Ink compositions for waterless plates

Abstract: An ink composition for waterless plates for lithography, which comprises as the vehicle a resin (III) obtained by copolymerizing a five-membered compound, such as cyclopentadiene, and/or a Diels-Alder adduct thereof with an unsaturated aromatic hydrocarbon monomer to obtain a resin (I), reacting the resin (I) with an unsaturated carboxylic acid and/or the anhydride thereof to obtain a resin (II) and then further reacting the resin (II) with a phenolic resin to obtain the resin (III).

Description: This invention relates to an ink composition which will exhibit excellent printability and satisfactory resistance to scumming when used in a waterless plate for lithography. In lithography which is mainly used in the printing field, there is employed a plate consisting of hydrophilic non-image area and oleophilic printing area. In the plate, a dampening solution is attached to the hydrophilic non-image area while an oleophilic ink is attached to the oleophilic printing area by making use of the tendency that water and an oleophilic ink repel each other and then the oleophilic ink so attached to the printing area is transferred to a to-be-printed substrate thereby obtaining a desired print. In such conventional lithography, however, it is difficult to control the dampening solution which serves to prevent the ink from adhering to the non-image area and it constitutes a serious technical obstacle to use such a dampening solution from the viewpoint of printability and printing effects. In attempts to overcome these disadvantages, there have heretofore been proposed various lithographical methods using waterless lithographical plates. As the newest practicable lithographical method using a waterless plate, there has been proposed a printing method using a plate in which the non-image area are covered with non-tacky thin films of silicone rubber or the like. In this printing method so proposed, it is reported that printing can be effected with a usual oleophilic ink without the supply of a dampening solution. It has now been found to be undesirable, however, in that scumming will disadvantageously be caused when a conventional oleophilic ink is used for printing since the printability of the conventional ink is unsatisfactory. The reason why scumming is caused in waterless lithography is that the cohesion of the ink used drops due to a rise in temperature of the plate caused by friction friction in the moving parts and rolls of the printing press used during printing whereby the ink adheres to the non-image area which originally repel such inks. To avoid this drawback, there have been proposed, inter alia, a method using a printing ink with a silicone compound incorporated (Japanese Patent Gazette No. 50-11287, Japanese Pat. Appln. Laid Open Gazette No. 55-31885) and a method using a printing ink which contains a resin modified with a silicone compound (Japanese Pat. Gazettes Nos. 51-10124, 52-10041 and 52-10042). These methods, however, have still not satisfactorily solved problems as to scumming and have left unsolved problems as to unsatisfactory levelling of inks, unsatisfactory gloss, and the like. There has also proposed an improved method in which is used a varnish gelled by incorporation of, for example, an aluminum compound such as aluminum stearate or aluminum octoate. When a high anti-scumming property is sought with the above improved method, the ink used will greatly increase in viscosity with problems arising as to ink transferability, such as for transfer of the ink on the printing press or to the plate or blanket, proving that said improved method is still not satisfactory at the present. Also known for example from GB-A-1458219 are toluene gravure inks which contain as a basic component a hydrocarbon resin modified with α,β-olefinically saturated dicarboxylic acid or an hydride thereof and by a phenol-aldehyde condensate. According to GB-A-1458219, the hydrocarbon resin comprises styrene, vinyltoluene, methylstyrene, cyclopentadiene and/or dicyclopentadiene and, in addition, indine to an extent of at most 20%. It has been observed that when indine is present, it is difficult to achieve a very high polymerisation and to obtain an ink composition for waterless plates which possesses the desired properties in respect of scumming resistance and printability in waterless lithography. The primary object of this invention is to provide an ink for waterless plate composition which eliminates the above drawbacks of the conventional inks and is excellent in scumming resistance, gloss and printability. The present inventors made intensive studies in attempts to solve the above-mentioned problems and, as a results of their studies, found that the problems can be solved by having present in a drying oil and/or semi-drying