WO2016104283A1 - Lithographic ink composition - Google Patents
Lithographic ink composition Download PDFInfo
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- WO2016104283A1 WO2016104283A1 PCT/JP2015/085216 JP2015085216W WO2016104283A1 WO 2016104283 A1 WO2016104283 A1 WO 2016104283A1 JP 2015085216 W JP2015085216 W JP 2015085216W WO 2016104283 A1 WO2016104283 A1 WO 2016104283A1
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- WIPO (PCT)
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- water
- ink composition
- printing ink
- lithographic printing
- mass
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
Definitions
- the present invention relates to a lithographic printing ink composition that stably retains water in ink.
- Lithographic printing using fountain solution forms an image on the printing plate using the repulsion between water and oil (ink is equivalent to oil).
- Ink adheres to the image area (lipophilic area) on the printing plate, and the surface of the non-image area (hydrophilic area) is covered with dampening water to repel the ink. Then, the ink is transferred from the plate surface to the paper or the like, and an image is formed on the paper.
- VOC volatile organic compounds
- VOC volatile organic compound
- VOC means a combination of VVOC and VOC in the World Health Organization VOC classification. This is also the Eco Mark standard for printing inks.
- One way to reduce VOC contained in printing ink is to replace the petroleum solvent, which is the raw material of printing ink, with water.
- water-soluble polysaccharides are used to retain water in the ink.
- Patent Document 1 describes a lithographic printing ink containing 0.1 to 15% by weight of cellulose or a water-insoluble cellulose derivative. It is said that the non-image area does not become sensitized and no smear occurs during printing. However, since the printing ink of this document does not contain water, VOC is not reduced. Moreover, it is said that it is not preferable that a cellulose derivative is water-soluble.
- Patent Document 2 describes an ink characterized in that it contains fine particles made of a water-insoluble superabsorbent resin, and that the resin absorbs 50 times or less of its own weight of water. This ink is said to be able to maintain good printability without causing stain even when the supply amount of dampening water becomes insufficient.
- Patent Document 3 describes a lithographic printing ink characterized in that a water-absorbing polymer that has absorbed water at least 100 times its own weight is dispersed in an ink vehicle. This ink can expand the range of the appropriate amount of fountain solution without affecting the other properties of the ink (that is, it can print properly over a wide range with less or more fountain solution). Has been. This document does not describe the water solubility of the polymer and the viscosity of the aqueous solution.
- Patent Document 4 describes a water-based ink for offset lithography newspaper printing that does not use a fountain solution (fountain solution).
- a fountain solution fountain solution
- water and water-soluble resin and resin binder are included.
- the ink of this document can be printed only with a waterless printing plate. It cannot be used for lithographic printing using a conventional fountain solution.
- An object of the present invention is to provide a lithographic printing ink composition having a reduced volatile organic solvent (VOC) content in printing ink and having excellent printability.
- VOC volatile organic solvent
- the present invention is a lithographic printing ink composition that satisfies all the following conditions (a) to (d).
- (A) Contains 0.01 to 3% by mass of a water-soluble cellulose derivative.
- (B) 1-30% by mass of water is contained.
- (C) The viscosity of a 2% aqueous solution of the cellulose derivative is 2.5 to 1500 mPa ⁇ s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa ⁇ s.
- D The degree of etherification of the cellulose derivative is 0.45 to 1.00.
- this invention is a lithographic printing ink composition as described in said (1) which further satisfies the following conditions.
- E The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less.
- this invention is a lithographic printing ink composition which satisfies all the following conditions.
- A It contains 0.01 to 3% by mass of a water-soluble polysaccharide.
- B 1-30% by mass of water is contained.
- C The viscosity of the 2% aqueous solution of the water-soluble polysaccharide is 2.5 to 1500 mPa ⁇ s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa ⁇ s.
- E The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less.
