JP2015160918A - lithographic printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing Indian ink that solves a problem of poor dispersibility relating to wettability of conventional carbon black, such as aggregation property of carbon black, by improving wettability of carbon black, and thereby, that has increased dispersibility of the ink and has excellent fluidity, transferring property, and stability, deposition property and stability with time on a printing machine, and to provide a printed matter using the ink.SOLUTION: In the lithographic printing Indian ink, wettability of carbon black is improved by using the following varnish and an indigo pigment derivative, and thereby problems relating to dispersibility of the ink is solved. The obtained ink has excellent fluidity, transferring property, and stability, deposition property and stability with time on a printing machine. The varnish is obtained by dissolving a gilsonite resin (having a softening point of 135°C to 205°C) comprising a specific aliphatic hydrocarbon extracted from hard asphalt that exists in the nature, in the presence of a petroleum resin and a fatty acid ester. A printed matter is obtained by printing with the above ink.

Description

  The present invention uses a dissolved component obtained by dissolving a gilsonite resin having a softening point of 135 ° C. to 205 ° C. extracted from natural asphalt in the presence of a petroleum resin and a fatty acid ester, and a specific phthalocyanine derivative, thereby providing an excellent carbon. The present invention relates to a black ink for lithographic printing which can obtain black wettability and is excellent in fluidity, low tackiness, transferability and on-machine stability.

  In black ink for lithographic printing, carbon black is generally used as a pigment. In offset printing, since the ink film thickness on the paper after printing becomes thin, the blending ratio of carbon black is usually as high as 10 to 30% in order to ensure the printing density. For this reason, it is difficult to disperse carbon, and ink is produced by improving the performance of a disperser or using easily dispersible carbon black.

In recent years, a solvent in which aromatic hydrocarbons are made non-aromatic components by hydrogenation is used for printing ink from the environmental aspect, and it has become the main environmentally friendly ink. In particular, a solvent containing three or more polycyclic aromatic hydrocarbons has been pointed out as a problem in environmental health.
As an environmentally friendly ink standard, the Japan Environment Association has certified the “Eco Mark”. The “Eco Mark” label can be displayed on the ink label for those certified by the Eco Mark Secretariat.
According to the certification criteria of the Eco Mark Office of the Japan Environment Association, the solvent for aromatic components is less than 1% by volume as the solvent used in ink.
Currently in Japan, printing inks certified by “Eco Mark” that clear this standard are mainly used.

  In order to maintain the stability of the ink during high-speed printing, the lithographic printing ink needs to suppress the evaporation of the solvent on the printing press, and it is indispensable to use a high boiling point solvent. For this reason, a solvent having a high boiling point during petroleum refining is desired. However, since the high boiling point solvent has a high aromatic component content, a non-aromatic solvent from which this aromatic component has been removed is currently used.

  However, a solvent mainly composed of non-aromatic components has a high aniline point and has a problem of solubility in a resin. In particular, many non-aromatic solvents with a high boiling point have an aniline point of 120 ° C or higher, and when they are made into inks, drying and fluidity deteriorate due to poor solubility in the resin, resulting in stable deterioration and transition on the machine. Troubles in printing such as defects occur.

  In lithographic printing, dampening water is supplied to the non-image area, and an image is formed by utilizing the ink repellency. The ink is emulsified in this dampening water and transferred between the rollers. Since printing is performed on paper, the fluidity of the emulsified ink emulsified in the ink and the fountain solution greatly affects the transferability between the rollers and the inking property on the paper. Ink using carbon black has a problem that if the wettability of carbon black is poor, the fluidity of the ink and the emulsified ink is inferior, so that the transfer between rollers and the inking property on paper are inferior.

  On the other hand, vegetable oils based on fatty acid esters have good resin solubility and low volatile content. In lithographic printing inks that use an oxidation polymerization type drying method, vegetable oils mainly composed of unsaturated fatty acid esters called drying oils are used, and after printing, a film is formed by oxidative polymerization of unsaturated portions in fatty acids. Is established. However, when the vegetable oil content is increased, the solvent is hardly removed due to excessive resin solubility, and the drying property after printing (hereinafter referred to as a set) is deteriorated. On the other hand, since the ratio of unsaturated components in the ink increases, the ink itself tends to form a dry film on the surface and the workability deteriorates.

  In general, in lithographic printing inks that use oxidation polymerization or osmotic drying type drying systems, increasing the content of drying oil contributes to improved on-machine stability, but is set due to slow solvent removal from the resin. Deteriorates. On-machine stability refers to the degree of fluidity degradation due to solvent evaporation on an ink printer. The ink performance is excellent when there is little fluid deterioration or long time until fluidity is deteriorated.

  The drying mechanism of osmotic drying type lithographic printing ink is that the solvent or vegetable oil that makes up the printing ink penetrates into the fiber part of the paper by capillary action, and some solid matter of pigment and resin on the paper surface. The drying method is used to form a solid film image.

The drying mechanism of the heat-set type lithographic printing ink employs a drying method in which a solvent in the ink is dried using a heating oven (dryer) to form a solid film.
The drying mechanism of the oxidation polymerization type lithographic printing ink employs a drying method in which the drying oil in the ink is oxidized and polymerized with oxygen in the air to form a solid film.

  Regarding the production method of lithographic printing ink, the dispersion of carbon black is important. That is, when the dispersion of carbon black is poor, problems such as significant gloss deterioration and accumulation of carbon particles on the plate, guide roll, etc. during printing occur.

  For this reason, various studies have been made to improve the dispersibility of carbon black.

