DE3132081A1 - OFFSET PRINT INK - Google Patents

Description

The invention "relates to an offset printing ink.

For the production of printed matter were widely used in Scope of relief printing processes, lithographic printing processes including offset printing processes and gravure printing processes applied. In the offset printing method, the image formed with printing ink is once by a printing roller transferred to a rubber blanket and then printed on a sheet of paper. The pressure roller has a surface those made up of hydrophilic areas (non-image areas) that contain water and repel oily paint, and those that contain paint Areas (image areas) that contain oily paint and repel water. The most widely used Offset inks are resin varnishes that are resins like Alkylphenol resins, with rosin, modified phenolic resins or contain maleic acid resins dissolved in drying oils such as linseed oil. The ones modified with rosin Phenolic resins are the most common of the resins used. Albeit an ink binder that comes out of one with Rosin modified phenolic resin, a solvent and / or a drying oil, excellent quality it is disadvantageous in that it is expensive and contains rosin, which is a natural product Is of origin and its accessibility is therefore uncertain

is. Instead of the phenolic resin modified with colophony, so-called petroleum resins were used or petroleum resins, which are synthesized by polymerization of cracked oil fractions, which as by-products of the petroleum or petrochemical industry can be obtained. These petroleum resins have the advantage that their procurement and their price are stable, theirs However, the quality is not satisfactory when they are used as binder resins for printing inks.

The essential properties, i.e. printability, which are required for a printing ink, in particular, if it is to be used as an offset printing ink, are the following:

(1) The paint must have suitable fluidity, expressed due to the viscosity and the yield.

(2) Good balance should be achieved at the interface between the hydrophilic area and the paint containing area can be obtained so that an image is formed on a plane on which Water "and a color come into contact with each other.

(3) A pigment must uniformly dis- in the color '* are pergiert 23rd

(4) The printed area should show a nice gloss * and uniform printed matter must be available be.

(5) The necessary for solidification or drying

Time must be short and the color must not show any "blocking" (unwanted sticking).

(6) The printed area should have abrasion resistance.

In order to produce an offset printing ink which has the required properties specified above, j the resin present in the paint must have the following requirements

fulfill nits:

(1) It is required to have a high softening point, but it should not have a high molecular weight incidentally

5 (2) It must contain a polar group in order to avoid the

To improve the dispersibility of a pigment, i.e. it must have a polar group which has good affinity for a pigment.

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

and contains only a small proportion of aromatic compounds.

(4) There must be sufficient solubility in a drying Oil such as linseed oil.

Especially in the course of the development of printing technology in recent years, it has become necessary to increase the printing speed. As a result of this requirement one has increasingly the offset rotary printing process applied. In the rotary offset printing process, in which the ink is heated to dryness, is it is highly desirable to use a high boiling point hydrocarbon solvent such as a paraffin solvent, that contains aromatic compounds in as low a proportion as possible and that preferably no aromatic compounds Contains compounds to improve the environmental conditions in the workplace and to address pollution problems to be excluded due to exhaust gases. However, one has not yet had a satisfactory offset printing ink Printing properties as described above developed. Because of this, there is an increasing There is a need for an offset printing ink with satisfactory printing properties.

It is already known from US Pat. No. 3,084,147 that thermal polymerization of cyclopentadiene at high

Temperatures from 250 to 350 ⁰ C in the presence of an inert

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Room

Hydrocarbon solvents / such as benzene, toluene, xylene or isooctane _r a resin can be obtained that is soluble in hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane or isooctane.

The dicyclopentadiene resin produced using this "known method" is soluble in a hydrocarbon solvent including benzene, toluene, xylene, Solvent naphtha and Solvent No. 5 (product of Nippon Oil Co. Ltd.). However, since this dicyclopentadiene resin does not have any having polar group, it can be opposed because of its poor miscibility with and its poor adhesiveness other materials cannot be used for numerous purposes. One by adding different ones The printing ink made from solvents and pigments to the aforementioned resin cannot be used as an offset printing ink can be used because the dispersibility of pigments in the paint is unsatisfactory, resulting in uneven printed areas with poor gloss.

Further, it was described in JA-OS 24 405/1972 that a carboxylic acid group-containing resin is prepared by adding a _r acrylate or maleic anhydride is added to this dicyclopentadiene resin and then the product is subjected to hydrolysis. The obtained carboxylic acid group-containing resin is then reacted with a polyhydric alcohol and a higher unsaturated carboxylic acid to prepare a resin for printing inks. The resin produced by this method, which has a high softening point, so that an offset printing ink is obtained which can be solidified and dried within a time practically equal to that for solidification and drying of conventional offset printing inks poor solubility in a petroleum-derived hydrocarbon solvent used as a solvent for offset printing ink. As a result, the fluidity of the printing ink produced therefrom is poor and the gloss of the printing ink is extremely deteriorated. Another disadvantage of this

Resin consists in the fact that it forms a gel in the stage of making a varnish, so that a cloudy varnish with bad shade is obtained. On the contrary, the softening point of this resin must be lowered, to improve the solubility in solvents, which leads to an extension of the solidification and drying required time leads. For the reasons mentioned above, this can be prepared using the known method Resin not intended for practical use

10 suitable offset printing inks can be used.

On the other hand, in U.S. Patent No. 2,608,550, a thermal Copolymerization of dicyclopentadiene and maleic anhydride produced resin described. That in this However, the resin indicated in the patent, which has a relatively low content of maleic acid, generally has has an unacceptably high softening point and has poor dispersibility for pigments and above in addition, poor miscibility with other filling materials. When the level of maleic anhydride is increased, the To overcome the above-mentioned disadvantages, discoloration and gelation tend to occur and the resultant Resin gets poor weather resistance.

In addition, US Pat. No. 2,605,550 describes an alkyd resin which is formed from a so-called alkyd mixture which comprises a polybasic acid component composed of one obtained by thermal polymerization of dicyclopentadiene resin made with maleic anhydride. Have the alkyd resins described in this patent however, generally high molecular weights, poor solubilities in high boiling hydrocarbon solvents for printing inks and in drying oils. As a result, one made from any of these alkyd resins shows Printing ink has poor flowability, insufficient gloss of the printed matter and tends to become in the form of a mist from the printing roller and to contaminate the paper, so that serious Problems caused by stray mist formation.

