FR2488613A1 - INK COMPOSITION FOR REPORT PRINTING - Google Patents

Abstract

THE INK COMPOSITION OF THE INVENTION CONTAINS A RESINOUS VEHICLE III PREPARED BY REACTION OF 5 TO 100 PARTS BY WEIGHT OF A PHENOLIC RESIN (COMPONENT D) WITH 100 PARTS BY WEIGHT OF AN ACID-MODIFIED II MODIFIED RESIN, SAID. PHENOLIC RESIN (COMPONENT D) BEING PREPARED BY CONDENSATION OF A PHENOL CONTAINING AN ALKYL SUBSTITUTE IN CC WITH FORMALDEHYDE, THE SAID MODIFIED RESIN II MODIFIED BY AN ACID BEING PREPARED BY REACTION OF 1 TO 15 PARTS BY WEIGHT OF A CHOSEN COMPONENT C UNSATURATED CARBOXYLIC ACIDS, ANHYDRIDES OF UNSATURATED CARBOXYLIC ACIDS AND THEIR MIXTURES WITH 100 PARTS BY WEIGHT OF RESIN I OBTAINED BY COPOLYMERIZATION OF 5 TO 100 PARTS BY WEIGHT OF COMPONENT B CHOSEN FROM RIGHT CHAIN A-OLEFINS, SICCATIVE OILS, FATTY ACIDS AND THEIR MIXTURES WITH 100 PARTS BY WEIGHT OF A 5-CHAIN CYCLIC COMPOUND (COMPONENT A) HAVING ONE OR DOUBLE CONJUGATE BONDS AND REPRESENTED BY THE GENERAL FORMULA (CF DRAWING DA) NS BOPI) IN WHICH H IS HYDROGEN, R IS AN ALKYL GROUP IN CC, N AND M ARE EACH ZERO OR A WHOLE NUMBER AT LEAST EQUAL TO 1 AND SATISFY THE RELATION MN6, ANDOR ONE OF ITS PRODUCTS OF ADDITION OF DIELS-ALDER.

Description

The present invention relates to an ink composition

  for offset printing or offset printing.

  [0002] Printed printing methods generally have been used extensively in relief printing processes, photographic printing methods including an offset printing process, and gravure printing methods. In the offset printing process, the inked image is transferred once from a printing cylinder to a rubber blanket and then printed on a sheet of paper. The printing cylinder has a surface composed of hydrophilic portions (non-image portions) containing water and repelling the oily ink and ink retaining portions (image portions) containing oily ink and repelling the ink. 'water. The most widely used offset printing inks are

  resins containing resins, such as resins of alkyl-

  phenol, rosin-modified phenolic resins or

  maleic acid resins, which are dissolved in sicca-

  such as linseed oil. Rosin-modified phenolic resins are the most widely used resins. Although a vehicle for printing ink composed of a rosin-modified phenolic resin, a solvent and / or a drying oil is of excellent quality, it has the disadvantage that it is expensive and

  contains rosin, a substance of natural origin and

  unstable. Instead of the rosin-modified phenolic resin, it has been proposed to use resins known as petroleum resins synthesized by polymerization of petroleum cracking fractions obtained as petroleum by-products or petrochemical industries. Although these petroleum resins have the advantage that their supply and cost are stable, their qualities are not satisfactory when used as

  resinous vehicles for printing inks.

  The main properties, i.e. the ionability, required for the printing ink, particularly an offset printing ink, are the

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  (2) A good balance should be maintained at the interface between the hydrophilic portion and the ink-holding portion so as to form an image on a plane on which water and ink come into contact with each other. 'other.

  (3) A pigment must be uniformly dispersed in the ink.

  (4) The printed side has a beautiful gloss and can be obtained

uniform printed materials.

  (5) The time required for curing or drying

  is short and the ink does not show a "hang".

  (6) The printed side is resistant to friction.

  To prepare an offset printing ink which satisfies the properties mentioned above, the resin used in this ink must satisfy the following conditions: (1) It must have a high softening point,

  but do not have a high molecular weight.

  (2) It must have a polar group to improve the dispersibility of a pigment, i.e. it must have a polar group having good

affinity with a pigment.

  (3) It must be easily soluble in a hydrocarbon solvent having a high boiling point and

  containing a small amount of aromatic compound.

  (4) It must have sufficient solubility in a

  drying oil, such as linseed oil.

  In particular, with the development of printing technology in recent years, it is necessary to increase the printing speed. To meet this need, the rotocalcographic printing process is increasingly used. In the rotocalcographic process where the ink is heated to dryness, it is strongly desired to use a hydrocarbon solvent of high boiling point, such as a paraffinic solvent, which contains a

  aromatic compound in as small a quantity as possible, preferably

  There is no need for an aromatic compound to improve the environment in the workplace and to exclude the problem of pollution caused by waste gases. However, there has not been developed so far offset printing ink having satisfactory printability as described above. As a result, there is a growing demand for offset printing ink having an aptitude

satisfactory to print.

  It is already known from US Pat. No. 3,084,147 that a resin soluble in a hydrocarbon solvent such as benzene, toluene, xylene, cyclohexane or isooctane can be prepared by thermal polymerization of cyclopentadiene. at

  high temperature of 250 to 350C in the presence of a hydrocarbon solvent

  inert beer, such as benzene, toluene, xylene or isooctane. The dicyclopentadiene resin prepared by this known process is soluble in a solvent containing benzene, toluene, xylene, the solvent naphtha and the solvent sold by the Applicant under the name of solvent No. 5. However, as this resin dicyclopentadiene n There is no polar grouping, it can not be used for various uses because of its miscibility and poor adhesion property with other materials. An ink prepared by addition of various solvents and pigments to the aforementioned resin can not be used as an offset printing ink since the dispersibility of the pigments in the ink is unsatisfactory.

  and leads to an irregular printed face having a bad gloss.

  In another proposal made by the publica-

  Japanese Provisional Patent No. 24405/1972, an ester is added

  acrylic acid or maleic anhydride to said dicyclopenta resin

  diene and then hydrolyzed to prepare a carboxylic acid-containing resin, which is then reacted with a polyalcohol and a higher unsaturated carboxylic acid to produce a resin for

  printing inks. However, the resin prepared according to this proposal

  and having a high softening point to give an offset printing ink which cures and dries in a time substantially equal to that required for curing and drying conventional offset printing inks has poor solubility in a hydrocarbon solvent derived from petroleum which is used as a solvent for the offset printing ink. As a result, the fluidity of the ink thus prepared is poor and the gloss of the ink becomes extremely poor. Another disadvantage of this resin is that it forms gels in the step of preparing a varnish, giving a hazy varnish having a poor shade. In contrast, the softening point of this resin should be lowered to improve solubility in solvents, resulting in an extension of the time required for curing and drying. For the reasons mentioned above, the resin prepared according to this suggestion can not be used in an offset printing ink for

practical use.