oil vehicle for an ink for waterless plates, a specific resin prepared by copolymerizing (A) a compound containing a cyclopentadiene ring or a Diels-Alder adduct of said compound with (B) an unsaturated aromatic hydrocarbon monomer having a carbon-carbon double bond and a benzene ring in the molecule to obtain a hydrocarbon resin and thereafter modifying the thus obtained resin with an acid and then with a resol-type phenol resin to obtain the specific resin. More specifically, the specific resin contained in the vehicle in the ink composition of this invention for use in waterless plates may be obtained by copolymerizing 100 parts by weight of (A) a five-membered cyclic compound having a conjugated double bond represented by the following general formula; wherein H is hydrogen, R is an alkyl group having 1-3 carbon atoms, m and n are each zero or an integer of at least one, and m+n=6 , and/or a Diels-Alder adduct, with 5-200 parts by weight of (B) at least one unsaturated aromatic hydrocarbon component selected from styrene, vinyltoluene, α-methylstyrene and an aromatic fraction obtained by decomposition of naphtha and containing unsaturated aromatic ingredients thereof to obtain a hydrocarbon resin (I), reacting 100 parts by by weight of the thus obtained hydrocarbon resin (I) with (C) 0.5-20 parts by weight of an unsaturated carboxylic acid and/or the anhydride thereof to obtain an acid-modified resin (II) and then thermally reacting 100 parts by weight of the thus obtained acid-modified resin(II) with 5-100 parts by weight of (D) a phenol resin prepared by condensing a phenol compound with formaldehyde (in the form of formalin), thereby to obtain the specific or final modified resin (III). The compound (A) used in this invention is either a five-membered cyclic compound having a conjugated double bond represented by the following general formula; wherein H is hydrogen, R is an alkyl group having 1-3 carbon atoms, m and n are each zero or an integer of at least one, and m+n=6 , or a Diels-Alder adduct of said five-membered cyclic compound having a conjugated double bond. The five-membered cyclic compounds according to this invention include cyclopentadiene and methylcyclopentadiene, and the Diels-Alder adducts according to this invention include dicyclopentadiene, cyclopentadiene-methylcyclopentadiene comonomer and tricyclopentadiene. These five-membered cyclic compounds and Diels-Alder adducts thereof may be used singly or jointly as the compound (A) with cyclopentadiene, dicyclopentadiene and mixtures thereof being particularly preferred. Cyclopentadiene, dicyclopentadiene or an alkyl-substituted derivative thereof, which may be used in this invention, is not necessarily required to be highly pure but is desired to be at least 80 wt.% pure. The compound (A) used in this invention may also be a concentrated fraction obtained by thermally dimerizing cyclopentadiene and methylcyclopentadiene contained in a C₅ fraction which is a by-product oil obtained by the high-temperature pyrolysis of naphtha and/or the like, to obtain a mixture of dicyclopentadiene, dimethylcyclopentadiene, cyclopentadiene-methylcyclopentadiene comonomer, cyclopentadiene-isoprene comonomer, cyclopentadiene-piperylene comonomer and the like and then removing the greater part of the C₅ ingredients such as C₅ olefins and C₅ paraffins from the dimer mixture-containing C₅ fraction thereby to obtain the concentrated fraction. The compound (B) used in this invention is an unsaturated aromatic hydrocarbon monomer having a carbon-carbon double bond and a benzene ring, and is specifically styrene, vinyltoluene, α - methylstyrene, and an aromatic fraction containing unsaturated aromatic ingredients. The aforesaid three monomers are of value since they, together with the compound (A), are very effective in producing a high molecular-weight resin whereby the resulting ink composition will have very satisfactory resistance to scumming. The compound (B) may also be an aromatic fraction containing unsaturated aromatic ingredients, the fraction being obtained by the decomposition of naphtha. In this case, it is particularly preferred that the aromatic fraction be further refined to obtain a vinyltoluene-rich fraction for use as the compound (B). According to this invention, 100 parts by weight of the above compound (A) are reacted with 5-200, preferably 10-180, parts by weight of the above compound (B) in the absence or presence of a suitable catalyst to produce a hydrocarbon resin (I). In a case where the reaction is effected in the absence of a catalyst, the above mixture of the compounds (A) and (B) may be heated to 200-300°C for 30 minutes to 15 hours, preferably 1-12 hours, to produce the hydrocarbon resin (I). On the other hand, in a case where the reaction is effected in the presence of a