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For these reasons, those mentioned in the above Patent specification specified alkyd resins are not put to practical use.

Although drying oils, such as linseed oil, are found in common offset printing varnishes have been applied, their applied amount tends to decrease as the printing speed is increased to the problems of soil pollution caused by the application of drying Oils are caused to be avoided and to prevent the occurrence to eliminate the formation of scattered fog and delayed solidification »

Usual offset ink varnishes include a high boiling point Hydrocarbon solvent, an oil component, such as a drying oil; and a binder resin. For this purpose, alkylphenol resins, phenolic and maleic resins modified with rosin are used. A color lake composition that one Contains a reduced amount of drying oil, but does not result in glossy and good-looking printed matter by itself when any of the known binder resins are added.

In addition, none of the known resins are far from being satisfactory Solubility in paraffin solvents, making them almost useless as binder resins for offset printing inks that contain paraffin solvents.

It is therefore an object of the invention to provide a composition for an offset printing ink which leads to uniform printed matter with printed surfaces with a beautiful gloss.

A further object of the invention is to provide a composition for an offset printing ink which solidifies and dries over a short period of time and does not show any blocking.
The invention is also based on the object of providing an offset printing ink which has improved emulsifying properties and which does not have the problem of

Stray mist formation occurs.

According to the invention, an offset printing ink should also be included

suitable fluidity can be formed.

The offset printing ink of the present invention is said to be excellent Interfacial equilibrium at the interfaces the hydrophilic areas and the colored areas

exhibit.

It is also an object of the invention to provide an offset printing ink composition to create that does not gel and does not become cloudy in the stage of making a varnish,

so that a color lake with a good hue is formed.

It is also an object of the invention to provide an offset printing ink to make available, which contains a binder resin or carrier resin, the good solubility in high-boiling Owns hydrocarbon solvents for the paint and in drying oils.

The offset printing ink of the present invention is said to be a binder resin which is soluble in paraffin solvents and has excellent printing properties.

In addition, the binder resin of the offset printing ink of the present invention is said to be excellent in printability show even when a relatively small amount of a drying oil is added.

The foregoing and other objects of the invention and its advantageous features are from the following detailed description.

The offset printing ink provided according to the invention comprises a binder resin (III) obtained by reacting 5 to 100 parts by weight a phenolic resin (component D) with 100 parts by weight of an acid-modified resin (II), this phenolic resin (component D) by condensation of a phenol having an alkyl substituent group with 4 to 9 carbon atoms is produced with formalin and the modified resin (II) which is produced with an acid is modified by reacting 1 to 15 parts by weight

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a component C from the group of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and their mixtures with 100 parts by weight of a resin (I). is prepared by copolymerizing 5 to 100 parts by weight of a component B from the group of straight chain a-01efine, the drying oils, fatty acids or * · their mixtures with 100 parts by weight of a five-membered cyclic compound (component A) that has a conjugated double bond or bonds

10 and by the general formula

can be represented in which H is a hydrogen atom, R is an alkyl group having 1 to 3 carbon atoms, m and η are 0 or integers of not less than 1 and satisfy the condition m + η = 6,
and / or a Diels-Alder addition product of such

20 connection is available.

The invention is described in more detail below.

To form the composition according to the invention, a five-membered cyclic compound is used as component (A) which has a conjugated double bond or bonds, and / or a Diels-Alder addition product of a such connection applied. This compound can be expressed by the following general formula

represent, in which H is an hydrogen atom, R is an alkyl group having 1 to 3 carbon atoms, m and η are zero or integers of not less than 1 and in which Relationship m + η = 6 with each other.

Specific examples of five-membered cyclic compounds, which are preferably used on an industrial scale may be used include cyclopentadiene and methylcyclopentadiene, and preferred examples of Diels-Alder addition products include dicyclopentadiene, Cyclopentadiene-Methylcyclopentadiene-Codimeres and Tricyclopentadiene. Mixtures of compounds as above mentioned can also be used to advantage. Among these are cyclopentadiene, dicyclopentadiene and mixtures thereof are most preferred.

It is not essential that the component (A) is used in a high purity. However, it is preferred that in the starting material one or more of the compounds cyclopentadiene, dicyclopentadiene or their alkyl substitution derivatives are present in a purity of more than 80% by weight. For example, it may be possible to use a to use concentrated fraction obtained by thermal dimerization of cyclopentadiene and / or methylcyclopentadiene, which is obtained in a by cracking of Naphtha formed at high temperature C, fraction are included, with a mixture of dicyclopentadiene, dimethylcyclopentadiene, Cyclopentadiene-methylcyclopentadiene-codimer, cyclopentadiene-isoprene-codimer and cyclopentadiene-piperylene-codimer is obtained, after which the majority of the C ^ fractions, such as Cc-01efine and

C _c ~ paraffins is removed by distillation. 5

In addition, component (A) of the starting material can contain an additional unsaturated compound, in particular an unsaturated aromatic compound, but its amount is less than that of the five-membered cyclic compound Compound and / or its Diels-Alder addition product amounts to. For example, styrene, a-methylstyrene, Vinyl toluene, indene, methyl indene and mixtures thereof as additional unsaturated compound are present and from the industrial point of view the so-called Cg fraction, obtained as a by-product of cracking naphtha and the like is preferred.

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The component (B) used according to the invention is from the group of the straight-chain α-01efine, the drying Oils, fatty acids or mixtures of such compounds are selected.

Preferred straight-chain α-olefins are those with 4 to 40 carbon atoms, with 6 to 20 carbon atoms being most preferred.

Of course, straight-chain cc-olefins can be commercially available pure products are used. From a technical and economic point of view, however, it is advisable to to apply mixed α-01efine obtained by (1) oligomerization of ethylene or (2) thermal cracking of paraffin waxes.

As a result of the oligomerization of ethylene mentioned under (1) above, straight-chain α-olefins with even carbon numbers are separated off in high purity and the separated product does not contain any other isomers. Through the cracking of paraffin waxes mentioned under (2) above, α-olefins are formed in a purity of about 90 % , the remainder of the product consisting of branched olefins, diolefins and naphthenes. This product can also be used as such for the purposes of the invention without difficulty.