  U.S. Patent No. 2,608,550 discloses

  a resin prepared by thermal copolymerization of dicyclopenta

  diene and maleic anhydride. However, the resin according to this patent having a relatively low maleic acid content generally has the drawback of a high softening point and a poor dispersibility of the pigments and poor miscibility with other filler materials. If the maleic anhydride content is increased to eliminate the aforementioned drawbacks, there is a tendency to stain and gel and the

  resulting resin acquires poor weathering properties.

  U.S. Patent No. 2,608,550 also discloses an alkyd resin produced from a so-called alkyd composition containing a polyacid component consisting of

  in a resin prepared by thermal polymerization of dicyclopenta

  diene with maleic anhydride. However, the alkyd resins of this prior patent generally have high molecular weights, poor solubilities in high boiling hydrocarbon solvents for printing inks and drying oils. As a result, a printing ink prepared from any of these alkyd resins has poor flowability, a lower gloss of the printed materials, and tends to disperse from the fog-like impression cylinder. staining the papers, causing a serious fog problem. For these reasons, the alkyd resins of this patent can not be

  applied for practical use.

  Although a drying oil, such as linseed oil, has been used in conventional offset printing ink, there is a tendency to reduce the amount used when increasing the printing speed to eliminate problems. stains in the bottom zone caused by the use of a drying oil

  and to compensate for fog production and retardation

  ment. The conventional offset printing ink varnish comprises a high boiling hydrocarbon solvent, an oily component such as a drying oil and a resinous binder. Conventional binders for this purpose have been used, for example, alkylphenol resins, rosin-modified phenolic resins and maleic acid resins. However, a varnish composition containing a reduced amount of a drying oil does not yield glossy and beautiful printed materials, even when added

  any of the known resinous binders.

  In addition, any of the known resins have a solubility in paraffins far from being satisfactory, so that they are almost unusable as resinous binders in the

  Offset printing inks in dissolving paraffinic solvents

picnics.

  The subject of the invention is an ink composition for printing

  offset printing which yields uniform printed matter with

  printed surfaces of a beautiful gloss.

  The invention also relates to an offset printing ink composition which hardens and dries for a short period of time.

and does not present a blockage.

  The invention also relates to an offset printing ink composition having improved emulsification properties

  and not causing a fog problem.

  The invention also relates to an ink composition

  for offset printing having an appropriate fluidity.

  The invention also relates to an ink composition for offset printing having an excellent balance at the interface

  between the hydrophilic portions and the ink retaining portions.

  The invention also relates to an ink composition for offset printing that does not form a gel or haze in the step of preparing a varnish to give an ink varnish

having a good hue.

  The invention also relates to an offset printing ink composition containing a resinous vehicle which has a

  good solubility in a hydrocarbon solvent of high boiling point

  for the ink and in a drying oil.

  The invention also relates to an offset printing ink composition containing a resinous vehicle which is soluble in a paraffinic solvent and which has excellent printability. The invention also relates to an offset printing ink composition containing a resinous vehicle which gives excellent printability, even with the addition of a quantity

  relatively low of a drying oil.

  The invention will be better understood on reading the

description that will follow.

  More specifically, the offset printing ink composition according to the invention contains a resinous carrier (III) prepared by reacting 5 to 100 parts by weight of a phenolic resin (component D) with 100 parts by weight of a an acid modified resin (II), said phenolic resin (component D) being prepared by condensing a phenol containing a C 4 -C 9 alkyl substituent with formaldehyde, said acid modified resin (II) being prepared by reaction of 1 to 15 parts by weight of a component C selected from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and mixtures thereof with 100 parts by weight of a resin (1) obtained by copolymerization of 5 to 100 parts by weight of a compound B selected from straight-chain α-olefins, drying oils, fatty acids and mixtures thereof with 100 parts by weight of a 5-membered cyclic compound (component A) having a e or conjugated double bonds and represented by the general formula R n wherein H is hydrogen, R is a C 1 -C 3 alkyl group, m and n are each zero or an integer at least 1 and satisfy the relation m + n = 6,

  and / or one of its Diels-Alder adducts.

  The invention is now described in more detail. In the composition according to the invention, there is used as component (A) a 5-membered ring compound having one or more conjugated double bonds and / or its Diels-Alder adduct represented by the general formula n wherein H is hydrogen, R is a C 1 -C 3 alkyl group, m and n are each zero or an integer of at least 1 and

satisfy the relation m + n = 6.

  Examples of cyclic cyclon compounds which can preferably be used on an industrial scale are cyclopentadiene and methylcyclopentadiene, and as examples of preferred Diels-Alder adducts. , we will quote

  dicyclopentadiene, the cyclopentadiene-methylcyclopenta codimer

  diene and tricyclopentadiene. It is also possible to use

  mixtures of the above compounds. Of these, cyclopentadiene, dicyclopentadiene and mixtures thereof are particularly preferred. It is not essential that the purity of component (A) be high. However, it is preferred that the starting material contains wt% or more of cyclopentadiene, dicyclopentadiene or a derivative thereof. For example, it may be possible to use

  a concentrated fraction obtained by thermal dimerization of the cyclo-

  pentadiene and / or methylcyclopentadiene contained in a C5 fraction produced by cracking naphtha at elevated temperature to obtain a mixture of dicyclopentadiene, dimethylcyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, cyclopentadiene-disoprene codimer and cyclopentadiene-piperylene codimer, followed by removal of the most of the fractions in C5 such

  C5 -olefins and C5 paraffins by distillation.

  In addition, component (A) may contain an additional unsaturated compound, particularly an unsaturated aromatic compound in a smaller amount than the 5-membered ring compound and / or its Diels-Alder adduct. For example, we can

  use as additional unsaturated compound styrene, α-methyl-

  styrene, vinyltoluene, indene, methylindene and mixtures thereof, and the so-called C9 fraction is preferred from the industrial point of view

  obtained as a by-product of cracking naphtha and the like.