Japanese Patent Application Laid-Open No. 11-349911 discloses carbon black having good dispersibility in a mineral oil having a low polycyclic aromatic component content. However, when an ink is produced, such a mineral oil is simply added. Just having good dispersibility does not necessarily mean good physical properties as an ink.
Furthermore, the following examples can be given as examples in which carbon black is used as the black pigment as in the present invention and rosin-modified phenol resin is used as the resin varnish.

  That is, JP-A-9-25444 uses carbon black as a black pigment, rosin-modified phenolic resin as a resin varnish, and an example of using a black ink composition for offset printing using a pigment dispersant. It is disclosed. However, although the stability (dispersibility) of the printing ink is improved, a high-quality printed matter cannot be obtained simply by selecting carbon black.

  In JP-A-2002-322407, JP-A-2002-322408, and JP-A-2002-327143, carbon black and a resin varnish that is solid at room temperature are preliminarily dry-ground and added with a solvent or the like. A method of mixing and manufacturing is disclosed. Moreover, although it is described that specific carbon black is used, when these carbons are used and this manufacturing method is performed, the structure is destroyed, such as uncoated paper or finely coated paper. It is not suitable for low-grade paper applications.

  Thus, in an environmentally friendly ink using a non-aromatic solvent, it is very difficult to optimally disperse carbon black.

Japanese Patent Laid-Open No. 9-25444 JP 2002-322407 A JP 2002-322408 A

  The present invention improves the dispersibility of ink by improving the wettability of carbon black, and uses a black ink for lithographic printing excellent in fluidity, low tackiness, transferability, and on-machine stability, and An object is to provide a printed matter obtained by printing. Furthermore, it aims at providing the lithographic printing ink etc. with a small environmental load.

  As a result of sincere research to solve the above problems, a dissolved component obtained by dissolving a gilsonite resin having a specific softening point extracted from natural asphalt in the presence of petroleum resin and fatty acid ester and a specific phthalocyanine derivative are used. This makes it possible to significantly improve the wettability of carbon black, solve the problem of ink dispersibility, and provide ink for lithographic printing with excellent fluidity, low tack, transferability and on-machine stability. The headline, the present invention has been reached.

  That is, the present invention has a content of pigment, 1 gyrsonite resin having a softening point of 135 ° C. to 205 ° C. extracted from natural asphalt, petroleum resin, synthetic resin, phthalocyanine derivative, and aromatic hydrocarbon. The present invention relates to a black ink for lithographic printing containing a petroleum solvent of not more than% by weight, a fatty acid ester, and a vegetable oil.

Further, the present invention is based on the total amount of ink.
Gilsonite resin having a softening point of 135 ° C. to 205 ° C. extracted from natural asphaltum is 0.5 to 20% by weight,
Petroleum resin is 0.2 to 30% by weight,
5-40% by weight of synthetic resin
And 0.3 to 10% by weight of fatty acid ester
It is related with the said black ink for lithographic printing characterized by these.

  The present invention also relates to the black ink for lithographic printing according to claim 1 or 2, wherein the phthalocyanine derivative is a compound represented by the following general formula (1).

General formula (1)

Pc- (XY) m

(Wherein Pc represents a phthalocyanine residue,
X represents —CH ₂ —, —OCO—, or —SO ₂ CH ₂ —,
Y represents —NH— (CH ₂ ) _n —NR ₁ R ₂ or — (CH ₂ ) _n —NR ₁ R ₂ .
R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. Here, R ₁ and R ₂ may be combined to form a heterocyclic ring containing a nitrogen atom.
n represents an integer of 0 to 3.
m represents an integer of 1 to 4. )

  The present invention also relates to the above-described black ink for lithographic printing, wherein the content of the phthalocyanine derivative is 0.05 to 1% by weight with respect to the total amount of indigo ink for lithographic printing.

  The present invention also relates to the above-described black ink for lithographic printing, wherein the synthetic resin is a rosin-modified phenol resin.

In the present invention, the rosin-modified phenol resin is
1) Weight average molecular weight 10,000 to 200,000
2) Tolerance is 20 to 49% by weight
The above-described black ink for lithographic printing.

In the present invention, the petroleum solvent is 1) The aniline point is 60 ° C to 130 ° C.
2) Boiling point is 240 ° C to 400 ° C
The above-described black ink for lithographic printing.

The present invention also provides:
The present invention relates to a printed matter obtained by printing the lithographic ink.

  In printing of newspapers, books, leaflets, etc., the indigo ink for lithographic printing provided by the present invention is a problem in a production method that greatly simplifies the conventional pigmentation process, and is due to the primary aggregation of pigments when converted into ink. The problem of ink smear has been solved, and it is possible to provide printability and stability over time that are excellent in fluidity, low tackiness, transferability, and on-machine stability, and the industrial value is enormous.

  Next, the present invention will be described more specifically with reference to preferred embodiments.

  Gilsonite of the present invention is a resin composed of aliphatic hydrocarbons extracted from natural asphalt, and contains a slight amount of aromatic hydrocarbons, ash and light fractions.

  This gilsonite is further refined to completely remove aromatic hydrocarbons, ash, and light fractions, which is called ER-125 resin, which has a low softening point of 120 ° C to 125 ° C and is effective for carbon wetting. is there. However, ER-125 resin consumes enormous energy for purification, so it is obvious that the load on the environment is large. Accordingly, there is a demand for improving the wettability to carbon without purification. In the present application, if the ER-125 resin is used, the reduction of the environmental load, which is the subject of the present invention, cannot be solved, so the ER-125 resin is out of the scope of the study.

  Problems with the gilsonite resin that has not undergone purification are problems of viscosity instability and clogging during filtration due to aggregates.

