JP2008179691A - Ink composition for water-less lithography - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for a water-less lithography, performed with the improvement of paper peeling resistance and inking property to cope with the high speeding and use of the low grade paper in the printing by the water-less lithography without requiring dampening water and also excellent in greasing resistance. <P>SOLUTION: This ink composition for water-less lithography is characterized by containing 5 to 30 wt.% pigment, 20-50 wt.% binder resin, 1 to 40 wt.% α-olefin, 0.1 to 10 wt.% amine compound and 20 to 70 wt.% solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  In the waterless planographic printing that does not require fountain solution, the present invention responds to higher printing speed and lower paper quality, thereby improving paper-peeling resistance and fleshing resistance, and excellent scumming resistance. A waterless lithographic ink composition is provided.

In lithographic printing, which is the mainstream of current printing, dampening water is supplied to the non-image area, and the image is formed by utilizing the ink repellency. However, in this lithographic printing, the cause of variations in print quality is largely due to dampening water, and a great deal of equipment, consumables, time and skill are required to control it.
In recent years, a waterless lithographic printing method has been proposed as a method for solving this problem related to fountain solution. In particular, printing is performed by providing silicone rubber on the non-image area in order to show ink repellency instead of fountain solution. The method has been put into practical use. In such waterless lithographic printing, it is known that printing with a conventional oil-based ink is not preferable because sufficient ink repulsion at a non-image area cannot be obtained, and background staining occurs. The phenomenon of scumming in waterless printing is due to the temperature rise caused by friction of the drive unit and rollers of the printing press during printing, and the plate surface due to the absence of cooling water due to water evaporation because no dampening water is used. The increase in temperature means that the cohesive force of the ink itself decreases, and the ink adheres to the non-image area where the ink should repel.

  In order to solve the problems peculiar to waterless printing, a method of using a silicone-modified resin as a binder resin or adding a silicone oil as an ink composition has been performed in the past (Japanese Patent Laid-Open No. 02-22369, (Sho 59-147072, JP 50-71410, JP 48-4107). Addition of silicone oil improves scum resistance, but its application is limited because there are difficulties in post-processing and silicone oil volatilized in the dryer for off-wheel printing becomes the catalyst poison of the catalyst deodorizer. It had been. In view of this, Japanese Patent Application Laid-Open No. 06-157960 discloses a method in which powdered silica is contained in an ink composition and an organometallic gelling agent is used as a thickener, but there is a risk that the powdered silica may damage the plate surface. For this reason, there are concerns about long-time printing.

  In addition, since silicone oil has poor compatibility with ink components and is easily separated, the stability on the printing press may be inferior and transfer defects between rollers may occur. In JP-A-10-292145 and JP-A-2002-97398, an organopolysiloxane that is compatible with ink is selected, an ink composition containing a specific rosin-modified phenolic resin is invented, and ink and plate adhesion Although a technique for improving stain resistance by lowering energy is disclosed, there is a problem that sufficient stain resistance cannot be obtained due to the low viscosity ink composition.

  As other inventions for reducing the adhesion energy between the ink and the plate, a method using a cyclized rubber, an α-olefin, and an α-olefin polymer (JP 2005-126579 A, JP 2005-290083 A), Although a technique using a fluoropolyether (Japanese Patent Laid-Open No. 2006-298948) is disclosed, the cyclized rubber and perfluoropolyether are expensive, leading to an increase in cost.

Further, the invention of a binder resin for waterless lithographic printing ink has been advanced, and Japanese Patent Application Laid-Open No. 05-279613 discloses a technique for polymerizing a resin to increase ink cohesion and improve scumming resistance. Due to its high tack, it is not suitable for printing on low-grade paper with low paper strength. Also disclosed is a method of using a polycarboxylic acid or an amine compound as a molecular chain extender of a phenol resin during synthesis of a binder resin (Japanese Patent Laid-Open Nos. 02-206662 and 63-191871). .
Waterless lithographic printing has been remarkably popular in recent years, but because the speed of printing is progressing and the use of low-grade paper is increasing, lowering the tack of ink to impart paper peeling resistance, It is necessary to improve the inking property on paper. Further, since waterless printing is also being performed on the additional paper, there is a demand for an ink that has a lower tack than that of the current ink and has a good thickness. In order to improve the paper peeling resistance and the inking property, it is sufficient to increase the amount of the solvent in the ink. However, as the adverse effect, the viscosity is lowered and the stain resistance is deteriorated. Designing inks that are excellent in soil resistance, low tack, and good inking properties is a difficult task.
Japanese Patent Laid-Open No. 02-22369 JP 59-147072 A JP 50-71410 A JP 48-4107 A Japanese Patent Laid-Open No. 06-157960 JP-A-10-292145 JP 2002-97398 A JP 2005-126579 A JP 2005-290083 A JP 2006-298948 A JP 05-279613 A Japanese Patent Laid-Open No. 02-206662 JP 63-191871 A