  The component (B) used in the invention is selected from straight-chain α-olefins, drying oils, acids and the like.

fat and their mixtures.

  Preferred straight chain α-olefins are those

  C4-C40, more particularly C6-C20.

  The pure commercial products can, of course, be used as straight chain α-olefins. However, from the industrial point of view, it is recommended to use mixed α-olefins prepared (1) by oligomerization of ethylene or (2) by cracking

thermal paraffin waxes.

  By oligomerization of ethylene as indicated in (1) above, straight chain α-olefins having even numbers of carbon atoms of high purity are separated and the separated product does not contain other isomers. By thermal cracking of the paraffin waxes as indicated in (2) above, α-olefins with a purity of about 90% are produced, the remainder being branched chain olefins, diolefins and naphthene. and the product can

  be used as without inconvenience in the process of the invention.

  More particular examples of α-olefins include 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, eicosene and mixtures thereof. An olefin blend produced by the process described in (1) above is sold by Mitsubishi Kasei Co., Ltd. under the name "Dialene" and a product obtained by the process

  under (2) above is sold by Shevron Corp.

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  ration under the name "Shevron α-olefin". A mixture of two or more of the α-olefins described above may be used as component (B). The drying oils which can be used in the invention as components (B) include vegetable and animal oils and fats having iodine numbers of not less than 120; drying vegetable oils such as linseed oil, tung oil, soybean oil and castor oil are particularly preferred.

  dehydrated. The boiled oils obtained in

  placing the drying oils mentioned above in a heat treatment. The fatty acids that can be used as components (B) in the invention include saturated or unsaturated synthetic fatty acids, such as myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid, and fatty acids of the present invention. 'natural origins', such as the fatty acids of

  flaxseed oil and tall oil fatty acids. Tall oil mainly

  also composed of fatty acids can also be used as

component (B) according to the invention.

  Component (B) may be a mixture of two

  or more of the above-mentioned compounds.

  In the invention, the resin (I) is prepared by reacting 100 parts by weight of the component (A) with 5 to 100 parts by weight, preferably 5 to 50 parts, of the component (B) in the presence or in the absence of a catalyst. When the reaction is carried out in the absence of catalyst, the mixture of said components (A) and (B) is heated at 200-300 ° C for 30 minutes to 15 hours, preferably 1 to 7 hours. to prepare a resin (I). When using a catalyst, a Friedel-Crafts catalyst, such as boron trifluoride, its complexes with phenol, ether or acetic acid or aluminum chloride, is added to the monomer mixture in an amount from 0.1 to 10% by weight, preferably from 0.3 to 2% by weight, relative to the total weight of the monomers, and the mixture is reacted at a reaction temperature of -30 to 100.degree. preferably from 0 to 500C, for a period of 10 min to 20 h, preferably 1 to 15 h.

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  To obtain a final binder or resinous vehicle having

  a particularly excellent solubility in a paraffinic solvent

  nique, one incorporates in the component (B) any of the α-olefins mentioned above to occupy at least a portion of the latter. By adding a α-olefin as component (B), the solubility of the final binder or resinous vehicle in a paraffinic solvent is remarkably improved, which also improves

  the printability of the printing ink containing the resin.

  If the amount of component (B) used in the preparation

  When the resin (I) of the invention is below the range mentioned above, the advantageous effect obtained by its addition does not reach a satisfactory degree. On the contrary, if the amount of the component (B) exceeds the defined range, the yield of the resin is considerably reduced and the softening point of the resin

is lowered.

  According to the invention, the resin (I) prepared as mentioned above is reacted with the component (C) chosen from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and mixtures thereof. Preferred examples of the unsaturated carboxylic acids and anhydrides which can be used according to the invention include the unsaturated mono- and polycarboxylic acids and their anhydrides having generally from 3 to 32, preferably from 3 to 15 carbon atoms, for example acid acrylic,

  methacrylic acid, maleic acid, maleic anhydride, tetra-

  hydrophobic and its anhydride, fumaric acid, citraconic acid, itaconic acid and fatty acids drying oils, such as

  fatty acids of linseed oil and mixtures thereof. In particular,

  include maleic acid and maleic anhydride.

  The proportion of the unsaturated carboxylic acid or its

  anhydride added to the resin (I) is 1 to 15 parts, preferably

  1 to 10 parts by weight, per 100 parts by weight of the resin (I).

  If the amount of unsaturated carboxylic acid or its anhydride is less than the range mentioned above, the resin formed is little improved as a resin having polar groups due to the absence of polar groups. When this resin is used as a resin carrier for the printing ink, the dispersibility of the pigments, the fluidity of the ink and its printability

are not satisfactory.

  On the contrary, if the amount of unsaturated carboxylic acid or its anhydride is above the defined range, the content of polar groups in the resulting resin becomes too high, leading to poor solubility in the solvent and the disadvantage of a tendency of the resin to change color or

  to gel. When using this resin in a printer ink,

  However, the solubility of the resin in a hydrocarbon solvent in the step of preparing an ink varnish becomes poor and alters the fluidity of the ink and the gloss of the printed material. The above-mentioned reaction for modifying the resin with an acid can be carried out at a temperature of 100 to 3000C, preferably 150 to 2500C, in the presence of a radical reaction initiator, such as an organic peroxide, for 30 minutes. 15 h, preferably 1 to 8 h. If an unsaturated polycarboxylic acid or its anhydride is used, it is preferred to carry out the reaction without a catalyst. If an unsaturated monocarboxylic acid or its anhydride is used,

  It is preferred to carry out the reaction in the presence of a catalyst.

  The resin modified according to the invention and modified with an acid may be produced by the process in one of the following stages: An unsaturated carboxylic acid or its

  anhydride at the initial or intermediate stage of the polymerization step

  mixture of components (A) and (B) and polymerizes

  the mixture at a temperature of 200 to 300 ° C in the presence or in the

the absence of solvent.