  Since conventional lithographic printing inks use a solvent containing an aromatic component, even a gilsonite resin that has not undergone purification can be dissolved. Therefore, the above problems of instability of viscosity and clogging during filtration due to aggregates are difficult to occur. The conventional solvent containing an aromatic component is considered to be because the aniline point is very low and the solubility of the resin is high.

  However, solvents containing aromatic components are subject to regulation in countries around the world because of their large environmental impact, and efforts are being made to switch to solvents that do not contain aromatic components. However, a solvent that does not contain an aromatic component has a high aniline point, and it is very difficult to dissolve the gilsonite resin without purification.

  In the present invention, by simultaneously using a petroleum resin, a fatty acid ester, and a solvent that does not contain an aromatic component, the gilsonite resin can be dissolved to solve the above-described problems.

  The gilsonite resin used in the present invention is a product of American gilsonite under the trade name of natural hydrocarbon resin (natural asphaltum) produced in Utah, USA.

  In the present invention, the gilsonite resins having different softening points used in the verification in the examples were used by mixing products having different softening points and adjusting the softening points. Specifically, “Gilsonite Select 325A (manufactured by American Kangil Sonite)” whose softening point is usually 130 ° C. to 170 ° C. and “Gilsonite Select 437 (American) whose softening point is usually 160 to 205 ° C. After obtaining several lots of two types of resins “manufactured by Kangilsonite Co., Ltd.” and investigating the softening point of each resin, the softening point can be adjusted by mixing these resins.

  As described above, since the gilsonite resin is a natural product, the deflection width of the softening point is large. Therefore, the Gilsonite having a softening point of 210 ° C. described in the Examples of the present application was selected by adjusting a lot (210 ° C. or higher) having a high softening point from several lots of Gilsonite Select 437.

  The softening point was measured by the ring and ball method. The measurement of the softening point by the ring-and-ball method is a method widely used in the standard test method, and JIS K 2046 can be mentioned. Specifically, a brass ring filled with a sample is held horizontally in a water bath, a steel ball of a constant weight is placed on the center of the sample, the bath temperature is increased at a constant speed, the sample gradually softens, and the steel ball is The softening point is determined by the reading of the thermometer when it descends and finally reaches the bottom plate at a thickness of 25 mm.

  The addition amount of the gilsonite resin of this invention is 0.5 to 20 weight% with respect to the printing ink whole quantity, Preferably it is 1.0 to 15 weight%. If it is less than the lower limit of the above numerical value, the carbon black is poorly wet and the fluidity is insufficient, and if it exceeds the upper limit of the numerical value, the inking property of the ink emulsified in the fountain solution is deteriorated.

  The petroleum-based solvent used in the present invention has an aromatic hydrocarbon content of 1% or less, an aniline point of 60 to 130 ° C, preferably 80 to 100 ° C, and a boiling point of 240 ° C to 400 ° C, preferably 270. It is a petroleum solvent in the range of from ℃ to 350 ℃. When the aniline point is higher than 130 ° C., the solubility of the gilsonite resin is deteriorated and the ink cannot be formed. On the other hand, when the aniline point is lower than 60 ° C., the gilsonite resin is dissolved, but the ability to dissolve is too high.

In the present invention, the phthalocyanine derivative represented by the general formula (1) is a metal phthalocyanine or metal-free phthalocyanine derivative such as copper, nickel, cobalt, aluminum, iron, zinc, manganese, or neodymium. Furthermore, a metal halide having a valence of 3 or more may be used as the central nucleus of phthalocyanine.
Phthalocyanine derivatives are produced by a method known per se, but are synthesized using phthalocyanine raw materials such as phthalonitrile, phthalic acid, phthalic anhydride, phthalimide, etc., which have a substituent on the benzene nucleus. It can be produced by modifying the substitution or later modifying the phthalocyanine.
Next, an example of a synthesis example of a phthalocyanine derivative will be briefly described.

_{CuPc- [SO 2 (CH 2)} n -N (R 1 R 2)] m

(Wherein CuPc represents a copper phthalocyanine residue,
R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. Here, R ₁ and R ₂ may be combined to form a heterocyclic ring containing a nitrogen atom.
n represents an integer of 0 to 3.
m represents an integer of 1 to 4. )

The compound represented by can be obtained, for example, by dissolving copper phthalocyanine in chlorosulfonic acid, reacting with a chlorinating agent such as thionyl chloride to obtain sulfonic acid chloride, and then reacting with amines according to a known method. it can.

  Typical amines that can react with sulfonic acid chloride are diethylamine, piperidine, N, N-diethylaminopropylamine, N, N-dimethylaminopropylamine, N, N-diethylamine, NN-dibutylaminopropylamine, N-amino. Propylmorpholine, N-aminoethylpiperidine, N-aminoethylpyrrolidine, NN-diisobutylaminopentylamine, N, N-dimethylaminopentylamine, N-aminopropyl-2-pipecoline, N, N-diethyl-N- And oleylethylenediamine.

Also,

_{CuPc- [OCO- (CH 2) n} -N (R 1 R 2)] m

(Wherein CuPc represents a copper phthalocyanine residue,
R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. Here, R ₁ and R ₂ may be combined to form a heterocyclic ring containing a nitrogen atom.
n represents an integer of 0 to 3.
m represents an integer of 1 to 4. )

The phthalocyanine derivative represented by can be obtained by esterifying copper phthalocyanine introduced with a carboxyl group with an alcohol according to a known method.

  As alcohols, for example, N, N-diethylaminoethanol, N, N-dimethylaminopropanol and the like can be used.