catalyst, the catalyst may be a Friedel-Crafts type catalyst such as boron trifluoride, a complex thereof with phenol, an ether, acetic acid or the like, or aluminum chloride. These catalysts may be used in amounts by weight of 0.1-10%, preferably 0.3-2%, and, in this case, the reaction may be carried out at a reaction temperature of from -30 to 100°C, preferably 0 to 50°C, for a reaction time of 10 minutes to 20 hours, preferably 1 to 15 hours. In the production of the hydrocarbon resin (I) according to this invention, the use of the compound (B) in amounts of less than said range of amount will result in the production of a final modified resin having an insufficiently high molecular weight and insufficient resistance to scumming, while the use thereof in amounts of more than said range of amount will result in producing a final modified resin having insufficient solubility in solvents having a high boiling point whereby the resulting ink composition decreases in gloss. The hydrocarbon resin (I) obtained as mentioned above is then reacted with an unsaturated carboxylic acid or the anhydride thereof (C). The compound (C) may preferably be an unsaturated monocarboxylic or polycarboxylic acid having 3-32, preferably 3-15, carbon atoms and is typified by acrylic acid, methacrylic acid, maleic acid, maleic anhydride, tetrahydrophthalic acid or the anhydride thereof, fumaric acid, citraconic acid, itaconic acid or a mixture thereof as well as by the fatty acid of a drying oil such as linseed oil. Among these compounds, maleic acid and maleic anhydride are preferred. The compound (C) is used in amounts by weight of 0.5-20, preferably 1-10, parts per 100 parts by weight of the hydrocarbon resin (I). The use of the compound (C) in amounts less than said range of amount will result in the production of an acid-modified resin having less polar groups. Thus, the resin so produced is poor in pigment dispersibility and in characteristics as a resin having polar groups and will produce an ink having undesirably unsatisfactory fluidity and printability when contained as the vehicle in the ink. On the other hand, the use of the compound (C) in amounts more than said range of amount, will result in producing a resin having too many polar groups whereupon the resin is unsatisfactorily soluble in solvents and undesirably tends to discolor and gel. When the resin so produced is used in the preparation of an ink, it is unsatisfactorily soluble in a hydrocarbon solvent for making a varnish and the resulting ink will undesirably have poor fluidity and produce a print having poor gloss. The acid-modifying reaction according to this invention may be carried out at 100-300°C, preferably 150-250°C, for 30 minutes to 15 hours, preferably 1-8 hours, in the absence of a catalyst or in the presence of a radical initiator such as an organic peroxide. It is preferable that no catalyst be employed when an unsaturated polycarboxylic acid or its anhydride is used as the acid-modifier and that a suitable catalyst be employed when an unsaturated monocarboxylic acid or its anhydride is used in the reaction. The acid-modified resin (II) may alternatively be produced by the following one-step method. A mixture of the compounds (A) and (B) is copolymerized under heat at 200-300°C while adding an unsaturated carboxylic acid or its anhydride to the copolymerizing reaction system, the addition being started at the initial stage of the reaction or halfway on the reaction, to obtain an acid-modified resin according to this invention. It is also possible to esterify the acid-modified resin (II) with an alcohol in order to adjust the solubility and softening point of the acid-modified resin (II) or adjust the molecular weight of the final modified resin (III). In this case, a monohydric or polyhydric alcohol may be used for the esterification. The use of a monohydric alcohol having at least 6, preferably 8-18, carbon atoms will result in producing a final modified resin (III) having particularly good solubility. The amount of such an alcohol used is either 0-1.0 mol equivalent per mol equivalent of the carboxyl group in the acid-modified resin (II) or 0-2.0 mol equivalent per mol equivalent of acid anhydride group in the acid-modified resin (II). The esterifying reaction is carried out by heat melting the acid-modified resin or dissolving it in a hydrocarbon solvent such as benzene, toluene or xylene, adding an alcohol to the molten or dissolved resin and then reacting them, for example, at 150-250°C for 30 minutes-10 hours, preferably 1-5 hours. According to this invention, the acid-modified resin (II) is further reacted with a phenol resin (D) to obtain a final modified resin (III). A phenol resin which may be used in this invention is preferably obtained by the condensation of phenol having an alkyl substituent of 4-9 carbon atoms and formaldehyde. The phenol resin industrially preferred includes p-tert.