More specific examples of the α-01efine include hexene-1, heptene-1, octene-1, wonen-1, dodecene-1, tetradecene-1, Hexadecene-1, Octadecene-1, Eicosen-1 and mixtures of such connections. An olefin mixture formed with the aid of the process mentioned under (1) above is im Commercially available, for example, from Mitsubishi Kasei Co. Ltd. under the trade designation Dialen. One with help of the process indicated above under (2) manufactured product is under the trade name Shevron a-01efin commercially available from Shevron Corporation. A mixture of two or more of the α-olefins described above can also be used as component (B) will.

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The drying oils usable as component (B) for the purpose of the invention include vegetable and vegetable oils animal oils and fats with iodine numbers of not less than 120. Desiccant vegetable oils are particularly preferred Oils such as linseed oil, tung oil, soybean oil and dehydrated Castor oil. It can also be cooked oils obtained by thermal processing of the aforementioned drying Oils obtained are used.

Fatty acids that can be used according to the invention as component (B) include saturated or unsaturated synthetic fatty acids, such as myristic acid, Palmitic acid, stearic acid, oleic acid, linoleic acid and Linolenic acid, as well as fatty acids of natural origin, like fatty acids from linseed oil and fatty acids from tall oil. Tall oil, which is mostly made up of fatty acids, can can also be used as component (B) for the purposes of the invention.

A mixture of two or more of the above-mentioned compounds is also suitable as component (B).

According to the invention, the resin (I) is prepared by reacting 100 parts by weight of component (A) with 5 to 100 parts by weight, preferably 5 to 50 parts by weight, of component (B) in the presence or absence of a catalyst. If the reaction is carried out in the absence of a catalyst, the mixture of components (A) and (B) is heated to 200 to 300 ° C. for 30 minutes to 15 hours, preferably 1 to 7 hours, to give the resin (I. ) to produce. When using a catalyst, a Friedel-Crafts catalyst, such as boron trifluoride, complexes of boron trifluoride with phenol, ether or acetic acid, or aluminum chloride, the monomer mixture in an amount of 0.1 to 10 wt .- ^, preferably 0.3 to 2 wt .-%, based on the total weight of the monomers added, and the mixture is stirred at a reaction temperature of minus 30 ° C to plus 100 ° C _s is preferably 0 to 50 ⁰ C, for a reaction period of 10 minutes to 20 hours ^ preferably 1 up to 15 hours,

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To get a finished binder or carrier resin, · Which shows particularly excellent solubility in a paraffin solvent becomes any of the aforementioned a-01efine is incorporated into component (B) so that there is at least a portion thereof Component. Adding an α-olefin as part of component (B) increases the solubility of the finished product Binder or carrier resin in a paraffin solvent improves remarkably, thereby reducing the Printability of the ink containing the resin is also improved.

When the amount of the component (B) used in the present invention to prepare the resin (I) is below the above specified and defined in the claims range is reached by adding them beneficial effect not a satisfactory level. On the contrary, when the amount of the component (B) exceeds the above exceeds the defined range, the yield of resin (I) is considerably reduced and the

20 softening point of the resin lowered.

According to the invention, the resin (I) prepared in the manner explained above with the component (C) for Implementation brought from the group of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and mixtures of which is selected. Preferred examples of unsaturated carboxylic acids or their anhydrides, the Can be used in the invention include monobasic or polybasic unsaturated carboxylic acids and their anhydrides, which generally have 3 to 32, in particular 3 to 15 carbon atoms. Representative examples for this are acrylic acid, methacrylic acid, maleic acid, maleic anhydride, tetrahydrophthalic acid and their anhydride, Fumaric acid, citraconic acid, itaconic acid and fatty acids from drying oils such as linseed oil fatty acids, as well Mixtures of such compounds. Most preferred are maleic acid and maleic anhydride.

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The ratio of the unsaturated carboxylic acid added or the anhydride thereof to the resin (I) is such that 1 to 15 parts by weight, preferably 1 to 10 parts by weight the former compound to 100 parts by weight of the resin

(I) can be added. When the amount of unsaturated Carboxylic acid or its anhydride below the range mentioned above and defined in the claims is, the resin formed is slightly improved than resin with polar groups because it is deficient having polar groups. When such a resin is used as a carrier resin or binder resin for printing ink becomes, the dispersibility of pigments, fluidity of color and printability are unsatisfactory.

If in contrast, the amount of unsaturated carboxylic acid or whose anhydride is above the defined range, the proportion of polar groups in the resin formed are present too high, resulting in poor solubility in solvents and an adverse Tends to discolour or gel in the resin. When such a resin is used in a printing ink becomes the solubility of the resin in a hydrocarbon solvent in the step of preparation of a color varnish poor, the flowability of the color and the gloss of the printed matter in disadvantageous

25 ways to be affected.

The above-mentioned reaction for modifying the resin with an acid can be carried out at a temperature in the range from 100 to 300 ° C, preferably 150 to 250 ° C, in Presence of a known radical-forming reaction initiator, such as an organic peroxide, for 30 minutes to 15 hours, preferably 1 to 8 hours. When an unsaturated polycarboxylic acid or the anhydride thereof is used, it is preferred to carry out the reaction without using a catalyst. When an unsaturated monocarboxylic acid or its anhydride is used, the reaction is preferred in Made in the presence of a catalyst.

The modified resin of the invention modified with an acid can be one-step by means of the following Process: An unsaturated carboxylic acid or an anhydride thereof can at the beginning or in an intermediate stage of the process step for thermal polymerization of the mixture of Components (A) and (B) are added and the mixture is made in the presence or absence of a solvent at a temperature of 200 to 300 C thermally polymer

10 ringed.

According to the invention, the resin (II) modified with the aid of an acid can be esterified with the aid of an alcohol in order to to regulate the solubility and the softening point of the resin (II) formed or the molecular weight of the Control binder resin (III). Alcohols used for this purpose include monohydric alcohols or polyhydric alcohols. Monohydric alcohols having not less than 6 carbon atoms, preferably 8 to 18 Carbon atoms, are particularly preferred in order to increase the solubility of the final binder or carrier resin (III) to improve. The amount of alcohol should be chosen so that the molar ratio of the carboxyl groups to the alcohol groups in the modified resin (II) is in the range from 1: 0 to 1: 1 and the molar ratio the carboxylic anhydride groups to the alcohol groups in the modified resin (II) in the range of 1: 0 to 2.0 lies.