  Copper phthalocyanine is generally obtained by heating phthalic anhydride, urea and cuprous chloride in an aromatic solvent in the presence of a catalyst such as ammonium molybdate. Alternatively, pipemellitic anhydride can be added and reacted in the same manner to obtain a copper phthalocyanine having a carboxyl group. The thus obtained carboxyl phthalocyanine-containing copper phthalocyanine is esterified with the above alcohols and then converted into a carboxylic acid chloride with a chlorinating agent such as thionyl chloride in an aromatic solvent such as benzene, and then the same amine as described above. A phthalocyanine derivative is obtained by reacting with a phthalocyanine.

Also,

_{CuPc - [- (CH 2)} n -N (R 1 R 2)] m

(Wherein CuPc represents a copper phthalocyanine residue,
R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. Here, R ₁ and R ₂ may be combined to form a heterocyclic ring containing a nitrogen atom.
n represents an integer of 0 to 3.
m represents an integer of 1 to 4. )

The phthalocyanine derivative represented by is obtained by chlormethylating copper phthalocyanine and then reacting with a secondary amine such as diethylamine or piperidine.

  In the present invention, the addition amount of the phthalocyanine derivative represented by the general formula (1) is preferably 0.05 to 1 part by weight, more preferably 0.2 to 0.7 part by weight with respect to the total amount of the ink. If the amount is less than 0.05 parts by weight, the effect of the phthalocyanine derivative represented by the general formula (1) cannot be obtained, and even if it is used in an amount of more than 1 part by weight, the effect of the amount used can be obtained up to 2% by weight. It is not preferred because it makes the plate sensitized and adversely affects printing. If the amount is 2% by weight or more, the effect of the amount used cannot be obtained, and printing is also adversely affected.

  In order to disperse carbon black efficiently, it is desirable to add an optimum amount of the specific phthalocyanine derivative. However, if the optimum amount is added, the printability is adversely affected. For this reason, in order to supplement the dispersibility, the present invention makes it possible to maintain printability while maintaining sufficient dispersibility by using a specific gilsonite resin.

  If the boiling point of the petroleum solvent is less than 240 ° C, the evaporation of the solvent on the printing press increases, and the transferability of the ink to rollers, blankets, plates, etc. deteriorates due to the deterioration of the fluidity of the ink. It is not preferable. When the boiling point exceeds 400 ° C., the drying property of the heat-set type ink is inferior, which is not preferable.

The blending amount of the non-aromatic petroleum solvent is 0 to 40% by weight with respect to the total amount of the printing ink. Examples of such non-aromatic petroleum solvents include AF5, AF6 and AF7 manufactured by JX Nippon Oil & Energy Corporation.

  The fatty acid ester in the present invention is not particularly limited. Preferably, in the triglycerides of glycerin and fatty acids, which are compounds derived from vegetable oils and animal oils, use of fatty acid esters obtained from the esterification reaction of these triglycerides with saturated or unsaturated alcohols is preferable from the environmental viewpoint. .

  The addition amount of the fatty acid ester is 0.3 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the printing ink. If it is less than the lower limit of the above numerical value, the blanket of the printing press is thinned and the problem of poor inking occurs. On the other hand, if it exceeds the upper limit of the above numerical value, the blanket of the printing press is swollen to cause the problem of plate wear.

  The amount of fatty acid ester used when dissolving the gilsonite resin is 1 to 20% by weight, preferably 2 to 10% by weight, based on the total amount of gilsonite resin varnish. If it is less than the lower limit of the above numerical value, the solubility of the Gilsonite resin is inferior, so that the dissolution time is very long and many undissolved substances remain, so that the filtration time becomes long and the production cost is very high. Furthermore, the gilsonite resin varnish produced in this way has very poor viscosity stability and cannot produce a stable lithographic printing ink. In addition, if it exceeds the upper limit of the above numerical value, the solubility of the Gilsonite resin is improved and the filtration time is shortened, but when producing and printing lithographic printing ink using this varnish, the blanket of the printing press is swollen, Problems with plate wear occur.

  The vegetable oil used in the present invention is preferably a semi-drying oil or non-drying oil such as soybean oil or coconut oil, but a drying oil such as linseed oil or tung oil can be used in combination as required. As for the compounding quantity of vegetable oil, 10 to 60 weight% is desirable with respect to the printing ink whole quantity. If it is less than the lower limit of the above numerical value, the fluidity of the ink is insufficient due to insufficient solubility with the resin, and in some cases, there is a problem in on-machine stability. If the number exceeds the upper limit, the set deteriorates.

  The petroleum resins used in the present invention include DCPD petroleum resins made from cyclopentadiene and dicyclopentadiene, C5 petroleum resins such as pentene, pentadiene and isoprene, indene, methylindene, vinyltoluene, styrene, α- C9 petroleum resin made from methyl styrene, β-methyl styrene, etc., copolymer petroleum resin consisting of DCPD raw material and C5 raw material, copolymer petroleum resin consisting of DCPD raw material and C9 raw material, previous C5 series Copolymer petroleum resin composed of raw materials and C9-based materials, Copolymer petroleum resins composed of the above-mentioned DCPD-based materials, C5-based materials and C9-based materials, etc. are raised, using non-catalyzed or Friedel-Crafts type catalysts (cationic polymerization), etc. Manufactured.

  In addition, the addition amount of petroleum resin is 0.2-30 weight% with respect to printing ink whole quantity, Preferably it is 1-10 weight%. If it is less than the lower limit of the above value, the ink transferability is poor in printing, causing problems of poor inking, and if it exceeds the upper limit of the above numerical value, the setability is poor in printing and the stability on the machine is deteriorated, and there is no pile or paper peeling. Problems arise.