  According to the invention, the modified acid modified resin (II) can be esterified with an alcohol to control the solubility and softening point of the resulting resin (II) or to adjust the molecular weight of the resinous vehicle (III). The alcohols used for this purpose include mono- and polyalcohols. Particularly preferred are monoalcohols of not less than C6, preferably C to C18, for improving the solubility of the final binder or resinous vehicle (III). The amount of the alcohol should be such that the molar ratio of the carboxylic groups to the alcohol groups in the modified resin (II) is in the range of 1: 0-1.0 and the molar ratio of the carboxylic acids to the alcohol groups contained in the modified resin (II) is in the range of 1: 0 to 2.0. Esterification may be carried out first by heating to melt the acid modified resin (II) or dissolve it in a hydrocarbon solvent, such as benzene, toluene or xylene, followed by the addition of an alcohol and reaction to 150-2500C for 30 minutes to 10 hours, preferably 1 to 15 hours. According to the invention, the modified acid modified resin (II) reacts with an alkylsulphonated phenolic resin (component D) to obtain the binder or resinous vehicle (III)

  research. The phenolic resins used according to the invention

  take the condensation products of phenols containing C 4 -C 4 alkyl groups with formaldehyde. Particular examples of phenols which are industrially preferred include ptert-butylphenol, sec-butylphenol, p-tert-octylphenol and nonylphenol. Phenolic resins prepared from phenols

  having no substituents or from cresols are not preferred.

  because the solubility of the binders or resinous

  in high-boiling hydrocarbon solvents are poor. If a phenolic resin prepared from formaldehyde and a phenol containing a group of not less than GC- is used, the softening point of the resulting binder or resinous vehicle is extremely lowered to a level unsuitable for the ink. printing. Instead of reacting the modified resin (II) with a phenolic resin, formaldehyde and a phenol can be reacted in the presence of the modified resin (II) using an alkaline or acid catalyst or without catalyst to obtain the binder or vehicle

  researched softwood modified with a phenolic resin.

  5 to 100 parts, preferably 10 parts, by weight of the modifying phenolic resin can be added to 100 parts by weight of the modified acid modified resin (II). If the amount of the phenolic resin is below the aforementioned range, the printing ink produced using the resulting resinous vehicle does not have a satisfactory fluidity and does not

  can not give printed materials having a satisfactory gloss.

  On the contrary, if the amount of the phenolic resin exceeds the above mentioned range, the solubility of the resulting resinous vehicle in a solvent of the printing ink becomes bad.

and the cost price is increased.

  The resin (II) can be modified with a phenolic resin simply by mixing the resin (II) with the phenolic resin to obtain a mixture which is melted and heated at 150 ° C to 250 ° C for 30 min. 10 h, preferably 1 to 5 h. If necessary, an acid catalyst, such as oxalic acid, toluenesulfonic acid, or a Friedel-Crafts catalyst, or a catalyst can be used.

  alkali, such as a metal oxide or metal hydroxide or ammonia

  niac. It is desirable that the binder or resinous vehicle (III) has a softening point of at least 1000C, preferably greater than 130 ° C. If the softening point of the resinous vehicle (III) is less than 100 ° C, the printing ink prepared therefrom has fogging and blockage problems and the

  Drying speed of the printing ink is extremely lowered.

  It is desirable that the acid number of the resinous vehicle (III) be from 5 to 50, preferably from 5 to 20. If the acid number of the resin (III) is below the above-mentioned range, the printing ink prepared therefrom has poor solubility. On the contrary, if the acid number of the resin (III) exceeds the aforementioned range, its solubility in a paraffinic solvent becomes poor and the offset printing ink

  prepared from it has poor resistance to emulsification.

  cation. The offset printing ink according to the invention can be prepared using the acid-modified resin vehicle (III).

  and a phenolic resin as described above according to a known method.

  For example, 100 parts by weight of the resinous vehicle (III) are dissolved at room temperature or by heating in a mixture of

  to 200 parts by weight of a hydrocarbon solvent having a boiling point

  high level and 0 to 150 parts, preferably 5 to 50 parts,

  the weight of a drying oil to prepare a varnish having a viscosity

  20 to 60 Pa.s (200 to 600 poises) at room temperature.

  An ink composition according to the invention can be obtained by adding one or more pigments to the varnish and kneading using

rolls or other kneaders.

  The hydrocarbon solvents of high boiling point which can be used according to the invention must have boiling points of between 200 and 350 ° C., preferably of 250 ° C. to 350 ° C., and their content of aromatic compounds must not be greater than at

  % by weight, preferably less than 30% by weight.

  Particularly preferred solvents according to the invention are high-boiling paraffinic solvents having

  boiling points between 200 and 350 C and not containing sensi-

  no aromatic compound. As oil components, long-chain alkyd resins can be used in oils other than

  drying oils including linseed oil and tung oil.

  The following examples illustrate the invention without however

limit the scope.

EXAMPLE OF SYNTHESIS 1

  820 g of 97% dicyclopentadiene and 180 g of 1-hexene are charged to an autoclave with a capacity of 2 liters and heated at 260 ° C. for 5 hours in a nitrogen atmosphere with stirring. The autoclave is cooled when heating is complete and the contents of the autoclave are distilled at 210 ° C / 2,969 mbar (2 mm Hg) to separate the unreacted products and the oligomers. 893 g of a resin (I-1) remain in the autoclave. The softening point of the resin (I-1)

is 139.0 C.

  100 g of the resin (II) are heated to 200 ° C. in order to melt it and 3.0 g of maleic anhydride are added and the mixture is reacted for 4 hours with stirring to obtain a modified resin (II-1) modified with maleic anhydride. The softening point of the modified resin (II-1) is 151.0 C and its acid number is 13.7. Then, to 85 g of the modified resin (II-1), 15 g

  of a resol type phenolic resin which has been prepared by condensation

  between p-tert-octylphenol and formaldehyde, and reacted at 200 ° C. for 2 hours, to obtain a resinous vehicle (III-1) having a softening point of 173.5 ° C. and an acid number of 13.0.

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EXAMPLE OF SYNTHESIS 2

  760 g of 97% dicyclopentadiene and 240 g of 1-decene are charged to an autoclave with a capacity of 2 liters and

  react at 280 C for 5 h. The following operating modes are -

  similar to those of Synthesis Example 1 and 930 g of a resin (I-2) are obtained. The softening point of the resin (I-2)

is 137.00C.

  100 g of the resin (I-2) are heated to 200 ° C. in order to melt it and 5.0 g of maleic anhydride are added and the mixture is reacted.

  stirring for 3 hours to obtain modified modified resin (II-2)

  maleic anhydride. The softening point of the resin

  modified (II-2) is 152.0 C, and its acid number is 24.3.