The esterification can be carried out by first heating the modified resin (II) modified with an acid to melt it or by dissolving it in a hydrocarbon solvent such as benzene, toluene or xylene, followed by adding an alcohol takes place and the mixture at 150 to 250 ⁰ C for 30 minutes to 10 hours, preferably 1 to 15 hours, to

35 is set.

According to the invention, the modified resin (II) modified with an acid is further substituted with an alkyl-substituted one Phenolic resin (component D) reacted to the

desired binder or carrier resin (III) to be obtained. Phenolic resins which can be used according to the invention include the condensation products of phenols that have alkyl substituent groups with 4 to 9 carbon atoms, with formaldehyde. For specific examples of Phenols preferred from an industrial point of view include p-tert-butylphenol, sec-butylphenol, p-tert-octylphenol and nonylphenol. Phenolic resins obtained from phenols without substituent groups or cresols are not preferred, since in this case the solubility of the binder or carrier resin formed in high-boiling hydrocarbon solvents is low. If a phenolic resin is used, it is made from formaldehyde and a phenol having a substituent group with not less than 10 carbon atoms is obtained, the softening point of the binder or carrier resin formed becomes extremely lowered to a value unsuitable for a printing ink.

Instead of reacting the modified resin (II) with a phenolic resin, formaldehyde and a phenol can be used in Presence of the modified resin (II) with the use of an acid or alkali catalyst or without application a catalyst are converted to odor the desired binder modified with a phenolic resin To obtain carrier resin.

5 to 100 parts by weight, preferably 10 to 50 parts by weight of the modifying phenolic resin can add up to 100 parts by weight of the modified resin (II) modified with an acid can be added. When the crowd of the phenolic resin is below the above-mentioned range, that using the binder formed is medium-resin made printing ink unsatisfactory in terms of flowability and cannot be imprinted with a satisfactory gloss. On the contrary, when the amount of the phenolic resin falls within the above range exceeds, the solubility of the carrier resin formed in a solvent for the printing ink is

deteriorates and, moreover, the cost becomes undesirable Way increased.

The resin (II) can be modified with a phenolic resin by simply mixing the resin (II) with the phenolic resin to give a mixture which is melted and for 30 minutes to 10 hours, preferably 1 to 5 hours to 150 "to 250 ⁰ C is heated. If necessary, an acid catalyst, such as oxalic acid, toluenesulfonic acid or a Friedel-Craft catalyst, and also an alkali catalyst, such as a metal oxide or metal hydroxide or ammonia, can be used.

It is desirable that the binder or support resin (III) has a softening point of not less than 100 having ⁰ C, but preferably higher than 130 ⁰ C. If the softening point of the resin support is of the (III) is less than 100 ⁰ C, there is a tendency that the printing ink prepared therefrom for stray mist formation and leads to blocking and that the drying rate of the ink is extremely reduced.

It is desirable that the acid value of the carrier resin (III) is 5 to 50, preferably 5 to 20. When the acid value of the resin (III) is below the above-mentioned range, the printing ink produced therefrom shows poor solubility. On the contrary, if the acid value of the resin (III) exceeds the above-mentioned range, its solubility in paraffin solvents is lowered and the offset printing ink produced therefrom has poor resistance to emulsification.

The offset printing ink according to the invention can be used using the carrier resin (III) modified with an acid and a phenolic resin in the manner described above can be prepared according to a known method. For example, 100 parts by weight of the carrier or binder resin (III) at room temperature or with heating in a mixture of 50 to 200 parts by weight of a high boiling point Hydrocarbon solvent and 0 to 150 parts by weight, preferably 5 to 50 parts by weight, one

drying oil for the production of a paint dissolved _? which has a viscosity of 200 to 600 poise (20 to 60 Pa.s) at room temperature. A printing ink according to the invention can be obtained by adding one or more pigments to the lacquer and kneading them in with the aid of rollers or other kneaders.

The hochsiedendenJKohlenwasserstoff-solvents which can be used according to the invention should have boiling points in the range of 200 to 35O ⁰ C, preferably 250 to 330 include ⁰ C and its content of aromatic compounds should

not more than 50% by weight, but preferably less than ■ 30% by weight.

Particularly preferred solvents for the purposes of the invention are high-boiling paraffin solvents with boiling points in the range between 200 and 35O ° C, which contain practically no aromatic compounds. As an oil component In addition to drying oils, including linseed oil and tung oil, we can also use long-oil alky resins ». (long oil alkyd resins) be used.

The invention will now be described in more detail with reference to examples.

However, the examples are for illustrative purposes only and the invention is not intended to be limited to them.

25 Production example 1

820 g of 97 percent dicyclopentadiene and 180 g of hexene-1 were placed in an autoclave with a capacity of 2 liters and ^{heated to 260 °} C. for 5 hours under a nitrogen atmosphere with stirring. The autoclave was cooled after the heating was completed and the contents of the autoclave were distilled at 210 ° C / 266.6 Pa (2 mm Hg) to remove unreacted materials and oligomers. 893 g of a resin (1-1) remained in the autoclave. The softening point of the resin (1-1) was 139.0 ⁰ C.

• ^ 100 g of the resin (1-1) were ^{heated to 200 °} C. in order to melt it, after which 3.0 g. Maleic anhydride was added

and the mixture was 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) was 151.0 ° C. and its acid number was 13.7 p-tert.-octylphenol and formaldehyde was obtained, was added and reacted for 2 hours at 200 ⁰ C, whereby a binder resin (III-1) having a softening point of 173 "5 ° C and an acid number of 13.0 became.

Production example 2

760 g of 97 percent dicyclopentadiene and 240 g of decene-1 were placed in an autoclave having a capacity of 2 liters and reacted at 280 ° C. for 5 hours. The following procedures were carried out in the same manner as in Production Example 1, whereby 930 g of a resin (1-2) were obtained. The softening point of this resin (1-2) was 137.0 ⁰ C.