-butylphenol, sec.-butylphenol, p-tert.-octylphenol or nonylphenol. In substitution for the reaction with a phenol, formaldehyde and a phenolic compound may be reacted with each other in the presence of the acid-modified resin (II) using oxalic acid or maleic acid as the catalyst or using no catalyst, to obtain a desired phenol resin-modified resin. The amount of a phenol resin used for the modification may preferably be 5-100, more preferably 7-50, parts by weight per 100 parts by weight of the above acid-modified resin (II). In a case where a final modified resin prepared using the phenol resin in amounts less than said range of amount is used as the vehicle for an ink composition, the resulting ink composition will have unsatisfactory fluidity and will not give satisfactorily glossy prints when used for printing. On the other hand, a final modified resin prepared using the phenol resin in amounts more than said range of amount is not only unsatisfactory in solubility in solvents for inks but also industrially uneconomical, this being undesirable. The final reaction stage to produce resin (III) may be completed only by mixing the acid-modified resin (II) with the phenol resin, melting them and then heating the molten material at 150-250°C for 30 minutes -10 hours, preferably 1-5 hours. As required, there may be used an acid catalyst, such as oxalic acid, toluenesulfonic acid or a Friedel-Crafts' type catalyst, in the reaction. It is preferable that the final modified resin (III) have a softening point of at least 120°C, preferably at least 140°C. If a final modified resin having a softening point of lower than 120°C is used in the preparation of a printing ink, the resulting printing ink will exhibit much misting, low drying speed and decreased resistance to scumming when used for printing. The final modified resin (III) so obtained may be contained in an ink in an amount by weight of preferably 5-50%, more preferably 7-50% and further more preferably 10-45% of the ink. In a case where the final modified resin (III) is used in amounts outside of said range of amount in the preparation of an ink, the resulting ink will be likely to be unbalanced as such. For example, the use of the resin (III) in amounts by weight of less than 5% will result in producing an ink which tends to cause scumming when used for printing because of its low cohesion. On the other hand, the use thereof in amounts by weight of more than 50% will result in producing an ink which, when used, will not only tend to be unsatisfactorily transferred from roll to roll and unsatisfactorily attached to the blanket because of its too high cohesion, but also tend to worsen its levelling on a to-be-printed substrate whereby the gloss is degraded. The final modified resin (III) may be further modified with a compound containing a silicone component, or the vehicle in a varnish may be wholly modified by adding a silicone ingredient-containing compound to the varnish when cooking the varnish. The silicone ingredient-containing compound used herein is usually typified by an organopolysiloxane which includes an organopolysiloxane having one or more hydroxyl groups or alkoxy group in the molecule or having one or more Si-H bonds in the molecule. It is preferable that these compounds have molecular weight of 3,000,000 - 150,000. Also used in the preparation of ink compositions of this invention are drying and semi-drying oils which are known ingredients for use in conventional lithography, such as linseed oil, tung oil, soybean oil, safflower oil and castor oil. Other substances used in conventional lithography which may be present in the ink compositions are solvents such as petroleum-derived solvents boiling within 200-350°C; and gelling agents such as organoaluminum compounds, organotitanate compounds, organozinc compounds and organocalcium compounds. Coloring agents which may be used in the preparation of ink compositions of this invention are such inorganic and organic ones that have heretofore been used in conventional ink compositions. Known ingredients such as waxes, greases, desiccants, dispersants and fillers, may be used in this invention as required. In addition to these, other resins such as resin-modified phenol resins, alkyd resins and petroleum resins, may also be used in such amounts that they do not impair the performances of the resulting ink compositions. Inks prepared by kneading such ingredients as mentioned above with a three-roll unit do not cause scumming except at high temperatures and are excellent in printability. Further, printed matter produced with the above inks have satisfactory gloss without piling being caused. DESCRIPTION OF THE PREFERRED EMBODIMENTS This invention will be better