  The problem to be solved by the present invention is to provide a waterless lithographic printing ink composition which is improved in paper resistance, inking property and transferability and excellent in stain resistance.

  As a result of intensive studies by the present inventors, a waterless lithographic printing ink containing a pigment, a rosin-modified phenol, a solvent and an amine compound increases the viscosity of the ink by adding an amine compound, and has a low tack and high viscosity. And the peeling effect of the ink and the plate is promoted by the action of the α-olefin. As a result, an ink excellent in fluidity, fleshing property, stain resistance, and paper peeling resistance is provided, and printing on lower paper is enabled.

  That is, the present invention includes 5 to 30% by weight of pigment, 20 to 50% by weight of binder resin, 1 to 40% by weight of α-olefin, 0.1 to 10% by weight of amine compound, and 20 to 70% by weight of solvent. It is related with the ink composition for waterless planographic printing characterized by containing%.

  The present invention also relates to the waterless lithographic printing ink composition described above, further comprising an organopolysiloxane.

  Furthermore, the present invention relates to the waterless lithographic printing ink composition, wherein the binder resin is an α-olefin polymer.

  The present invention also relates to the above-described waterless lithographic printing ink composition, wherein the binder resin has a weight average molecular weight of 10,000 to 400,000.

  Furthermore, the present invention relates to the above waterless lithographic printing ink composition, wherein the binder resin is a rosin-modified phenol resin having a normal heptane tolerance of 1 ml to 40 ml.

  The present invention also relates to the above waterless lithographic printing ink composition, wherein the α-olefin has 12 to 18 carbon atoms.

  Furthermore, the present invention provides the above waterless lithographic printing, wherein the amine compound is a monomer or a polyamide compound having a molecular weight of 500 to 20,000 comprising an acid having 6 to 60 carbon atoms and an amine. The present invention relates to an ink composition.

  The present invention also relates to the above waterless lithographic printing ink composition, wherein the solvent is at least one selected from the group consisting of petroleum solvents, mineral oils, vegetable oils and vegetable oil esters.

  Furthermore, the present invention relates to the waterless lithographic printing ink composition described above, wherein the solvent contains at least one vegetable oil selected from the group consisting of soybean oil, coconut oil, linseed oil, and rapeseed oil. .

  The present invention also relates to the above waterless lithographic printing ink composition, characterized in that it is a permeation dry type.

  Furthermore, the present invention relates to a printed matter obtained by printing the above waterless lithographic printing ink on uncoated paper or finely coated paper.

  According to the present invention, it is possible to obtain a waterless lithographic printing ink that is excellent in stain resistance and printability and enables printing on low-grade paper. That is, by adjusting the addition amount of the amine compound of the present invention, it is possible to control the ink properties (tack, flow, viscosity), and it is possible to prepare a waterless lithographic printing ink suitable for the printing environment and printing paper. . In addition, it is possible to obtain a printing ink that has excellent stain resistance due to the increased viscosity of the ink and the effect of the α-olefin.

  Hereinafter, the present invention will be described in detail.

  Examples of the pigment used in the present invention include general inorganic pigments and organic pigments. Examples of inorganic pigments include chrome-lead, zinc-yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, dial, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, and bengara. . Organic pigments include azo pigments, soluble azo pigments such as C-based (β-naphthol-based), 2B-based and 6B-based (β-oxynaphthoic-based), β-naphthol-based, β-oxynaphthoic acid anilide-based, monoazo yellow-based, disazo Insoluble azo pigments such as yellow and pyrazolone, condensed azo pigments such as allyl acetoacetate, copper phthalocyanine (α blue, β blue, ε blue), halogenated copper phthalocyanine such as chlorine and bromine, metal Examples of free phthalocyanine pigments and polycyclic pigments include perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, and quinophthalone pigments.