100 g of the resin (1-2) were ^{heated to 200 °} C. in order to melt this, after which 5.0 g of maleic anhydride were added and the mixture was reacted for 3 hours with stirring, whereby a modified resin (II-2), the modified with maleic anhydride was obtained. The softening point of the modified resin (II-2) was 152, ⁰ ° C, and its acid number was 24.3. Thereafter, to 82 (2-II) 3.0 g decanol added g of the modified resin and the mixture was heated 1st hour at 200 ⁰ C,

, ₀ after which 21 g of a resol type phenolic resin, which had been prepared by the condensation reaction of p-nonylphenol with formaldehyde, was added. The mixture was reacted at 200 ° C. for 3 hours to obtain a binder resin (III-2) having a softening point

35 of 165.5 was ⁰ C and an acid number of 19.6.

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Production example 3

790 g of 97 percent dicyclopentadiene vmd 210 g of an α-olefin mixture consisting of α-olefins having 6 to 10 carbon atoms (Dialene 610 from Mitsubishi Kasei Co. Ltd.) were placed in an autoclave with a capacity of 2 liters and implemented at 280 ⁰ C for 2.5 hours. The subsequent process steps were the same as in Production Example 1. In this manner, 920 g of a resin (1-3) with a softening point of 143.0 ⁰ C obtained.

100 g of the resin (1-3) was ^{heated to 200 °} C. to melt it, then 3 »0 g of maleic anhydride was added and the reaction was carried out for 4 hours with stirring to obtain a modified resin (II-3) . The softening point of the modified resin (II-3) was 155 ° C. and its acid value was 13.9. Then 85 g of the modified resin (II-3) were mixed with 15 g of a phenolic resin of the resol type, which had been produced by condensation of p-tert-butylphenol and formaldehyde, and reacted for 2 hours at 220 ^° C., with a binder resin was obtained (III-3) had a softening point of 183.5 ⁰ C and an acid number of 13.1.

Production example 4

The by-product C ^ fraction (boiling range 28 to 60 ⁰ C), which had been obtained in the process of steam cracking naphtha for the production of ethylene and propylene, was ^{heated to 120 0} C for 4 hours and distilled to remove the unreacted Cc -Fraction to remove. In this way a mixture was obtained which contained 85% dicyclopentadiene and which consisted for the remainder of codimers of cyclopentadiene with isoprene or piperylene. 850 g of this mixture containing 85% dicyclopentadiene and 150 g of decene-1 were placed in an autoclave with a capacity of 2 liters and reacted at 260 ° C. for 6 hours. The following process steps were the same as in Preparation Example 1. On this

840 g of a resin (1-4) with a softening point of 135 ^° C. were obtained.

10og of the resin (1-4) was heated to 200 ⁰ C, to melt it, then 4.0 g of maleic anhydride were added and the mixture was reacted for 4 hours with stirring, whereby a modified resin (II-4) was obtained, which was modified with maleic anhydride. The softening point of the modified resin (II-4) was 144.5 ° C and its acid value was 17.7. Thereafter, 90 g of the modified resin (II-4) were added to 3.0 g of 2-ethylhexanol and the mixture was heated to 200 ° C. for 1 hour with stirring from p-tert. -Octyl phenol and formalin had been obtained and the reaction was carried out for 3 hours at 200 ⁰ C, whereby a binder resin was obtained (III-4) having a softening point of 158.5 ⁰ C and an acid number of 16.0.

Comparative manufacturing example 1

1000 g of 97 percent dicyclopentadiene and 400 g. Xylene as a solvent was placed in an autoclave having a capacity of 2 liters and reacted at 260 ° C. for 2 hours. The following process steps were the same as in Preparation Example 1. In this way, 820 g of a resin (Ia) with a softening point of 150 ^° C. were obtained.

100 g of the resin (Ia) was ^{heated to 200 °} C. to melt it, then 3.0 g of maleic anhydride was added and the mixture was reacted for 4 hours to form a modified resin (II-a). The softening point of the modified resin (II-a) was 159-5 ° C. and its acid number was 13.0. Thereafter, 85 g of the modified resin (II-a) were mixed with 15 g of a phenolic resin of the resol type, which had been prepared by condensation of p-tert-octylphenol and formaldehyde, and reacted for 2 hours at 200 ^° C., with a binder -

Resin (III-a) obtained \ iurde, which had a softening point of 176.5 ^° C. and an acid number of 12.7.

Comparative manufacturing example 2

10og of the resin obtained in Preparation Example 1 (1-1) was heated to 200 ⁰ C, to melt it, and then a phenolic resin, 25 g of mixed resol type, which had been obtained by condensation of p-tert-octylphenol and formalin . The mixture was heated for 2 hours with stirring to 200 ⁰ C, whereby a resin (Ill-b) was formed with a softening point of 169.0 ⁰ C.

Comparative manufacturing example 3

800 g of 97 percent dicyclopentadiene and 200 g of 2,4-dimethyl-hepten-1 with a methyl side group bonded to a double bond, which had been obtained by trimerization of propylene, were placed in an autoclave with a capacity of 2 1 and 5 Implemented at 280 ⁰ C hours. The contents of the autoclave were distilled at 210 ° C / 266.6 Pa (2 mm Hg) to remove unreacted materials and oligomers. After the distillation, 780 g of a resin (Ic) remained in the autoclave. The softening point of the resin (Ic) was 145 ° C

² ^ 100 g of the resin (Ic) was heated to 200 ° C. to melt it, mixed with 3.0 g of maleic anhydride and reacted for 4 hours to form a modified resin (II-c). The softening point of the modified resin (II-c) was 158.0 ⁰ C and its acid number was 14.0.

Then 85 g of the modified resin (II-c) were mixed with 15 g of a phenolic resin of the resol type, which had been produced by condensation of p-tert-octylphenol and formaldehyde, and ^{reacted at 200 °} C. for 2 hours. In this way, a binder resin (III-c) with a softening puj
number of 13.0 received.

with a softening point of 178.0 ⁰ C and an acid

Paints were made using the binder resins (III-1) to (III-4) and (III-a) to (III-c) used in the preparation examples 1 to 4 and Manufacturing Comparative Examples 1 to 3, and further below Use of the modified resin (II-1) obtained in Production Example 1 and a comparative resin manufactured. Using these varnishes, printing inks were produced, the properties of which were tested. The test results are shown in Table 1 below under the heading of Examples 1 to 4 and Comparative Examples 1 to 5.

Manufacture of varnish; .