  Then, to 82 g of the modified resin (II-2), 3.0 g of decanol are added and heated at 200 ° C. for 1 h and then 21 g of resol type phenolic resin which has been prepared are added. by condensation between pnonylphenol and formaldehyde. The mixture is reacted at 200 ° C. for 3 hours to obtain a resinous vehicle (III-2) having

  a softening point of 165.5 C and an acid number of 19.6.

EXAMPLE OF SYNTHESIS 3

  790 g of 97% dicyclopentadiene and 210 g of a mixture of C6-C10 aolefins ("Dialene 610" from Mitsubishi Kasei Co., Ltd) are charged to a 2-liter autoclave and reacted. at 280 C for 2 h 30 min. The following procedures are similar to those of Synthesis Example 1 and 920 g are obtained.

  a resin (I-3) having a softening point of 143.0 C.

  100 g of the resin (I-3) is heated to 2000C to melt, 3.0 g of maleic anhydride is added and reacted for 4 hours with stirring to obtain a modified resin (II-3). The softening point of the modified resin (II-3) is 155.0 ° C, and its acid number is 13.9. Then, to 85 g of the modified resin (11-3) is added 15 g of a resol type phenolic resin which has been prepared by condensation of p-tert-butylphenol and formaldehyde,

  and reacted at 2200C for 2 hours to obtain a residence vehicle.

  (III-3) having a softening point of 183.50C and an index

of acid of 13.1.

EXAMPLE OF SYNTHESIS 4

  The fraction of sub-

  C5 products (boiling point 28-60 C) obtained in the step of producing ethylene and propylene by cracking the naphtha vapor, to separate the unreacted C5 fraction to obtain a mixture containing 85% of dicyclopentadiene and the remainder of codimers of cyclopentadiene with isoprene or piperylene. 850 g of this mixture containing 85% of dicyclopentadiene and 150 g of 1-decene are charged into a 2 liter autoclave and reacted at 260 ° C. for 6 hours. The following procedures are similar to those of Synthesis Example 1 and 840 g of a resin (I-4) having a dot are obtained.

softening of 135 C.

  100 g of the resin (I-4) are heated to 200 ° C. in order to melt it, 4.0 g of maleic anhydride are added and the mixture is reacted for 4 hours with stirring to obtain a modified modified resin (II-4). by maleic anhydride. The softening point of the modified resin (II-4) is 144.5 C and its acid number is 17.7. Then, 3.0 g of ethylhexanol was added to 90 g of the modified resin (II-4) and heated with stirring at 200 ° C. for 1 hour. 16.4 g are then added

  of a resol type phenolic resin which has been prepared by condensation

  of p-tert-octylphenol and formaldehyde and reacted at 2000C for 3 h to obtain a resinous vehicle (III-4) having a

  softening point 158.5 C and an acid value of 16.0.

EXAMPLE OF COMPARATIVE SYNTHESIS 1

  1000 g of 97% dicyclopentadiene and 400 g of xylene as solvent are charged to an autoclave having a capacity of 2 liters and reacted at 260 ° C. for 2 hours. Subsequent procedures are similar to those of Synthesis Example 1 and 820 g of a resin (I-a) having a softening point of

150 C.

  100 g of the resin (I-a) are heated to 200 ° C. in order to melt it, 3.0 g of maleic anhydride are added and the mixture is reacted during

  4 h to obtain a modified resin (II-a). The softening point

  The amount of the modified resin (II-a) is 159.5 ° C and its acid number is 13.0. Then, to 85 g of the modified resin (II-a), a resol type phenolic resin prepared by reaction of p-tertoctylphenol with formaldehyde is added and reacted at 200 ° C. for 2 hours to obtain a vehicle. softwood (III-a) having a point

  softening of 176.5 C and an acid number of 12.7.

EXAMPLE OF COMPARATIVE SYNTHESIS 2

  100 g of the resin (I-1) obtained in Synthesis Example 1 are heated to 200 ° C. in order to melt it and 25 g of

  phenolic resin of the resol type prepared by condensation of p-tert-

  octylphenol with formaldehyde. The mixture is heated and stirred at 200 ° C. for 2 hours to obtain a resin (III-b) having a point

of softening 169.0 C.

EXAMPLE OF COMPARATIVE SYNTHESIS 3

  800 g of 97% dicyclopentadiene and 200 g of 2,4-dimethyl-1-heptene having a methyl side-chain group are loaded onto a double-bonded portion, obtained by trimerization of propylene, in an autoclave with a capacity of 2 liters. and reacted at 280 ° C. for 5 hours. The contents of the autoclave are distilled at 210 ° C / 2 mmHg to remove the unreacted products and the oligomers. After distillation, 780 g of a resin (I-c) remain in the autoclave. The

  softening point of the resin (I-c) is 145 C.

  100 g of the resin (I-c) are heated to 200 ° C. in order to melt it, 3.0 g of maleic anhydride are added and the mixture is reacted for

  4 h to obtain a modified resin (II-c). The softening point

  The amount of the modified resin (II-c) is 158.0 C and its acid number is 14.0. Then, to 85 g of the modified resin (II-c) is added g of a resol type phenolic resin prepared by condensation of p-tertoctylphenol with formaldehyde and reacted for 2 hours at 200 C to obtain a vehicle softwood (III-c) having a point

  softening point of 178.0 C and an acid value of 13.0.

  Varnishes are prepared using the resinous (III-1) to (III4) and (III-a) a (III-c) vehicles obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 3 and also using the modified resin (II-1) obtained in Synthesis Example 1 and a control resin. Inks are prepared using these varnishes and the properties of the inks are determined. The results

  tests are shown in Table I below.

PREPARATION OF VARNISH

  - To 50 g of each of the resinous vehicles, 10 g of linseed oil and 20 to 40 g of a high-boiling paraffinic solvent (solvent NISSEKI n OH, see note 1 below) are added and heat to 180 C to melt the resin and

  prepare a varnish with a viscosity of 30-40 Pa.s (300-400 poises).

PREPARATION OF INK

  By using each of the varnishes, an ink is prepared

  according to the following formula using a three-roll mixer.

INK FORMULA

  Pigment (carmine 6B: see note 2 below) 14 g Varnish 50 g Solvent (solvent NISSEKI n O-H) 15 g

  DETERMINATION OF THE PROPERTIES OF INK AND RESULTS OBTAINED

  Brilliant: 0.4 ml of each ink is applied to an art paper using the "RI Tester" (note 3 below) and

  dry for 10 seconds in an oven maintained at 150 ° C.

  mine the gloss by means of a measuring device

brilliant at 60-60.