  As the binder resin used in the present invention, rosin-modified phenol resin, rosin-modified maleic acid resin, alkyd resin, petroleum resin, α-olefin polymer and the like can be used alone or in combination of two or more.

  The rosin-modified phenolic resin used in the present invention is not particularly limited, and gum rosin, wood rosin, tall oil rosin and the like can be typically used as the rosin. As the phenol resin, a novolac type, a resol type, or a novolak-resol composite type phenol resin can be used. As the polyol, glycerin, pentaerythritol and the like can be typically used. The production method of the rosin-modified phenol resin is not particularly limited, such as the order of introduction of these resin raw materials, the reaction catalyst, and the properties such as molecular weight and solubility, but the resin viscosity at 25 ° C. is preferably 18 to 50 Pa · s. . Here, the resin viscosity is defined as a viscosity of a varnish obtained by heating and dissolving a mixture of resin / linseed oil = 1/2 at 180 to 200 ° C. while stirring and dissolving at 25 ° C. If the resin viscosity is less than 18 Pa · s, the cohesive force as an ink is insufficient and the stain resistance is inferior, and if it exceeds 50 Pa · s, the fluidity is deteriorated when the ink is used.

  In normal heptane tolerance in the present invention, 1 g of resin is weighed in a beaker, dissolved in 9 g of toluene at room temperature, and normal heptane is dropped with a burette until the solution becomes cloudy and the newspaper type under the beaker cannot be determined. It is obtained by measuring the normal heptane dropping amount. The rosin-modified phenol resin used in the present invention preferably has a normal heptane tolerance of 1 ml to 40 ml, more preferably a normal heptane tolerance of 5 ml to 35 ml. When the normal heptane tolerance is 1 ml or less, the fluidity of the ink is deteriorated and the inking is deteriorated. When the normal heptane tolerance is 40 ml or more, the viscoelasticity is increased and the soiling property is deteriorated.

  The rosin-modified maleic resin used in the present invention preferably has a weight average molecular weight of 5,000 to 250,000. When the weight average molecular weight exceeds 250,000, there is a problem that troubles during production are likely to occur. In addition, if the acid value and hydroxyl value of the rosin-modified maleic resin are too high, the water resistance of the resulting printing ink tends to decrease, and offset printing tends to cause problems such as smudges. If the value is too low, unreacted gelling agent remains, and the aging stability of the resulting offset printing ink composition tends to deteriorate. Therefore, a rosin having an appropriate acid value and hydroxyl value It is preferable to select a modified maleic resin and adjust the amount of gelling agent used.

The petroleum resin used in the present invention contains indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, cyclopentadiene, dicyclopentadiene, methylbutene, isoprene, pentene, cyclopentene, pentadiene and the like as components. A petroleum resin having a double bond can be exemplified. The petroleum resin having a double bond, cyclopentadiene, DCPD-based petroleum resin is a dicyclopentadiene as a raw material; pentene, pentadiene, C ₅ petroleum resins such as isoprene; indene, methyl indene, vinyl toluene, styrene, alpha- C ₉ petroleum resin made from methyl styrene, β-methyl styrene or the like, copolymer petroleum resin made from DCPD and C ₅ materials, copolymer petroleum resin made from DCPD and C ₉ materials, C ₅ based copolymerized petroleum resin comprising C ₉ based material, wherein like DCPD-based and C ₅ based copolymerizable petroleum resin comprising C ₉ based material and the like, non-catalytic or Friedel-Crafts type catalyst (cationic polymerization), etc. It is manufactured using. In particular, polar groups giving is easy, since easily adjusted to a desired softening point, DCPD petroleum resins, copolymer petroleum resin comprising DCPC system and C ₅ based precursor, a copolymer consisting of DCPD-based and C ₉ based source petroleum resin, copolymer petroleum resin comprising DCPD-based and _{C 5} system and _{C 9} based material is preferred.

  The alkyd resin used in the present invention is preferably an oil-modified alkyd resin composed of a polybasic acid, a polyol and an oil.