understood by the following exemplifying Syntheses and Examples to which this invention is not limited. Synthesis 1 Three hundred and fifty (350) grams of 97% pure dicyclopentadiene, 350g of styrene and 300g of mixed xylenes were charged into a 2-liter autoclave and the whole was heated to 270°C under agitation for 6 hours in a nitrogen atmosphere. After the end of the heating, the autoclave was cooled and the contents therein were distilled to remove the unreacted monomers, low polymers and xylenes therefrom thereby to obtain 663g of a resin (1-I) as the bottoms. The resin (1-I) had a softening point of 144.0°C. Two hundred and forty (240) grams of the thus obtained resin (1-I) were heated to 220°C for melting, and incorporated therein were 7.2g of maleic anhydride, after which the whole was reacted under agitation for 4 hours thereby to obtain an acid-modified resin (1-II) having a softening point of 151.5°C and an acid value of 12.2mg KOH/g. To one hundred and eighty (180) grams of the thus obtained acid-modified resin (1-II) were added 20g of a resol-type phenol resin obtained from p-tert.-octylphenol and formaldehyde and the mixture obtained was reacted at 220°C for 3 hours thereby to obtain a final modified resin (1-III) having a softening point of 169.5°C and an acid value of 11.9mg KOH/g. Synthesis 2 Three hundred and twenty (320) grams of 97% pure dicyclopentadiene, 480g of an aromatic fraction boiling at 140-200°C (unsaturated aromatic components, 50%; saturated aromatic components, 50%; 70% of the unsaturated aromatic components being vinyltoluene) obtained by the pyrolysis of naphtha, and 200g of mixed xylenes were charged into a 2-liter autoclave, reacted under agitation at 270°C for 9.5 hours and then further treated in the same manner as in Synthesis 1 thereby to obtain 549g of a resin (2-I) having a softening point of 140.5°C. Two hundred and forty (240) grams of the thus obtained resin (2-I) were melted under heat, 9.6g of maleic anhydride were added and reaction took place under agitation for 4 hours to obtain an acid-modified resin (2-II) having a softening point of 156.5°C and an acid value of 15.1mg KOH/g. To 180g of the thus obtained acid-modified resin (2-II) were added 20g of a resol-type phenol resin obtained from p-tert.-octylphenol and formaldehyde, and then reaction took place at 220°C for 3 hours to obtain a final modified resin (2-III) having a softening point of 171.5°C and an acid value of 14.8mg KOH/g. Synthesis 3 A C₅ fraction (boiling at 28-60°C) obtained as a by-product by the steam cracking of naphtha to produce ethylene, propylene and the like, was heated to 120°C for 4 hours and freed from the remaining C₅ fraction by distillation to obtain a residue comprising 85% of dicyclopentadiene and 15% of "cyclopentadiene/isoprene comonomer or cyclopentadiene/piperylene" comonomer. Then, 427g of the thus obtained residue containing said 85% of dicyclopentadiene, 273g of styrene and 300g of mixed xylenes were charged into a 2-liter autoclave, reacted together at 270°C under agitation for 6.5 hours and then treated in the same manner as in Synthesis 1 to obtain 693g of a resin (3-I) having a softening point of 146.0°C. Then, 240g of the thus obtained resin (3-I) were heated and melted, 7.2g of maleic anhydride were added and then the mixture obtained was reacted under agitation for 4 hours to obtain an acid-modified resin (3-II) having a softening point of 152.0°C and an acid value of 11.9mg KOH/g. Thereafter, in 180g of the thus obtained acid-modified resin (3-II) were incorporated 45g of a resol-type phenol resin prepared from p-nonylphenol and formaldehyde and then the resins were reacted together at 220°C for 3 hours to obtain a final modified resin (3-III) having a softening point of 168.5°C and an acid value of 10.8mg KOH/g. Comparative Synthesis Seven hundred (700) grams of 97% pure dicyclopentadiene and 300g of mixed xylenes were charged into a 2-liter autoclave, reacted together under agitation at 260°C for 2.5 hours and then treated in the same manner as in Synthesis 1 to obtain 571g of a resin (4-I) having a softening point of 140.5°C. Then, 240g of the thus obtained resin (4-I) were heated to 220°C for melting, 7.2g of maleic anhydride were added and then the mixture obtained was reacted under agitation for 4 hours to obtain an acid-modified resin (4-II) having a softening point of 151.5°C and an acid value of 11.4mg KOH/g. Thereafter, to 180g of the thus obtained acid-modified resin (4-II) were added 20g of a resol-type phenol resin prepared from p-tert.