50 g each of the binder resins were mixed with 10 g of linseed oil and 20 to 40 g of a high boiling paraffin solvent (NISSEKI Solvent no. 0-H according to the following note 1) mixed and heated to 180 ⁰ C, to melt the resin. In this way, a varnish having a viscosity of 30 to 40 Pa.s (300 to 400 poise) was prepared.

Manufacture of printing ink;

Using each of the varnishes, a printing ink was made according to the following recipe using a mixing roller arrangement, consisting of 3 rollers.

Ink formulation;

Pigment (corresponding to carmine 6B

Note 2) below 14 g

Lacquer '50 g

Solvent (NISSEKI Solvent No. 0-H) 15g

Test method and test results obtained for the properties of the printing ink;

Shine; 0.4 ml of each ink was applied to art paper using the RI Tester (see Note 3 below) and applied for 10 seconds in

an oven maintained at 15O ⁰ C dried. The gloss of the dried paint was measured with the help of a 6O degree 6O degree

Gloss meter determined.

Drying time; 0.4 ml of each ink was applied using the above mentioned RI tester on parchment paper and dried in a room kept at 150 ⁰ C oven. The time required for the paint to reach the stage where the paint did not stick to the fingers was then measured.

Stray mist formation; 2.4 ml of each ink was placed on an inkometer rotating at 1200 tJpm (Note 4 below). Splashing of the paint onto art paper arranged next to the roller was observed after 3 minutes had elapsed.

Emulsion properties of color; Water was added to each of the prepared inks to emulsify the ink, and the flowability of the emulsified ink was determined. Offset printing inks are generally partially emulsified when they come into contact with water in the printing stage. Only the paints that give emulsions with good flowability can be used for practical purposes.

Note 1: Pure paraffinic hydrocarbon solvent with a boiling range from 250 to 265 ^° C., which does not contain any aromatic compounds (product of Nippon Oil Company Limited).

Note 2: Manufactured by Toyo Ink Mfg. Co., Ltd.

Note 3: Test device for checking the printability, manufactured by Akira Seisakusho Co., Ltd.

35 Note k% Manufactured by Toyo Seiko Co., Ltd.

Use τ viscosity Appearance Table 1 Drying scatter mist will
cloudy obtain worse 52 8th not obs Emulsifying no printing ink from this 361 I. t <ι !. OO ι it resin d.Lackes d.Lackes Time hue respect properties of (f at (Pa.s) 25 C. shine printed (see) will 66 6th not obs. colour OJ
in:
CZ
OC game Poise d. be area 41 cloudy 7th not obs. observed bad I ■ ' III-1 53, .7 (537) clear 71 clear 6th not obs. Well 50 ι ■ · 1 III-2 58.1 (581) clear 67 will Well observed bad ¹ III-3 58.9 (589) clear 67 cloudy Well ; ''; ' ; 2 III-4 52.8 (528 clear 65 Well not obs. a bit low 3 The solubility of the resin in a paraffin solvent was so bad ¹ 4th III-a that no clear varnish was and Ver could be presented not obs. a little-little gl. Rosin modified phenolic resin available from Arakawa at- ill-b 55.1 (551) 17th Chemical Co. Ltd., under the trade name Tamanol No. sp.1 Ver
gl. b.2 ii-1 51.6 (516) 12th Ver Control 58.6 (586) 7th gl. resin* b.3
See. b.4 III-c 57.0 (570) 10 See. * Note: control resin: b. 5

As shown in Examples 1 to 4 given in Table 1, the offset printing inks according to the invention lead to an excellent gloss and have good emulsifiability, good drying properties and good Properties with regard to the formation of scattered fog. From Table 1 it is clear that the binder resins according to the invention excellent offset printing inks result, when they are dissolved in paraffinic solvents.

As can be seen from Comparative Example 1, a binder resin containing no α-olefin cannot be used uniform ink composition can be prepared because of the solubility of such a resin in solvents bad is.

Comparative Example 2 is a comparative ink made using a resin that is not modified with an acid. This example shows that the drying and emulsifying properties of such Color are deteriorated because the modification reaction with a phenolic resin is incomplete, whereby a resin is obtained whose softening point is too low.

In Comparative Example 3, a resin is used which has not been modified with a phenolic resin. This comparative example shows that such a resin is not suitable for Preparation of a printing ink suitable for practical use can be used because the printing ink is unsatisfactory in terms of gloss, drying time and emulsifying property.

In Comparative Example 4, an ink is used made of a rosin modified phenolic resin that has excellent solubility in a paraffinic Owns solvent. When this comparative example is compared with the inventive examples it should be noted that the emulsifying properties of the offset printing inks according to the invention compared with these conventional printing ink in which a rosin-modified phenolic resin is used.

J I «5ZUÖ I

The binder resin used in Comparative Example 5 is made using 2,4-dimethyl-hepten-1, the one Has branching at a double bond, as a-01efin, produced. From this comparative example it can be seen that a connection with a branch. a double bond is relatively inactive and is hardly introduced into the resin. As a result, the solubility of the formed Resin is unsatisfactory in paraffinic solvents, making it difficult to obtain a clear varnish. It can also be seen that the gloss of the printed area is not satisfactory.

Production example 5

850 g of 97-percent dicyclopentadiene and 250 g of linseed oil were placed in an autoclave having a capacity of 2 1 and 3.5 hours with stirring in a nitrogen atmosphere to 26O ⁰ C heated. The autoclave was cooled after the heating was completed, and the contents of the autoclave were distilled at 210 ° C / 266.6 Pa (2 mm Hg) to remove unreacted materials and oligomers. 920 g of a resin (1-5) remained in the autoclave. The softening point of the resin (1-5) was 136.5 ° C.

150 g of the resin (1-5) was heated to 200 ⁰ C, to melt um.es, then mixed with 4.5 g of maleic anhydride and reacted for 4 hours with stirring to give a modified resin was obtained (II-5), which was modified with maleic anhydride. The softening point of the modified resin (II-5) was 147.0 ° C. and its acid value was 13.5. Thereafter, 100 g of the modified resin (II-5) with 17.6 g of a resol type phenol resin is mixed, which had been prepared by condensation reaction between p-tert.-octylphenol and formaldehyde, and reacted for 2 hours at 200 ⁰ C, wherein a binder resin (III-5) was obtained which had a softening point of 169.5 ° C and an acid value of 12.7.