The α-olefin polymer used in the present invention has a weight average molecular weight (polystyrene conversion value of gel permeation chromatography) of 1,000 to 30,000, preferably 4,000 to 25,000, and more preferably 10. , 20,000 to 20,000.
The viscosity at 25 ° C (Tokyo Keiki B-type viscometer, model BL3) is 300 to 4,000 mPa · s, preferably 500 to 3,500 mPa · s, more preferably 1,000 to 3,000 mPa · s. -S. If the weight average molecular weight is less than 1000 or the viscosity is less than 300 mPa · s, sufficient stain resistance cannot be obtained, and if the weight average molecular weight exceeds 30,000 or the viscosity exceeds 4,000 mPa · s, the ink Storage stability and inking properties are deteriorated.

  The waterless lithographic printing ink in the present invention may be any of sheet-fed printing ink, heat set-off wheel printing ink, non-heat set-off wheel printing ink, etc., preferably heat set-off wheel printing ink, Non-heat set-off wheel ink or newspaper printing ink is preferred. Sheet printed matter often has post-processing such as dry overprinting of special colors, overprint varnish or water-based varnishing, laminating film sticking, etc., and printed matter printed with ink added with α-olefin polymer Care must be taken because varnish may be repelled.

  The above solid resins (rosin-modified phenolic resin, rosin-modified maleic acid resin, alkyd, petroleum resin, etc.) are gelatinized like a solvent of vegetable oil or mineral oil alone or in combination of two or more and sometimes an aluminum chelate compound. An agent is added and melted at about 190 ° C. to be varnished. The addition amount of the solid resin is 20% by weight to 50% by weight with respect to the total amount of the printing ink composition.

  The vegetable oils used in the present invention are vegetable oils and compounds derived from vegetable oils. Among the triglycerides of glycerin and fatty acids, at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond, and those Fatty acid monoesters obtained by subjecting triglycerides to an ester reaction with saturated or unsaturated alcohols.

  Typical vegetable oils are: Asa seed oil, flaxseed oil, eno oil, psyllium oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil , Safflower oil, Japanese radish seed oil, soybean oil, daikon oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil Cottonseed oil, coconut oil, peanut oil, dehydrated castor oil, and the like.

  Examples of vegetable oil esters used in the present invention include fatty acid esters derived from vegetable oils such as soybean oil, cottonseed oil, linseed oil, safflower oil, tall oil, dehydrated castor oil, canola oil, and rapeseed oil. Examples of the fatty acid ester include monoalkyl ester compounds, and the fatty acid constituting the monoester is preferably a saturated or unsaturated fatty acid having 16 to 20 carbon atoms, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linol. Examples include acids, linolenic acid, eleostearic acid and the like. The alcohol-derived alkyl group constituting the fatty acid monoester preferably has 1 to 10 carbon atoms, and examples thereof include methyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and 2-ethylhexyl. These fatty acid monoesters can be used alone or in combination of two or more. In the present invention, vegetable oils and fatty acid esters may be used alone or in combination as vegetable oil components. The amount of the solvent added is preferably 10 to 50% by weight in the ink.

  The mineral oil used in the present invention is a crude oil-derived solvent (petroleum solvent) having an aromatic hydrocarbon content of 1% by weight or less. The petroleum solvent is suitably a petroleum solvent having an aniline point of 65 to 110 ° C, preferably 75 to 95 ° C and a boiling point of 230 ° C or higher. When the aniline point is less than 75 ° C., the ability to dissolve the resin is too high, and the viscosity of the ink becomes too low, resulting in insufficient stain resistance. On the other hand, if the temperature exceeds 95 ° C., the resin is poorly soluble, so that the fluidity of the ink is inferior, and as a result, only printed matter with poor gloss and inking properties can be obtained. When the boiling point is less than 230 ° C., the evaporation of the solvent in the ink on the printing machine is increased, and the ink is liable to be deposited on the roller, the plate or the blanket due to the deterioration of the fluidity of the ink.

  The α-olefin used in the present invention has a linear or branched structure having 12 to 18 carbon atoms, and the addition amount is preferably 1 to 40% by weight, more preferably 5 to 20% by weight. If the amount added is less than 1% by weight, sufficient stain resistance cannot be obtained, and if it exceeds 40% by weight, the ink does not adhere to the roller and printability is impaired.