-octylphenol and formaldehyde and then these were reacted together at 220°C for 3 hours thereby to obtain a final modified resin (4-III) having a soltening point of 170.5°C and an acid value of 11.2mg KOH/g. Example 1-3 and Comparative Examples 1-3 The final modified resins obtained in Syntheses 1-3 and Comparative Synthesis, and a control resin, were each used in preparing a varnish and gel varnish. An ink composition was prepared using each of the varnishes and gel varnishes and evaluated for ink characteristics or performances with the results being shown in the following Table 1. The control resin used in Comparative Examples 2-3 was a resin produced under the trademark "Tamanol 354" by Arakawa Chemical Co., Ltd., Japan, and the ink used in Comparative Example 3 was one which had been adjusted to cause scumming at 30°C by adding a solvent "Solvent No.5" (an organic solvent for inks, produced by Nippon Oil Co., Ltd.) to the ink of Comparative Example 2. Further, the varnishes, gel varnishes and ink compositions were respectively prepared as indicated hereunder, and the evaluations for ink characteristics as well as the results of printing are as shown hereunder. Preparation of varnish Forty (40) parts by weight of each of the final modified resins and 20 parts by weight of linseed oil No.4 (a drying oil for inks, produced by Toshin Oil and Fat Co., Ltd.) were boiled at 200-210°C for 30 minutes, 40 parts by weight of Solvent No.5 were added and the mixtures obtained were then heated to 140-150°C for 20 minutes thereby to obtain a varnish. Preparation of gel varnishes Forty (40) parts by weight of each of the final modified resins and 20 parts by weight of linseed oil No.4 were boiled at 200-210°C, 2.0 parts by weight of Optope Al (a gelling agent for varnishes, produced by Hope Pharmaceutical Co., Ltd.) and 38 parts by Solvent No.5 were added and the mixtures obtained were then heated to 140-150°C for 20 minutes thereby to obtain a gel varnish. Preparation of Ink Compositions The following ingredients were kneaded by the use of a three-roll unit to obtain ink compositions. Seika First Yellow 2340 (a pigment for inks, prepared by Dainichi Seika Co., Ltd., Japan) 15.0 parts by weight Respective varnish 64.7 parts by weight Respective gel varnish 20.0 parts by weight Cobalt naphthenate (a dryer for inks, produced by Nakarai Chemicals Ind. Co., Ltd., Japan) 0.3 parts by weight Characteristics of Ink Compositions and Prints A printing machine was used which was modified so that the drum surface could have its temperature raised by passing warmed water through the inside of the drum and to which a Toray-type waterless plate (positive type) was fixed. Printing was effected while raising the temperature of the surface of the plate without supplying a dampening solution, and the temperature of the plate surface at which the prints obtained with the test ink composition exhibit scumming at a certain fixed color density on solid was looked on as a scumming-occurring temperature. In practical printing, the higher the scumming-occurring temperature an ink composition has, the more difficult is it for the ink to cause scumming. Then, the ink compositions so prepared were measured at 30°C (i) for their fluidity (flow value) with a spread meter and (ii) for their tack value with an ink-o-meter. To obtain prints, the respective ink compositions were printed on a to-be-printed substrate using a waterless plate having non-image area made of silicone rubber and supplying no dampening solution to the plate. Printing was carried out on a Komori splint lithographic printing press. Then, the solid parts of the print at which the color density was 0.95 as determined by a Macbeth densitometer, were measured for their gloss value with a 60-degree specular reflection glossmeter. The results are as shown in Table 1. Kind of resin Scumming-occurring temperature (°C) Tack value Flow value Gloss Piling Example 1 1-III (Synthesis 1) 30 13.0 34.0 60 None Example 2 2-III (Synthesis 2) 29 14.0 36.0 62 None Example 3 3-III (Synthesis 3) 31 14.0 35.0 60 None Comp. Example 1 4-III (Comp. Synthesis) 24 13.0 36.0 59 None Comp. Example 2 Control 34 20.0 35.0 45 Severe Comp. Example 3 Control 30 17.0 36.0 50 Mild It is seen from Table 1 that the ink compositions of this invention obtained in Examples 1-3 have satisfactory resistance to scumming and excellent printability as compared with that obtained in Comparative Example 1, and that the prints obtained with the former ink compositions have satisfactory gloss as compared with that obtained with the latter. In addition, the ink compositions (using the control resin therein) obtained in Comparative Examples 2-3 exhibit satisfactory resistance to scumming, but they exhibit a high tack value thereby to cause piling during printing, and the prints obtained therewith have unsatisfactory gloss. Effects of this invention This invention has made it possible to provide ink compositions for waterless plates for lithography, which will exhibit not only satisfactory resistance to scumming but also excellent printability when used.