  The amount of petroleum resin used when dissolving the gilsonite resin is 1 to 20% by weight, preferably 3 to 10% by weight, based on the total amount of gilsonite resin varnish. If it is less than the lower limit of the above numerical value, the solubility of the Gilsonite resin is inferior, so that the dissolution time is very long and many undissolved substances remain, so that the filtration time becomes long and the production cost is very high. Furthermore, the gilsonite resin varnish produced in this way has very poor viscosity stability and cannot produce a stable lithographic printing ink. In addition, if it exceeds the upper limit of the above numerical value, the solubility of the Gilsonite resin will be improved and the filtration time will be shortened, but when printing with printing for lithographic printing, the setability will be poor and the stability on the machine will be poor, so And paper peeling problems occur.

  Examples of such petroleum resins include 120 grades (softening point 120 ° C.), 130 grades (softening point 130 ° C.), 140 grades (softening point 140 ° C.), 150 grades (softening point 150) manufactured by JX Nippon Oil & Energy Corporation. Etc., and other manufacturers also produce the same grade.

  Synthetic resins used with the gilsonite resin used in the present invention include rosin-modified phenolic resins and alkyd resins in addition to petroleum resins. Preferably, rosin modified phenolic resin is used. The rosin-modified phenol resin is not particularly limited, but preferably has a weight average molecular weight of 10,000 to 200,000, preferably 20000 to 80,000, and the solubility of the rosin-modified phenol resin is tolerance with No. 0 solvent solvent manufactured by Japan Petroleum Corporation. Is 20 to 49% by weight, preferably 22 to 30% by weight.

  When the weight average molecular weight is 10,000 or less, the viscoelasticity of the ink is lowered, and when it is 20000 or more, the fluidity and gloss of the ink are inferior. On the other hand, when the tolerance is 20% by weight or less, the ink setting property is lowered, and further, the set-off stains and the misting performance are deteriorated. When the tolerance is 49% by weight or more, the viscosity of the ink increases due to the promotion of solvent removal on the printing press, the fluidity decreases, the printability deteriorates due to the increase in tack, and the gloss is further decreased.

Tolerance is the minimum resin concentration at which the resin Xg is taken in a test tube, heated and dissolved in a solvent, and then cooled to 25 ° C. and then cooled to 25 ° C. The smaller the value, the better the solubility.

Tolerance (%) = [Resin (Xg)] ÷ [Resin (Xg) + Solvent (Yg)] × 100

The compounding quantity of a synthetic resin is 5 to 40 weight% with respect to the printing ink whole quantity, Preferably it is 10 to 30 weight%. If it exceeds the upper limit of the above numerical value, the ink is hardened and the fluidity becomes insufficient. On the other hand, if it decreases, the viscoelasticity of the ink is insufficient, which is not preferable.

  In the present invention, carbon black is used as the colorant for the printing ink. The compounding quantity of carbon black is 10-30 weight% with respect to the printing ink whole quantity.

  For the weight average molecular weight measurement, gel permeation chromatography (trade name: HLC-8020) manufactured by Tosoh Corporation and a column (trade name: TSK-GEL) manufactured by Tosoh Corporation were used (hereinafter, the weight average molecular weight was the same). Measured by the method).

  Further, the lithographic printing ink composition of the present invention includes a gelling agent, a pigment dispersant, a metal dryer, a drying inhibitor, an antioxidant, a friction improver, an anti-set-off agent, and a nonionic type as necessary. Additives such as sea surface activators and polyhydric alcohols can be conveniently used.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the present invention, “parts” and “%” respectively represent “parts by weight” and “% by weight” unless otherwise specified.

(Phenolic resin production example 1)
P-octylphenol 1000 parts, 35% formalin 850 parts, 93% sodium hydroxide 60 parts and toluene 1000 parts were added to a four-necked flask equipped with a stirrer, cooler and thermometer, and reacted at 90 ° C. for 6 hours. It is dripping. Then, 125 parts of 6N hydrochloric acid and 1000 parts of tap water were added, stirred and allowed to stand, and the upper layer part was taken out to obtain 2000 parts of a toluene solution of a resole type phenol resin having a nonvolatile content of 49%. X.

(Production Example 1 of rosin-modified phenolic resin)
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, added with 1400 parts of a resole solution, and toluene was removed. Then, after reacting at 230 ° C. for 4 hours, 100 parts of glycerin was charged, esterified at 250 to 260 ° C. until oxidation was 20 or less, and rosin-modified phenol resin A having a weight average molecular weight of 30000 and a tolerance of 20% by weight (hereinafter, Resin A) was obtained.

(Production Example 2 of rosin-modified phenolic resin)
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, added with 1600 parts of resole solution, and toluene was removed. Then, after reacting at 230 ° C. for 4 hours, 120 parts of glycerin was charged, esterified at 250 to 260 ° C. until oxidation was 20 or less, and rosin-modified phenol resin B (hereinafter referred to as “tolerance”) having a weight average molecular weight of 100,000 and a tolerance of 24% by weight. Resin B) was obtained.

(Production Example 3 of rosin-modified phenolic resin)
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, added with 1800 parts of a resole solution, and toluene was removed. Then, after reacting at 230 ° C. for 4 hours, 110 parts of glycerin was charged, esterified at 250 to 260 ° C. until oxidation was 20 or less, and rosin-modified phenol resin C (hereinafter referred to as “the rosin-modified phenol resin C having a weight average molecular weight of 130,000 and a tolerance of 27% by weight” Resin C) was obtained.

(Production Example 4 of rosin-modified phenolic resin)
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, added with 2000 parts of resole solution, and toluene was removed. Then, after reacting at 230 ° C. for 4 hours, 140 parts of glycerin was charged, esterified at 250 to 260 ° C. until oxidation was 20 or less, and rosin-modified phenol resin D (hereinafter referred to as “tolerance”) having a weight average molecular weight of 220,000 and a tolerance of 26% by weight. Resin D) was obtained.