Production example 6

800 g of 97 percent dicyclopenta diene and 200 g of tall oil were placed in an autoclave with a capacity of 2 liters and reacted at 260 ° C for 6 hours. The subsequent process steps were carried out in the same manner as in Preparation Example 5, wherein 925 g of a resin (1-6) was obtained. The softening point of this resin (1-6) was 138.5 ° C.

150 g of the resin (1-6) were ^{heated to 200 °} C. in order to melt it, mixed with 7.5 g of maleic anhydride and reacted for 3 hours with stirring to obtain a modified resin (II-6) which was obtained with Maleic anhydride was modified. The softening point of the modified resin (II-6) was 158 ^° C. and its acid number was 24.2. Thereafter, 100 g of the modified resin became (11-6). 4.2 g of decanol were added and the mixture was ^{heated to 200 °} C. for 1 hour while stirring. Thereafter, 20.2 g of a resol type phenolic resin, which had been produced by condensation of p-nonylphenol and formaldehyde, were added and the mixture was ^{reacted for 3 hours at 200 °} C., a binder resin (III-6) being obtained, which had a softening point of 160.5 ° C and an acid number of 19.4.

25 Production Example 7

800 g of 97 percent dicyclopentadiene, 100 g of linseed oil and 100 g of hexene-1 were placed in an autoclave with a capacity of 2 liters and reacted at 280 ° C. for 2 hours. The following procedures were carried out in the same manner as in Preparation Example 5, 932 g of a resin (1-7) was obtained, which had a softening point of 146 C ⁰ O,

150 g of the resin (1-7) were ^{heated to 200 °} C. in order to melt it, mixed with 4.5 g of maleic anhydride and reacted for 3 hours with stirring, a resin (II-7) modified with maleic anhydride being obtained.

I JZUÖ I

The softening point of the modified resin (II-7) was 155tO ⁰ Cuttci its acid number was 13.7. Subsequently, 100 g of the modified resin (II-7) were mixed with 17.6 g of a phenolic resin of the resol type, which had been prepared by condensation of p-tert-octylphenol and formaldehyde, and ^{reacted for 2 hours at 200 °} C., with a binder-resin was obtained (III-7) that had a softening point of 175.0 ⁰ C and an acid number of 12.2.

10 Production example 8

The Cc by-product fraction (boiling range 28 to 60 ° C), which was obtained in the process of producing ethylene and propylene by steaming naphtha, was ^{heated to 120 0} C for 4 hours and distilled to remove the unreacted C ^ - To remove fraction, a mixture was obtained which consisted of 85% of dicyclopentadiene and the remainder of codimers of cyclopentadiene with isoprene or piperylene. 850 g of this mixture containing 85% dicyclopentadiene and 250 g of linseed oil were placed in an autoclave having a capacity of 2 liters and reacted at 260 ° C. for 4 hours. The subsequent procedures were carried out in the same manner as in Preparation Example 5, 872 g of a resin (l ~ 8) having a softening point of 137.0 ⁰ C

25 were obtained.

150 g of the resin (1-8) were ^{heated to 200 °} C. to melt it, mixed with 5.3 g of maleic anhydride and reacted for 4 hours with stirring to obtain the modified resin (II-8). The softening point of the modified resin (II-8) was 148.5 ⁰ C and the acid value of this resin was 16.9.

Thereafter, 100 g of the modified resin (II-8) was mixed with 3.0 g of 2-ethylhexanol and heated for 2 hours with stirring at 200 ⁰ C .. Then, 18.2 g of a resol type phenolic resin, p, by condensation of -tert.-octylphenol and formaldehyde had been produced,

sets imd the mixture was ^{reacted for 2 hours at 200 0} C, whereby a binder resin (III-8) was obtained, which a softener
of 14.1 had.

a softening point of 157.5 ⁰ C and an acid number

Comparative manufacturing example 4

1000 g of 95 percent dicyclopentadiene and 400 g of xylene as a solvent were placed in an autoclave with a passability of 2 liters and reacted at 260 ° C. for 3 hours. The following procedures were carried out in the same manner as in Preparation Example 5 to obtain 800 g of a resin (Id) with a softening point of 152.0 ⁰ C were obtained.
150 g of the resin (Id) were ^{heated to 200 °} C. in order to melt it, mixed with 5.3 g of maleic anhydride and reacted for 3 hours with stirring, a modified resin (II-d) being obtained. The softening point of the modified resin (II-d) was 165.0 ° C. and the acid number of this resin was 16.5. 100 g of the modified resin (II-d) were then mixed with 3.0 g of decanol and ^{heated at 200 °} C. and stirred. Then, 18.2 g of a resol type phenolic resin prepared by condensing p-tert-octylphenol and formaldehyde was added, and the mixture was reacted at 200 ° C. for 2 hours to obtain a binder resin (III-d) which was one Expansion
13.9 had.

sets and the mixture was reacted for 2 hours at 200 C, a softening point of 170.5 C and an acid number of

Comparative manufacturing example 5

100 g of the resin obtained in Production Example 5 (1-5) were heated to 200 ⁰ C, to melt it, and 17.6 g of a resol type phenol resin mixed, the prepared by condensation of p-tert-octylphenol and formaldehyde had been. The mixture was heated 2 hours with stirring at 200 ⁰ C, whereby a binder resin (III-e) having a softening point of 155, was obtained O ⁰ C.

3 Ί 3208 Ί

Varnishes vTurden tinter use of carrier resins (III-5) to (III-8) and (III-d) to (III-e) used in the preparation examples 5 to 8 and in the manufacturing comparative examples 4 and 5 were obtained, as well as using the modified resin (II-5) and of a control resin. Printing inks were using these varnishes, and the properties of these inks were examined. The test results are in the following Table 2 under the details Examples 5 to 8 and Comparative Examples 6 to 9 listed.

Manufacture of varnish;

50 g of each of the binder resins were mixed with 20 g of linseed oil and heated at 240 ° C. for 90 minutes. Then became a suitable amount in the range of 20 to 40 g of a petroleum hydrocarbon solvent (NISSEKI Solvent No. 5 - Note 5 below) added to the viscosity of the paints formed within a range of 50.0 to 60.0 Pa. s (500 to 600 poise).