Claims: An ink composition for waterless plates which comprises a resin (III) and a vehicle which is selected from drying oils and semi-drying oils, the resin (III) being obtained by: copolymerizing 100 parts by weight of at least one compound (A) selected from the group consisting of (1) five-membered compounds having a conjugated double bond represented by the following general formula: wherein H is hydrogen, R is an alkyl group having 1-3 carbon atoms, m and n are zero or an integer of at least one, and m+n=6 , and (2) Diels-Alder adducts thereof, with 5-200 parts by weight of at least one unsaturated aromatic hydrocarbon component (B) selected from styrene, vinyltoluene, α-methylstyrene and an aromatic fraction obtained by decomposition of naphtha and containing unsaturated aromatic ingredients thereof, to obtain a hydrocarbon resin (I), reacting 100 parts by weight of the thus obtained resin (I) with 0.5-20 parts by weight of at least one compound (C) selected from unsaturated carboxylic acids and the anhydrides thereof to obtain an acid-modified resin (II), and thermally reacting 100 parts by weight of the thus obtained acid-modified resin (II) with 5-100 parts by weight of a phenol resin (D) obtained by the condensation of a phenolic compound and formalin, thereby to obtain a final modified resin (III). An ink composition according to Claim 1, wherein said compound (A) is at least one member selected from the group consisting of cyclopentadiene, methylcyclopentadiene, dicyclopentadiene, cyclopentadiene-methylcyclopentadiene comonomer and tricyclopentadiene. An ink composition according to Claim 1 or 2, wherein the phenol is selected from p-tert.butylphenol, sec.-butylphenol, p-tert.octylphenol and nonylphenol. An ink composition according to Claim 1, 2 or 3, wherein the acid-modified resin (II) is prepared by copolymerizing a mixture of compounds (A) and (B) at 200-300°C while adding the unsaturated carboxylic acid or its anhydride at the beginning of the copolymerizing or half-way through the copolymerizing. An ink composition according to any preceding claim, wherein the acid-modified resin (II) is esterified with an alcohol. An ink composition according to Claim 5, wherein the alcohol is a monohydric alcohol containing at least 6 carbon atoms. An ink composition according to Claim 5 or 6, wherein the alcohol is used either in an amount of 0-1.0 mol equivalent for mol equivalent of carboxyl groups in the acid-modified resin (II) or in an amount of 0-2 mol equivalent for mol equivalent of acid anhydride groups in the acid-modified resin (II). An ink composition according to any preceding claim, wherein resin (III) has a softening point of at least 120°C. An ink composition according to any preceding claim, which contains resin (III) in an amount of from 5-50 % by weight.

Inventors: IKEDA NORIMASA C O TORAY INDUS, SASAKI MAKOTO, SUEZAWA MITSURU C O TORAY INDU, TSUCHIYA SHOZO, IKEDA, NORIMASA C/O TORAY INDUSTRIES, INC., SASAKI, MAKOTO, SUEZAWA, MITSURU C/O TORAY INDUSTRIES, INC., TSUCHIYA, SHOZO
Applicants: NIPPON OIL CO LTD, TORAY INDUSTRIES, NIPPON OIL CO. LTD., TORAY INDUSTRIES, INC.
Application year: 1988
Main classification: C09D11
IPC codes: C09D11