  The viscosity of the organopolysiloxane used in the present invention is preferably in the range of 50 to 10,000 cSt, more preferably 50 to 3,000 cSt, and still more preferably 100 to 1,000 cSt. If the viscosity of the organopolysiloxane is less than 50 cSt, a large amount of low molecular weight organopolysiloxane is present, so that the amount of volatile components increases and the stability on the printing press is not good. When used in ink, it is not preferable because it adversely affects the catalyst deodorizing device of the dryer of the printing press. On the other hand, when the viscosity exceeds 10,000 cSt, the mixing with ink is inferior, so that the on-machine stability is deteriorated and the stain resistance is also deteriorated. The molecular weight of the organopolysiloxane is preferably in the range of 3,000 to 60,000. Organopolysiloxane having a molecular weight of less than 3,000 is not preferable because it has high volatility and therefore should not be contained. When the molecular weight exceeds 1, the miscibility with the ink is deteriorated, the transferability between the rollers is inferior, and the stability on the printing press is unfavorable.

  The organopolysiloxane must be liquid at room temperature, and the types are dimethylpolysiloxane, methylhydrogen, methylphenyl, carboxyl modification, epoxy modification, alcohol modification, fatty acid modification, polyether modification, alkyl modification, Organopolysiloxanes such as amino-modified can be used, but dimethylpolysiloxane, methylhydrogenpolysiloxane, alkyl-modified polysiloxane, and alcohol-modified polysiloxane are particularly preferable because they exhibit good soil resistance.

  The content of the organopolysiloxane in the ink is in the range of 0.1 to 7% by weight, preferably 0.5 to 5% by weight, and more preferably 0.5 to 3% by weight. If the content is less than 0.1% by weight, the soil resistance is insufficient, which is not preferable. If the content exceeds 7% by weight, not only the transferability between the rollers of the printing press is deteriorated but also the inking property is remarkably increased. It is not preferable because it gets worse. By containing a predetermined amount of the organopolysiloxane of the present invention in a waterless lithographic ink, the ink peelability from the non-image area of the waterless lithographic plate becomes very good, and the stain resistance as an ink is improved. In addition, it is suitable because there is little deterioration in ink transfer properties and inking properties.

The amine compound used in the present invention is achieved by a waterless lithographic printing ink composition characterized by containing 0.1 to 10% by weight of an amine compound containing active hydrogen in the molecule. Examples of amine compounds containing active hydrogen used in the present invention include ethylamine, n-propylamine, n-butylamine, hexylamine, laurylamine, stearylamine, ethanolamine, allylamine and other monoamines, ethylenediamine, trimethylenediamine, tetra Diamines such as methylenediamine, pentamethylenediamine and hexamethylenediamine, polyamines such as diethylenetriamine, triethylenetetraamine and bishydroxydiethylenetriamine, amine adducts and the like can be used effectively.
Amide compounds as amine derivatives include formic acid, acetic acid, propionic acid, itaconic acid, caprylic acid, glycolic acid, acrylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid Monocarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, dimer acid and other organic dicarboxylic acids, trimellitic acid and other organic Examples thereof include condensates of organic carboxylic acids such as tricarboxylic acid and 3,9-bis (2carboxyalkyl) 2,4,8,10-tetraoxaspiroundecane and the above amines, diamines, polyamines and the like.

  The amine compound used in the present invention has a structural composition as described above, but is preferably a polyamide resin in view of handling safety and the like, and has 6 to 60 carbon atoms from the viewpoint of compatibility with the resin and the solvent. A polyamide resin comprising an acid and a polyamine is particularly preferably used. The molecular weight of the polyamide resin is preferably in the range of 500 to 20,000, more preferably in the range of 500 to 10,000.

  As an addition amount of the amine compound used for this invention, it is necessary to select the range of 0.1-10 weight%. If the addition amount is less than 0.1% by weight, the effect of increasing the viscosity or improving the stain resistance is small, and if it exceeds 10% by weight, there is a problem in ink transferability.