Making the paint:

Using each of these varnishes, a printing ink was produced according to the recipe given in the following, For which a mixing roller arrangement consisting of 3 rollers was used.

Recipe of paint;

Pigment (carmine 6B - note 2)
paint

Solvent (NISSEKI Solvent No. 5)

Wax compound dryer (cobalt naphthenate)

14th G 50 G 5 G 2 G 0 , 3 g

Test methods for the properties of color and test results;

Shine; 0.4 ml of each color was applied to art paper using the RI tester (referring to Note 3 above) and allowed to stand for 24 hours. The gloss of the dried paint was determined using a 60-degree-60-degree gloss meter.

Setting time; 0.4 ml of each color was applied to a sheet of art paper using the aforementioned RI tester, and another blank sheet of art paper was placed on the painted area and pressed using the roller of the RI tester. The time interval from the time the paint was applied to the time the blank sheet of art paper was placed on the painted area was varied to determine the time interval required for the paint not to be more adhered to the blank sheet of art print paper.

Stray fog formation; 2.4 ml of each color was applied to the inkometer rotating at 1200 TJpm (note 4 above). The spraying or dusting of paint onto an art paper arranged next to the roller was observed after the lapse of 3 minutes.

Drying time; 0.4 ml of each color was applied to a sheet of art paper using the above-mentioned RI tester, and the time required for the paint to dry was determined using a test device to determine the dryness of the paint (Note 6 below ).

Emulsifying properties of the ink: Water was added to each of the resulting inks to emulsify the ink and the flowability of the emulsified ink was determined. Offset inks are generally partially emulsified when they are in the printing stage with water Only those inks that give emulsions with good flowability can be used for practical application.

10

Control resin; A rosin modified phenolic resin manufactured by Dainxppon Ink & Chemical Co. Ltd., commercially available under the tradename Beckacite 1126HV.

Note 5: A solvent for printing ink with a boiling range of 276 to, 311 ° C, with a content of 23% by weight of aromatic compounds by Nippon Oil Co. Ltd.

20th

Note 6: Tester. Manufactured by Toyo Seiki Co., Ltd.

Table 2

Example used viscosity of the

Lacquer (Pa.s, 25 C).

resin

(Poise) '

Gloss of the solidification, drying, scattering emulprinted time (h) nebula- tion area time formation intrinsic

(min) shafts

d. colour

Ex. 5 III-5 57.0 (570) 61 6th 3.0 not be
watch out Well Ex. 6th III-6 55.0 (550) 62 6th 3.0 not loading
watch out Well Ex. 7th III-7 56.0 (560) 66 8th 3.0 not be
watch out Well Ex. 8th III-8 52.0 (520) 62 6th 3.0 not be
watch out Well Cf.
ex. 6th III-d 51.0 (510) ' 46 7th 3.0 watch
tet some
small amount Cf.
example « 7th Ill-e 57.0 (570) 46 6th 3.0 watch
tet some
small amount Cf.
ex. 8th II-5 59.0 (590) 44 10 4.5 watch
tet small amount Cf.
ex. 9 Control
resin 55.0 (550) 57 6th 3.0 not be
watch out some
small amount

3 1 J 2 U Ö Ί

Examples 5 ″ to 8 shown in Table 2 can be used clearly shows that the offset printing inks according to the invention excellent in terms of gloss and good in terms of emulsifiability, the lack of scattering mist formation, the setting and drying properties are.

In contrast, a printing ink in which a carrier resin which contains neither a drying oil nor a fatty acid component is unsatisfactory in that the The printed surface has poor gloss and the color shows scattering mist formation and, in this, that the emulsifying properties are unsatisfactory, as can be clearly seen from Comparative Example 6 shown in the table.

Comparative Example 7 is an example of a printing ink composition made using a resin that does not modify with an acid became. This example shows that the gloss and the emulsifying properties of such a paint are unsatisfactory and that the resin leads to the formation of scattered fog.

In Comparative Example 8, a resin that was not modified with a phenolic resin was used. This comparative example shows that one using such Resin-made printing ink unsatisfactory in terms of gloss. Solidifying, drying and emulsifying properties

25 shafts and leads to the formation of scattered fog.

In Comparative Example 9, a paint is prepared using a known control resin that is commonly used is applied in the field. This well-known resin is a phenolic resin modified with rosin.

By comparing the examples according to the invention with this comparative example, it can be seen that the gloss and the Emulsification properties of the offset printing inks according to Invention are improved over the corresponding properties of the conventional printing ink that are used of the well-known phenolic resin modified with rosin was obtained.

- 3>

Although the invention has been described on the basis of exemplary embodiments, it is clear that they are not is limited to this.

Claims (3)

PATENT CLAIMS: 1. Offset printing ink containing a binder resin (III) obtained by reacting 5 "to 100 parts by weight of a phenolic resin (component D) with 100 parts by weight of a modified resin (II) formed by modification with an acid, the phenolic resin (Component D) by condensation of a phenol containing an alkyl group with 4 to 9 carbon atoms as a substituent, with formaldehyde - and using a modified resin (II) obtained by modification with an acid, which is obtained by reacting 1 to 15 parts by weight .. ^ a component C from the group of unsaturated carboxylic unsaturated carboxylic anhydrides and mixtures acids _v, such compounds, with 100 parts by weight of a resin (I) is produced, which by copolymerization of 5 to 100 parts by weight of component B selected from the group straight-chain α-01efine, drying oils, fatty acids and mixtures of such compounds with 100 parts by weight of a r five-membered cyclic compound (component A), which contains conjugated double bonds and due to the general my formula ^ 01 is represented, in which H is a hydrogen atom, R is a Alkyl group with 1 to 3 carbon atoms, m and η Ο or integers not less than 1 and satisfy the relationship m + η = 6, and / or a Diels-Alder addition product thereof, will be produced. 2. Offset printing ink according to claim 1, characterized in that it also contains from 50 to 200 parts by weight of a hydrocarbon solvent having a boiling point of 200 to 55O ⁰ C and 0 to 150 parts by weight of a drying oil, wherein the hydrocarbon solvent has a content of of aromatic compounds of less than 50% by weight. 3. Offset printing ink according to claim 2, characterized in that it is used as a hydrocarbon solvent contains a paraffin solvent.