  Drying time: 0.4 ml of each ink is applied to a parchment paper using the above-mentioned "RI Tester" and dried in an oven at 150 ° C. The time which elapses is measured. that the ink has reached the state at which

the ink does not stick to the finger anymore.

* Fog formation: 2.4 ml of each ink is placed in the "Inkometer" apparatus (note 4 below) rotating at 1200 rpm. We observe the dispersion of the ink on the

2,488,613

  art paper spread below the cylinder after an interval of 3 min. Ability to emulsify ink: Add water to each

  inks prepared to emulsify the ink and

  undermines the fluidity of the emulsified ink. Inks

  Offset printing is usually partially emulsified

  when they come into contact with water in the printing step. Only inks that give emulsions with good fluidity can be applied

for practical uses.

  Note 1 NISSEKI solvent No. O-H, paraffinic hydrocarbon solvent

  with a boiling range of 250-2650C and no aromatic compound, produced by

the plaintiff company.

  Note 2 Carmine 6B, manufactured by the Toyo Ink Mfg. Co., Ltd. Note 3 Apparatus for the determination of printability, manufactured by Akira Seisakusho Co., Ltd. Note 4 Apparatus manufactured by Toyo Seiki Co., Ltd. As shown in Examples 1 to 4 in Table I below, the offset printing ink compositions according to the invention have excellent gloss and excellent emulsification, fogging and drying properties. It is understood from Table I that softwood vehicles

  the invention, dissolved in a paraffinic solvent, give excellent

  slow offset printing ink compositions.

  As can be seen from Comparative Example 1, a uniform ink composition can not be prepared from a resinous vehicle that does not contain an α-olefin, since

  Solubility of this resin in a solvent is poor.

  Comparative Example 2 illustrates an ink composition prepared using a resin which has not been modified by an acid, and shows that the drying and emulsification properties of this ink are lower since the modification reaction with a phenolic resin is incomplete and gives a resin

  whose softening point is too weak.

  In Comparative Example 3, a resin which has not been modified by a phenolic resin is used. This comparative example shows that this resin can not be used to prepare a

  ink for practical application, since the ink does not have

  satisfactory gloss properties, drying time and emulsification. In Comparative Example 4, an ink is prepared using a rosin-modified phenolic resin which has excellent solubility in a paraffinic solvent. When comparing this comparative example with the examples of the invention, it should be noted that the emulsification ability of the offset printing ink compositions according to the invention is improved with respect to the ink composition. classic prepared using a resin

  phenolic modified with rosin.

  The resinous vehicle used in Comparative Example 5 was prepared using 2,4-dimethyl-1-heptene having a side chain on a double bond portion as α-olefin. As will be understood from this comparative example, a compound having a side chain on a double bond portion is relatively inactive and difficult to introduce into the resin. It follows that the solubility of the resulting resin in a paraffinic solvent is unsatisfactory and makes it difficult to prepare a clear varnish. We also see that the gloss of the printed side

is not satisfactory.

EXAMPLE OF SYNTHESIS 5

  850 g of 97% dicyclopentadiene and 250 g of linseed oil are charged in a 2 liter autoclave and heated at 260 ° C. for 3 h 30 min in a nitrogen atmosphere with stirring. The autoclave is cooled

  when the heating is finished and we distil the contents of the

  clave at 2100C / 2.7 mbar (2 mm Hg) to remove unreacted products and oligomers. It remains in the autoclave 920 g of a

  resin (1-5) with a softening point of 136.5 ° C.

  150 g of the resin (I-5) are heated to 200 ° C. in order to melt it, 4.5 g of maleic anhydride are added and the mixture is reacted for 4 hours with stirring to obtain a modified resin (II-5) modified with

248 8,613

  maleic anhydride. The softening point of the modified resin (II-5) is 147.0 C and its acid number is 13.5. Then, to 100 g of the modified resin (II-5), 17.6 g of a resin are added

  phenol of the resol type prepared by condensation of p-tert-octyl-

  phenol with formaldehyde, and reacted at 200 ° C. for 2 h

  to obtain a resinous vehicle (III-5) having a softening point

  169.5 C and an acid value of 12.7.

EXAMPLE OF SYNTHESIS 6

  800 g of 97% dicyclopentadiene and 200 g of tall

  in a 2 liter autoclave and reacted at 260 ° C. for 6 hours. Subsequent procedures are similar to those of Synthesis Example 5 and 925 g of a (I-6) resin of

softening point of 138.5 C.

  150 g of the resin (I-6) are heated to 200 ° C. to melt, 7.5 g of maleic anhydride are added and the mixture is reacted for 3 hours with stirring to obtain a modified modified resin (II-6). by maleic anhydride having a softening point of 158.0 C and an acid value of 24.2. Then, to 100 g of the modified resin (II-6), 4.2 g of decanol are added and heated with stirring at 200 ° C. for 1 h. 20.2 g of a resol type phenolic resin prepared by condensation of p-nonylphenol with formaldehyde are then added and reacted at 200 ° C. for 3 hours to obtain a resinous vehicle (III-6) having a softening point. 160.5 C and an index

of acid of 19.4.

EXAMPLE OF SYNTHESIS 7

  800 g of 97% dicyclopentadiene, 100 g of linseed oil and 100 g of 1-hexene are charged to a 2 liter autoclave and reacted at 280 ° C for 2 hours. The following procedures are similar to those of Synthesis Example 5 and 932 g are obtained.

  a resin (I-7) having a softening point of 146.0 C.

  150 g of the resin (I-7) are heated to 200 ° C. in order to melt it, 4.5 g of maleic anhydride are added and the mixture is reacted for 3 hours with stirring to obtain a modified modified resin (II-7). with maleic anhydride, having a softening point of 155.0 C and an acid number of 13.7. Then, to 100 g of the modified resin (II-7), 17.6 g of a resol type phenolic resin prepared by condensation between p-tert-octylphenol and formaldehyde are added and the reaction mixture is reacted at 200 ° C. for 2 hours. 2 h to obtain a resinous vehicle (III-7) having a softening point of 175.0 C and a hint

of acid of 12.2.