The amine compound used in the present invention is effective when used alone or in combination of two or more, and can be used effectively even if the amine compound is diluted with a non-reactive solvent, resin or the like.
The amine compound has an ink viscosity that increases depending on the amount added, and achieves a low tack by diluting with vegetable oil, mineral oil, or the like. A waterless lithographic printing ink having a high viscosity and a low tack can be obtained by adjusting the amount of amine compound added according to the target tack and viscosity.
In the present invention, extender pigments such as organic bentonite, calcium carbonate, barium sulfate, clay, and silica can be added when the pigment is dispersed in the varnish.

  As other auxiliaries used in the present invention, additives such as dispersants, drying inhibitors, antioxidants, and antifriction agents (waxes) can be used as appropriate.

  EXAMPLES Next, although this invention is demonstrated based on an Example, this invention is not what is limited to these Examples. In the following examples, “parts” and “%” respectively represent “parts by weight” and “% by weight” unless otherwise specified.

[Phenolic resin production example]
A mixture of 720 parts of p-octylphenol, 375 parts of p-decylphenol, 290 parts of paraformaldehyde, and 800 parts of xylene was heated and dissolved in a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and then 48% 80 parts of an aqueous sodium hydroxide solution is added and allowed to react at 80-90 ° C. for 5 hours. After the reaction, 125 parts of 6N hydrochloric acid and 200 parts of tap water are added and the mixture is left to stir. The supernatant layer is taken out and washed with water to obtain about 2100 parts of a xylene solution of a resol type phenol resin having a nonvolatile content of 63%. It was.

[Rosin modified phenolic resin production example]
A four-necked flask equipped with a stirrer, Liebig condenser, and thermometer was charged with 600 parts of gum rosin, heated and dissolved at 200 ° C. while blowing nitrogen gas, and 770 parts of A resole solution was reacted at 120 to 200 ° C., followed by glycerin. 67 parts were charged and esterified at 250 to 260 ° C. until the acid value was 25 or less to obtain a rosin-modified phenol resin A having a molecular weight of 80,000, a cloudiness temperature of 90 ° C., and a resin viscosity of 160 poise. (The cloudiness temperature was measured with NOVOCONTROL manufactured by CHEMOTRONIC in a 10% diluted state of AF Solvent 6 manufactured by Shin Nippon Oil Co., Ltd. The resin viscosity was 180 by weight ratio of resin / linseed oil = 1/2. (Viscosity value at 25 ° C. measured by cone plate viscometer of varnish obtained by stirring and dissolving at ˜200 ° C.)

[Examples of varnish production]
Varnish A, B, C, D, E of the following varnish manufacture examples 1-5 was obtained by the prescription shown in Table 1.

[Varnish production example 1]
42 parts of rosin modified phenolic resin A (normal heptane tolerance 30 ml), 15 parts of linseed oil, 42.5 parts of AF solvent 5 (manufactured by Nippon Oil Corporation), 0.5 part of aluminum chelate (manufactured by Kawaken Fine Chemicals, ALCH) Was heated and stirred at 190 ° C. for 1 hour to obtain varnish A.

[Varnish production example 2]
42 parts of rosin modified phenolic resin A, 15 parts of linseed oil, 10 parts of dialne 168 (Mitsubishi Chemical Corporation), 532.5 parts of AF solvent, 0.5 part of aluminum chelate (ALCH) are heated and stirred at 190 ° C for 1 hour. Thus, varnish B was obtained.

[Varnish production example 3]
42 parts of rosin modified phenolic resin A, 15 parts of linseed oil, 20 parts of diallen 168 (α-olefin, C _{16 to} C ₁₈ ), 522.5 parts of AF solvent, 0.5 part of aluminum chelate (ALCH) at 190 ° C. Varnish C was obtained by heating and stirring for a period of time.

[Varnish production example 4]
Rosin modified phenolic resin B (Arakawa Chemical Industries, Ltd., weight average molecular weight 80,000, acid value 20, softening point 180 ° C.) 45 parts, linseed oil 30 parts, soybean oil 14.5 parts, soybean oil fatty acid butyl ester 10 parts and 0.5 part of aluminum chelate (ALCH) were heated and stirred at 190 ° C. for 1 hour to obtain varnish D.

[Varnish production example 5]
Rosin modified phenolic resin B (normal heptane tolerance 20 ml) 45 parts, linseed oil 20 parts, diallen 168 10 parts, soybean oil 14.5 parts, soybean oil fatty acid butyl ester 10 parts, aluminum chelate (ALCH) 0.5 part 190 Varnish E was obtained by heating and stirring at 0 ° C. for 1 hour.

