. Printing ink according to claim 1, characterized by a mixing ratio of binder and pigment from 60 to 97: 3 to 40 parts by weight. 11. Printing ink according to claim 1, characterized in that a reinforcing one to improve the flexibility and abrasion resistance Filler such as B. ethyl cellulose is added.