EXAMPLE OF SYNTHESIS 8

  The fraction of C5 by-products (boiling range 28-60 ° C.) obtained in the step of producing ethylene and propylene by steam cracking of the naphtha is heated at 120 ° C. for 4 hours and distilled to give remove the unreacted C5 fraction, to obtain a mixture containing 85% of dicyclopentadiene and the remainder of codimers of cyclopentadiene and isoprene or of

  piperylene. 850 g of this mixture containing 85% dicyclo

  pentadiene and 250 g of linseed oil in a 2 liter autoclave and reacted at 260 ° C. for 4 hours. The following procedures are similar to those of Synthesis Example 5 and 872 g are obtained

  a resin (I-8) having a softening point of 137.0 C.

  150 g of the resin (I-8) are heated to 200 ° C. in order to melt it, 5.3 g of maleic anhydride are added and the mixture is reacted for 4 hours with stirring to obtain a modified resin (II-8) having a point

  softening of 148.5 ° C and an acid number of 16.9.

  Then, to 100 g of the modified resin (II-8), 3.0 g of 2-ethylhexanol are added and heated with stirring at 2000C for 2 hours.

  18.2 g of a pre-prepared phenolic resin of the resol type are then added.

  The reaction mixture was condensed between p-tert-octylphenol and formaldehyde and reacted at 200 ° C. for 2 hours to obtain a resinous vehicle (III-8) having a softening point of 157.5 ° C. and a cleavage index.

acid of 14.1.

EXAMPLE OF COMPARATIVE SYNTHESIS 4

  1000 g of 95% dicyclopentadiene and 400 g of xylene acting as a solvent are charged to a 2 liter autoclave and reacted at 260 ° C. for 3 hours. The following procedures are similar to those of Synthesis Example 5 and 800 g of a resin (I-d) having a softening point are obtained.

152.0 C.

  150 g of the resin (I-d) are heated to 200 ° C. in order to melt it, 5.3 g of maleic anhydride are added and the mixture is reacted for 3 hours with stirring to obtain a modified resin (II-d) having

  a softening point of 165.00C and an acid number of 16.5.

  Then, to 100 g of the modified resin (II-d), 3.0 g of decanol are added and heated with stirring at 200 ° C. 18.2 g of a phenol resin of the resol type prepared by condensation are then added. p-tert-octylphenol with formaldehyde and reacted at 200 ° C. for 2 hours to obtain a resinous vehicle (III-d) having a point

  softening 170.5 C and an acid number of 13.9.

EXAMPLE OF COMPARATIVE SYNTHESIS 5

  100 g of the resin (I-5) obtained in the synthesis example 5 are heated at 200 ° C. to melt it and 17.6 g of a phenolic resin of the resol type prepared by condensation between the p-tert are added. octylphenol and formaldehyde. The mixture is heated and stirred at 200 ° C. for 2 hours to obtain a resinous vehicle (III-e).

  having a softening point of 155.0 C.

  Varnishes are prepared using the resinous vehicles (III-5) to (III8) and (III-d) and (III-e) obtained in Synthetic Examples 5 to 8 and Comparative Synthesis Examples 4 and 5 and in also using the modified resin (II-5) and a control resin. Inks are prepared using these varnishes and the properties of the inks are determined. The results of the tests are indicated

in Table II below.

PREPARATION OF VARNISH

  50 g of each of the resinous vehicles are added 20 g of linseed oil and heated at 240 ° C. for 1 h 30 min. Then a suitable amount, between 20 and 40 g, of a hydrocarbon solvent derived from petroleum (solvent NISSEKI No. 5, see note 5 below) is added to adjust the viscosity of the resulting varnishes.

  in the range of 50-60 Pa.s (500-600 poises).

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PREPARATION OF INK

  By using each of the varnishes, an ink is prepared

  according to the following formula using a three-roll mixer.

INK FORMULA

  Pigment (carmine 6B, see note 2, page 18 above) 14 g Varnish 50 g Solvent (NISSEKI No. 5) 5 g Wax 2 g Siccative (cobalt naphthenate) 0.3 g

  DETERMINATION OF THE PROPERTIES OF INK AND RESULTS OBTAINED

  Gloss: 0.4 ml of each ink is applied to an art paper using the "RI Tester" apparatus (see note 3, page 19 above) and allowed to stand for 24 hours. Gloss is determined by means of a measuring device

  brilliance at 60 degrees-60 degrees.

  Fixation time: 0.4 ml of each ink is applied to a sheet

  of art paper using the "RI Tester" apparatus

  above mentioned and place another blank sheet of art paper over the sheet on the inked side

  and press it using the "RI Tester" cylinder.

  The interval of time between the instant at which the ink is applied and the instant at which the blank sheet of art paper is applied over the face is varied.

  inked to find the necessary time interval for-

  that the ink does not stick on the white sheet of art paper. Fog Formation: 2.4 ml of each ink is placed in the Inkometer apparatus (see note 4, page 19 above) rotating at 1200 rpm. The dispersion of the ink is observed on the art paper spread below the roll after an interval of 3 minutes. Drying Time: 0.4 ml of each ink is applied to an art paper sheet using the aforementioned "RI Tester" apparatus and the time required for the ink to be dried is determined. using a test device to detect the degree of drying of

  the ink (see note 6 below).

  Ink Emulsification Ability: Water is added to each of the inks prepared to emulsify the ink and the fluidity of the emulsified ink is determined. Inks

  Offset printing is usually partially emul-

  when they come into contact with water in the printing stage. Only inks that give

  emulsions with good fluidity can be applied

  for practical uses.

  Control resin: Rosin-modified phenol resin sold by Dainippon Ink & Chemical Co., Ltd. under

the name of Beckacite 1126HV.

  Note 5: Solvent for ink having a boiling range of

  276-31lC and containing 23% by weight of aromatics

  ticks, manufactured by the plaintiff Company.

  Note 6: Testing Device Produced by Toyo Seiki Co., Ltd.

  With reference to Examples 5 to 8 indicated in Table II below, it should be understood that the offset printing ink compositions according to the invention have excellent gloss and good emulsifying, fogging properties. ,

fixing and drying.

  On the other hand, an ink using a resinous vehicle which contains neither a drying oil nor a fatty acid component is unsatisfactory, because the gloss of the printed side is bad, with concomitant fog formation and in that its property of emulsification is not satisfactory as can be

  see it in Comparative Example 6 shown in the table.