(Manufacture of gel varnish for lithographic printing ink)
A stirrer, a Liebig condenser, a 4-neck flask with a thermometer, 40 parts by weight of resin B (weight average molecular weight 100,000), 33 parts by weight of soybean oil (iodine value 125 mg / 100 mg), AF Solvent No. 5 (Shin Nippon Oil ( Co., Ltd., aniline point 88 ° C., boiling range 279-307 ° C.) 26 parts by weight, heated to 190 ° C., stirred at the same temperature for 30 minutes, allowed to cool, and ethyl acetoacetate aluminum digel as a gelling agent 1 part by weight of isopropoxide (ALCH manufactured by Kawaken Fine Chemical Co., Ltd., hereinafter referred to as ALCH) was added and stirred at 190 ° C. for 30 minutes to obtain a gel varnish 1 for osmotic drying type offset printing ink (hereinafter referred to as varnish 1). It was.

  Furthermore, based on the composition of Table 1, the gel varnishes 2-4 (henceforth varnishes 2-4) were obtained with the gel varnish manufacturing method equivalent to the above.

(Manufacture of gilsonite varnish for lithographic printing ink)
Stirrer, Liebig condenser, 4-neck flask with thermometer, 30 parts by weight of Gilsonite resin E (softening point 162 ° C.), petroleum resin (manufactured by JX Nippon Mining & Energy Co., Ltd .: Nisseki Neopolymer 120 (softening point 120) ° C)) 5 parts by weight, soybean oil modified fatty acid ester 5 parts by weight, soybean oil (iodine value 125 mg / 100 mg) 50 parts by weight, AF Solvent No. 5 (manufactured by Shin Nippon Oil Co., Ltd., aniline point 88 ° C, boiling range) 279 to 307 ° C.) 10 parts by weight are charged, the temperature is raised to 195 ° C., and the mixture is stirred at the same temperature for 60 minutes and then allowed to cool. Thereafter, the mixture was filtered through a 150-mesh wire mesh filter to remove residues, and Gilsonite varnish 1 for lithographic printing ink was obtained.

  Furthermore, based on the composition of Table 2, Gilsonite varnishes 2 to 8 were obtained by the same Gilsonite gel varnish production method as described above.

  Table 3 shows the phthalocyanine derivatives used in this example.

(Manufacture of black ink for lithographic printing)
20 parts by weight of carbon black (Regal 99R (Cabot)), 0.5 parts by weight of phthalocyanine derivative 2 in Table 3, 17.0 parts by weight of gilsonite varnish 1, 34 parts by weight of gel varnish 2, and soybean oil fatty acid 3.0 parts by weight of butyl ester, 14.5 parts by weight of soybean oil (iodine value 125 mg / 100 mg), 5 parts by weight of AF Solvent No. 5 (manufactured by Shin Nippon Oil Co., Ltd.), a total of 92 parts by weight When charged on this roll and kneaded twice with three rolls at 60 ° C., the pigment particles were dispersed to 7.5 μm or less to obtain base ink 1. The viscosity of this base ink 1 was 5.0 ± 4 Pa. When the amount of soybean oil and AF solvent No. 5 was adjusted so as to be s and 100 parts by weight, 5 parts by weight of soybean oil and 2 parts by weight of AF solvent 5 were added to the base ink 1 to obtain 5 .0Pa · About 100 parts by weight of Ink Example 1 was obtained.

  A base ink was prepared by the same base ink preparation method as above, with the formulation shown in Tables 4 and 5, and the amount of soybean oil, AF solvent No. 5 and petroleum solvent H was adjusted to 5.0 ± When the viscosity of the ink was adjusted to 4 Pa · s, about 100 parts by weight of Ink Examples 2 to 14 and Ink Comparative Examples 1 to 9 were obtained.

(Evaluation results)
(Evaluation of Gilsonite varnish for lithographic printing ink)
The above-mentioned Gilsonite varnishes 1 to 8 were evaluated for particle diameter, filterability, varnish stability, rubber swellability, and environmental properties, and are shown in Table 6.

<Method for measuring particle size>
The produced gilsonite varnish is measured with a dispersion particle size measuring machine (grind meter) for the particle size of residue such as undissolved material. The greater the amount of undissolved material, the larger the particle size and the longer the ink production time for the next step. The smaller the particle size of the undissolved material or the like, the shorter the ink production time in the next step, which is better.
(Evaluation criteria)
○: 7.5 μm or less.
Δ: 7.5 μ to less than 10.0 μ.
×: 10.0 μm or more.

<Filterability measurement method>
The filtration time of the 150 mesh wire mesh filter filtration process at the time of manufacture of gilsonite varnish is measured and evaluated. If there are many residues, the residues accumulate on the filter and cannot be filtered, and the filter must be replaced, which takes man-hours and time. If the amount of residue is small, it is difficult for the residue to accumulate on the filter, there is no need to replace the filter, and the filtration time is short.
(Evaluation criteria)
○: Filter replacement is performed 1 to 3 times.
Δ: Filter exchange 4-9 times.
X: Filter exchange is 10 times or more.