[Example of ink preparation]
Lionol Blue FG7330 (manufactured by Toyo Ink Co., Ltd.), Varnish A to E, Silicone Oil A (Toshiba Silicone Co., Ltd. dimethylpolysiloxane, 100 cSt, molecular weight 6600), Silicone Oil B (Toshiba Silicone Co., Ltd. dimethyl) Polysiloxane, 6000 cSt, molecular weight 51000), polyamide A (condensate of dimer acid and diethylenetriamine, molecular weight 3000), α-olefin polymer A (manufactured by Toyo Petrolite Co., Ltd., Viper 825, Mw = 10000, 1350 mPa · s), α-olefin polymer B (prototype sample manufactured by Toyo Petrolite Co., Ltd., Mw = 24000, 3300 mPa · s), soybean oil, and AF solvent 5 are blended as shown in Table 2, using three rolls according to a conventional method. 80 Pa · s to 82 Pa · s Inks were prepared to be Examples 1 to 10 and Comparative Examples 1 and 2.

(Print test evaluation)
The inks of Examples 1 to 10 and Comparative Examples 1 and 2 were printed on art paper or further using a waterless lithographic TAP-HG2 manufactured by Toray Industries, Inc. on a Lislon 40-sheet printing machine manufactured by Komori Corporation. Paper was used and waterless printing was performed at 10,000 rph. Table 3 shows the results when the background soil temperature and the inking property are evaluated and the printing paper is art paper. Table 4 shows the results when the printing paper is replaced.

The background stain temperature refers to a temperature at which stain on the non-image area starts to appear on the printing paper surface when the plate surface temperature during printing is changed.

  The inking property is confirmed with a densitometer and visual evaluation of the state of the solid part when printed at the same key opening and the same temperature. The score was given by a five-step evaluation. (The higher the score, the better.)

印刷用紙＜アート紙＞

Printing paper <art paper>

印刷用紙＜更紙＞

Printing paper <replacement>

  In the waterless lithographic printing, a waterless lithographic printing ink comprising a vegetable oil or a mineral oil as a pigment, a binder resin, and a solvent component is used to form an ink composition of an α-olefin and an amine compound. It is possible to provide a waterless lithographic printing ink that has superior resistance to paper peeling, flaking, and stain resistance compared to a lithographic ink.

Claims (11)

  It contains 5 to 30% by weight of pigment, 20 to 50% by weight of binder resin, 1 to 40% by weight of α-olefin, 0.1 to 10% by weight of amine compound and 20 to 70% by weight of solvent. An ink composition for waterless lithographic printing.   2. The waterless lithographic printing ink composition according to claim 1, further comprising an organopolysiloxane.   The water-free lithographic printing ink composition according to claim 1 or 2, wherein the binder resin is an α-olefin polymer.   The water-free lithographic printing ink composition according to any one of claims 1 to 3, wherein the binder resin has a weight average molecular weight of 10,000 to 400,000.   The waterless lithographic printing ink composition according to any one of claims 1 to 4, wherein the binder resin is a rosin-modified phenol resin having a normal heptane tolerance of 1 ml to 40 ml.   The water-less lithographic printing ink composition according to any one of claims 1 to 5, wherein the α-olefin has 12 to 18 carbon atoms.   The waterless lithographic printing according to any one of claims 1 to 6, wherein the amine compound is a monomer or a polyamide compound having a molecular weight of 500 to 20,000 comprising an acid having 6 to 60 carbon atoms and an amine. Ink composition.   The waterless lithographic printing ink composition according to any one of claims 1 to 7, wherein the solvent is at least one selected from the group consisting of petroleum solvents, mineral oils, vegetable oils, and vegetable oil esters.   The waterless lithographic printing ink composition according to any one of claims 1 to 8, wherein the solvent comprises at least one vegetable oil selected from the group consisting of soybean oil, coconut oil, linseed oil, and rapeseed oil.   The ink composition for waterless lithographic printing according to any one of claims 1 to 9, wherein the ink composition is a permeation dry type.   A printed matter obtained by printing the waterless lithographic printing ink according to claim 1 on uncoated paper or finely coated paper.