  Comparative Example 7 illustrates an ink composition prepared using a resin which has not been modified by an acid, and shows that the gloss and the emulsification property of this ink are unsatisfactory and that the resin forms fog. In Comparative Example 8, a resin is used which

  has not been modified by a phenolic resin. This comparative example

  tif shows that an ink prepared using this resin does not have satisfactory properties of gloss, fixing, drying and emulsification and form of fog. In Comparative Example 9, an ink is prepared using a known control resin commonly used in the art. This known resin is a phenolic resin modified with rosin. It is understood, by comparison of the examples of the invention with the comparative example, that the gloss and the emulsification property of the offset printing ink compositions according to the invention are improved compared with those of the composition of the present invention. conventional ink prepared using known phenolic resin

modified by rosin.

  It is understood that the invention is not limited to

  preferred embodiments described above as illustrative

  and that those skilled in the art may make changes

  without departing from the scope of the invention.

TABLE I Resin Viscosity Shiny Appearance of Training Time Ability to

  of the varnish of the drying side of the emulsifi-

  (Pa.s at 25 ° C.) varnish printed ink mist Example 1 III-1 53.7 transparent 71 8 not observed good Example 2 III-2 58.1 transparent 67 6 not observed good Example 3 III-3 58 , 9 transparent 67 7 not observed good Example 4 III-4 52.8 transparent 65 6 not observed good Example III-a The solubility of the resin in a paraffinic solvent is so bad that no comparison is made of transparent varnish and ink composition can not be prepared Example III-b 55.1 becomes 41 17 observed poor comparative 2 disorder Example II-1 51.6 poor 52 12 observed poor comparative 3 hue Example resin 58.6 transparent 66 7 not observed Comparative Control 4 Control Example III-c 57.0 Unrequired 50 Concomitantly Uncontrolled 5 Disease * Control Resin: Rosin-Modified Phenolic Resin, manufactured by Arakawa Chemical Co., Ltd. under the brand name Tamanol n 361 N) Co co - O4A -J

TABLE II

Example 5

Example 6

Example 7

Example 8

Example

comparative 6 Exemp comparative 7

Example

comparative 8

Example

  comparative 9 Resin Viscosity used of varnish (Pa.s at 25 C)

III-5 57.0

III-6 55.0

III-7 56.0

III-8 52.0

  III-d III-e II-5 control resin 51.0 57.0 59.0, 0 Gloss of the printed side Fixing time (min) Drying time (s) 3,0 3,0 3,0 3, 0 3.0 3, 0 4.5 3.0 Fog formation not observed not observed not observed not observed observed observed observed not observed Ability to emulsify ink good good good good poor poor poor Co% uq

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Claims (14)

R E V E N D I C A T I 0 N S   An offset printing ink composition, characterized in that it contains a resinous vehicle (III) prepared by reacting 5 to 100 parts by weight of a phenolic resin (component D) with 100 parts by weight of an acid modified resin (II), said phenolic resin (component D) being prepared by condensing a phenol containing a C4-C9 alkyl substituent with formaldehyde, said modified acid modified resin (II) being prepared by reaction of 1 to 15 parts by weight of a component C selected from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and mixtures thereof with 100 parts by weight of a resin (I) obtained by copolymerization from 5 to 100 parts by weight of a component B selected from straight-chain olefins, drying oils, fatty acids and mixtures thereof with 100 parts by weight of a 5-membered ring compound (component A) having one or conjugated double bonds and represented by the general formula HRm n wherein H is hydrogen, R is C1-C3 alkyl, n and m are each zero or an integer at least 1 and satisfy the relation m + n = 6,   and / or one of its Diels-Alder adducts.   An offset printing ink composition according to claim 1, characterized in that said cyclic ring compound and / or its Diels-Alder adduct (component A) are selected from cyclopentadiene, methylcyclopentadiene, dicyclopentadiene, the cyclopentadiene-methylcyclopentadiene codimer,   tricyclopentadiene and mixtures thereof.   An offset printing ink composition according to claim 1, characterized in that said ring-shaped ring compound and / or its Diels-Alder adduct (component A) consist of a concentrated distillate obtained by separation of the most of the C5 fractions of a mixture prepared by thermal dimerization of cyclopentadiene and methylcyclopentadiene   contained in the C5 fractions of the oils formed as sub-   thermal cracking products of naphtha or the like at elevated temperatures. An offset printing ink composition according to claim 1, characterized in that said cyclic ring compound and / or its Diels-Alder adduct (component A) contains an unsaturated aromatic compound in an amount not exceeding the amount of said 5-membered ring compound and / or its Diels-Alder adduct.   An offset printing ink composition according to claim 1, characterized in that said long chain α-olefin is C4-C40o An offset printing ink composition according to claim 5, characterized in that said straight-chain α-olefin is selected from 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-dodecene, 1-tetradecene, 1-hexadecene,   1-octadecene, 1-eicosene and mixtures thereof.   An offset printing ink composition according to claim 1, characterized in that said drying oil has an iodine number of not less than 120 and in that it is selected from   vegetable and animal oils and fats and their mixtures.   8. Offset printing ink composition according to claim 7, characterized in that said vegetable oil is selected from linseed oil, tung oil, soybean oil, castor oil dehydrated, boiled linseed oil, boiled tung oil, boiled soybean oil, dehydrated castor oil boiled and their mixtures.   An offset printing ink composition according to claim 1, characterized in that said fatty acid is selected from myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, acids   flaxseed oil, tall oil fatty acids, tall oil mainly   composed of fatty acids and their mixtures.   An offset printing ink composition according to claim 1, characterized in that said component C is chosen   among acrylic acid, methacrylic acid, maleic acid,   maleic anhydride, tetrahydrophthalic acid and its anhydride, fumaric acid, citraconic acid, itaconic acid,   fatty acids of drying oils and mixtures thereof.   11. Offset printing ink composition according to claim 1, characterized in that said modified resin (II)   by an acid is esterified with a mono- or polyalcohol.   12. Offset printing ink composition according to claim 1, characterized in that said phenol is selected from p-tertbutylphenol, sec-butylphenol, p-tert-octylphenol, nonylphenol and their mixtures.   13. An offset printing ink composition according to claim 1, characterized in that it further comprises 50 parts by weight of a hydrocarbon solvent having a boiling range of 200 to 350 C and 0 to 150 parts by weight of a drying oil, the content of aromatic compound in said solvent   hydrocarbon being less than 50% by weight.   14. Offset printing ink composition according to claim 13, characterized in that said hydrodarbonated solvent is a paraffinic solvent.