<Method for measuring stability of gilsonite varnish>
Each manufactured Gilsonite varnish is weighed 180 cc into a maximum of 220 cc sealed container. The inside of the container is purged with nitrogen, then the lid is closed, and the container is stored in an oven at 70 ° C. for 1 week to accelerate. One week later, the product is taken out from the oven, the viscosity is measured again, and the viscosity difference (ΔPa · s) from each gilsonite varnish before storage in the oven is determined. The smaller the amount of change in viscosity, the better the stability over time.
(Evaluation criteria)
○: Less than 15 Pa · s Δ: 15 Pa · s or more, less than 25 P · s ×: 25 Pa · s or more

<Swellability evaluation>
Each manufactured Gilsonite varnish had a rubber roll cut into 4.00 cm (length) x 1.00 cm (width) x 0.200 cm (thickness) with a hardness of 30 (manufactured by M company used in a printing press) (Rubber roll) is immersed, taken out after 2 weeks, and after removing the Gilsonite varnish, the length is measured and the swelling property of the rubber is evaluated. The change from the original length is expressed by the expansion / contraction rate (%). When the rubber is contracted, problems such as poor ink transfer between the rollers and poor inking occur during printing on a printing press. Further, if the rubber swells greatly, plate wear occurs during printing, which causes a problem of poor inking. In order to keep the inking at the time of printing stable, it is better to swell a little (stretch rate 100% to 110%).
(Evaluation criteria)
○: The expansion / contraction rate is 100% or more and 110% or less. Δ: The expansion / contraction rate is more than 110% and 120% or less, or 90% or more and less than 100%.
X: The expansion / contraction rate is greater than 120% or less than 90%.

<Environmental evaluation>
About the solvent currently used for the manufactured gilsonite varnish, the ratio of the aromatic component in a solvent is investigated. For environmentally-friendly “Eco Mark” certified printing inks, the aromatic component is less than 1% by volume as the solvent used in the ink. This is standard in Japan. Overseas, solvents with an aromatic component of less than 3% by volume are mainly used as environmentally friendly inks.
(Evaluation criteria)
○: The aromatic component of the solvent is less than 1% by volume. Δ: The aromatic component of the solvent is from 1% to less than 3%. ×: The aromatic component of the solvent is 3% or more by volume.

In the lithographic printing inks of Ink Examples 1 to 14 and Ink Comparative Examples 1 to 9 produced above, fluidity, on-machine stability, stability over time, paper peeling, swelling, environmental properties, printability (misting) Property, fleshing property, and piling property) were evaluated, and the results are shown in Tables 7 and 8.

<Measurement method of fluidity>
After 2.1 cc of ink is set in a hemispherical container, the ink is immediately dropped on an inclined plate inclined at 60 °, and the length of the ink flowing for 10 minutes is measured. Higher values indicate less ink tightness and better fluidity.
(Evaluation criteria)
◎: 130 mm or more ○: 100 mm or more, less than 130 mm Δ: 60 mm or more, less than 100 mm ×: less than 60 mm

<Measurement method of on-board stability>
1.32 cc of ink is set in a digital incometer manufactured by Toyo Seiki Co., Ltd., and the time until the tack value reaches the maximum value at 40 ° C. and 1200 rpm is measured. The longer the time to reach the maximum value, the more slowly the ink tack value fluctuates, indicating that there is less ink viscosity increase and fluidity change on the printing press. Indicates that
(Evaluation criteria)
◎: 25 min or more ○: 20 min or more, less than 25 min Δ: 15 min or more, less than 20 min ×: less than 15 min

<Measurement method of stability over time>
About the ink whose viscosity was measured with a Raleigh viscometer (L-type viscometer (25 ° C.)), 180 cc of the ink was weighed out into a sealed container of maximum 220 cc. The inside of the container is purged with nitrogen, then the lid is closed, and the container is stored in an oven at 70 ° C. for 1 week to accelerate. One week later, the product is taken out from the oven, the viscosity is measured again, and the viscosity difference (ΔPa · s) from the ink before storing in the oven is obtained. The smaller the amount of change in viscosity, the better the stability over time.
(Evaluation criteria)
◎: Less than 0.5 Pa · s ○: 0.5 Pa · s or more, less than 1.0 P · s Δ: 1.0 Pa · s or more, less than 1.5 P · s ×: 1.5 Pa · s or more

<Measuring method of paper peelability>
When ink 2.5 cc is developed on newspaper renewal paper (20 × 25 cm) at 50 rpm with an RI tester (manufactured by Akira Mfg. Co., Ltd.), the ink is visually applied and applied to paper. It has excellent inking properties and does not peel off.
(Evaluation criteria)
○: Good inking, not for paper.
(Triangle | delta): There is some incompletely-thickening defect and paper peeling is also confirmed slightly.
X: Poorly inset and paper peeling is conspicuous.

<Swelling evaluation method>
A rubber roll (rubber roll manufactured by M company used in a printing press) cut into 4.00 cm (length) x 1.00 cm (width) x 0.200 cm (thickness) with a hardness of 30 is applied to each ink produced. It is immersed, taken out after 2 weeks, the ink is removed, the length is measured, and the swelling property of the rubber is evaluated. The change from the original length is expressed by the expansion / contraction rate (%). When the rubber is contracted, problems such as poor ink transfer between the rollers and poor inking occur during printing on a printing press. Further, if the rubber swells greatly, plate wear occurs during printing, which causes a problem of poor inking. In order to keep the inking at the time of printing stable, it is better to swell a little (stretch rate 100% to 110%).
(Evaluation criteria)
○: The expansion / contraction rate is 100% or more and 110% or less. Δ: The expansion / contraction rate is more than 110% and 120% or less, or 90% or more and less than 100%.
X: The expansion / contraction rate is greater than 120% or less than 90%.

<Environmental evaluation method>
About the solvent currently used for each manufactured ink, the ratio of the aromatic component in a solvent is investigated. For environmentally-friendly “Eco Mark” certified printing inks, the aromatic component is less than 1% by volume as the solvent used in the ink. This is standard in Japan. Overseas, solvents with an aromatic component of less than 3% by volume are mainly used as environmentally friendly inks.
(Evaluation criteria)
○: The aromatic component of the solvent is less than 1% by volume. Δ: The aromatic component of the solvent is from 1% to less than 3%. ×: The aromatic component of the solvent is 3% or more by volume.

<Method for evaluating printability>
Under the following printing conditions, single color solid and halftone dots (1 to 100% in 10% increments) printing and normal character printing were performed.

[Printing conditions]
Printing machine: LITHOPIA BT2-800 NEO (Mitsubishi Heavy Industries, Ltd.)
Paper: Newspaper renewal: Super lightweight paper (43 g / m ² ) (Nippon Paper Industries Co., Ltd.)
(Colorimetric value: L ^* : 83, a ^* : -0.25, b ^* : 5.5)
Dampening solution: NEWSKING ALKY (Toyo Ink Co., Ltd.) 0.5% tap aqueous solution Printing speed: 100,000 copies / hour Plate: CTP plate (Fuji Film Co., Ltd.)
Number of printed copies: 50,000

[Missing properties]
Set a blank sheet around the printer before printing and visually evaluate the degree of ink mist after printing 50,000 copies.
(Evaluation criteria)
○: A small amount of ink mist is scattered on a part of white paper.
Δ: A thin ink mist is scattered all over the white paper.
X: A solid and ink mist is scattered all over the white paper.

[Incarnation]
The solidity of the solid portion and halftone dot portion on the paper surface when printing 50,000 copies is visually evaluated.
(Evaluation criteria)
○: Good inking, not for paper.
(Triangle | delta): There is some incompletely-thickening defect and paper peeling is also confirmed slightly.
X: Poorly inset and paper peeling is conspicuous.

[Piling properties]
Visually evaluate the pileability of the paper surface when printing 50,000 copies.
(Evaluation criteria)
○: Good inking, no piling.
(Triangle | delta): There is a partly incompletely-imposed defect and a piling is also confirmed slightly.
X: Poorly infused and piling is conspicuous.

  From the results in Table 6, the Gilsonite varnishes 1 to 4 used in the examples are excellent in balance among productivity (particle diameter, filterability), varnish stability, rubber swellability, and environmental properties. On the other hand, the gilsonite varnish 5 using a gilsonite resin having a softening point of 210 ° C. has poor productivity and varnish stability of the gilsonite varnish. In addition, when producing gilsonite varnish, gilsonite varnish 6 to 8 to which no petroleum resin or fatty acid ester is added is also very poor in productivity and varnish stability.

  From the results shown in Tables 7 and 8, the fluidity, on-machine stability, aging stability, paper peelability, rubber swellability, environmental properties, and printability (misting properties, fleshing properties, and piling properties) are all well-balanced. Examples 1 to 14 are excellent. Ink Comparative Example 6 using a Gilsonite resin having a softening point of 210 ° C. has poor on-machine stability and stability over time. Furthermore, Comparative Examples 4 and 5 using the gilsonite varnish to which no petroleum resin or fatty acid ester is added at the time of producing the gilsonite varnish have very poor on-machine stability, stability over time, and printability. Comparative Example 7 with a small amount of derivative has very poor on-machine stability, stability over time, and printability, and Comparative Example 8 with a large amount of derivative improves on-machine stability and stability over time, but has good printability. It can be seen that the inking property is very poor.

  The black ink for lithographic printing according to the present invention improves the wettability of carbon black, thereby solving the problem of dispersibility such as agglomeration of carbon black when converted into an ink. It has excellent on-machine stability, stability and stability over time, and is also environmentally friendly, and can be used effectively in the printing field of newspapers, magazines, flyers and the like.

Claims (8)

Petroleum based on a pigment, a Gilsonite resin having a softening point of 135 ° C. to 205 ° C. extracted from natural asphalt, a petroleum resin, a synthetic resin, a phthalocyanine derivative, and an aromatic hydrocarbon content of 1% by weight or less A lithographic black ink containing a solvent, a fatty acid ester, and a vegetable oil. For the total amount of ink
Gilsonite resin having a softening point of 135 ° C. to 205 ° C. extracted from natural asphaltum is 0.5 to 20% by weight,
Petroleum resin is 0.2 to 30% by weight,
5-40% by weight of synthetic resin
And 0.3 to 10% by weight of fatty acid ester
2. The black ink for lithographic printing according to claim 1, wherein: The black ink for lithographic printing according to claim 1 or 2, wherein the phthalocyanine derivative is a compound represented by the following general formula (1).
General formula (1)

Pc- (XY) m

(Wherein Pc represents a phthalocyanine residue,
X represents —CH ₂ —, —OCO—, or —SO ₂ CH ₂ —,
Y represents —NH— (CH ₂ ) _n —NR ₁ R ₂ or — (CH ₂ ) _n —NR ₁ R ₂ .
R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. Here, R ₁ and R ₂ may be combined to form a heterocyclic ring containing a nitrogen atom.
n represents an integer of 0 to 3.
m represents an integer of 1 to 4. ) The black ink for lithographic printing according to any one of claims 1 to 3, wherein the content of the phthalocyanine derivative is 0.05 to 1% by weight based on the total amount of the indigo ink for lithographic printing. The black ink for lithographic printing according to any one of claims 1 to 4, wherein the synthetic resin is a rosin-modified phenol resin. Rosin modified phenolic resin
1) Weight average molecular weight 10,000 to 200,000
2) Tolerance is 20 to 49% by weight
The black ink for lithographic printing according to claim 5. Petroleum solvent is 1) Aniline point is 60 ℃ ~ 130 ℃
2) Boiling point is 240 ° C to 400 ° C
The black ink for lithographic printing according to any one of claims 1 to 6. A printed matter obtained by printing the black ink for lithographic printing according to any one of claims 1 to 7.