- this invention is a lithographic printing ink composition whose water-soluble polysaccharide is at least 1 type chosen from a water-soluble cellulose derivative, a xanthan gum, a diutane gum, and a carrageenan.
- this invention is the lithographic printing ink composition in any one of said (1) thru
- this invention is a lithographic printing ink composition in any one of said (1) thru
- this invention is the printed matter printed using the lithographic printing ink composition in any one of said (1) thru
- the lithographic printing ink composition of the present invention By using the lithographic printing ink composition of the present invention, it is possible to reduce the amount of volatile organic compounds generated from the printing ink and printed matter when using the printing ink (during printing), and to reduce the burden on the environment. . Further, the lithographic printing ink composition of the present invention has excellent printability and can stably perform high-quality printing with little occurrence of stains.
- composition ratio, part,%, etc. of the raw material blend are based on mass unless otherwise specified.
- the main components of the lithographic printing ink composition of the present invention include colorants, vehicles and auxiliaries.
- Colorants include pigments, dyes, etc., but pigments include those called almost colorless extender pigments.
- Inorganic pigments include yellow lead, zinc yellow, bitumen, cadmium red, zinc white, petal, alumina white, ultramarine, carbon black, graphite, aluminum powder, clay of clay, talc, barium sulfate, calcium carbonate, Examples include heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite, and titanium oxide.
- organic pigments examples include pigments used for offset inks such as azo, phthalocyanine, quinacridone, anthraquinone, and dioxazine.
- organic pigments for example, copper phthalocyanine pigments (CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, CI Pigment Green 7, 36) Monoazo pigments (CI Pigment Red 3, 4, 5, 23, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 53: 1, 57: 1 ), Disazo pigments (CI Pigment Yellow 12, 13, 14, 17, 83), anthraquinone pigments (CI Pigment Red 177), quinacridone pigments (CI Pigment Red 122, CI) Pigment Violet 19), dioxazine pigments (CI Pigment Violet 23), etc. It is, but not limited thereto.
- the vehicle comprises vegetable oil, vegetable oil fatty acid ester, oil made from vegetable oil as a raw material, oil such as mineral oil, natural resin and / or synthetic resin, plasticizer, wax and solvent.
- the solvent includes an organic solvent.
- the lithographic printing ink composition of the present invention contains water as one of the components constituting the solvent.
- the natural resin and / or synthetic resin contains at least a rosin-modified phenol resin, and a rosin-modified phenol resin varnish using the rosin-modified phenol resin.
- binder resins other than rosin-modified phenolic resins include petroleum resins, alkyd resins, rosin-modified alkyd resins, petroleum resin-modified alkyd resins, and rosin esters.
- the rosin-modified phenolic resin varnish used in the lithographic printing ink composition of the present invention preferably has an n-heptane tolerance value of 5 to 50 (mL / 3 g). L is liters.
- the tolerance value can be measured by a general method. For example, while maintaining 3 g of varnish at 25 ° C., n-heptane is dropped and mixed with the varnish and stirred, and the amount of n-heptane added (mL) when completely clouded is n-heptane tolerance (unit: mL / 3g).
- the rosin-modified phenolic resin varnish used in the lithographic printing ink composition of the present invention can be obtained by a known synthesis method.
- it is a method of adding a vegetable oil or an organic solvent to a known rosin-modified phenolic resin and dissolving it by heating, and performing a transesterification reaction with a vegetable oil component and / or a chelation reaction using an aluminum chelate.
- a rosin-modified phenolic resin having a different molecular weight, or as other binder resin petroleum resin, alkyd resin, rosin-modified alkyd resin, petroleum resin-modified alkyd resin, rosin ester, etc. are heated and dissolved together. Adjustment to a predetermined tolerance value is possible by using a method for changing the temperature of transesterification.
- the vegetable oil component used in the lithographic printing ink composition of the present invention includes oils such as soybean oil, linseed oil, rice oil, giraffe oil, castor oil, dehydrated castor oil, corn oil, safflower oil, south sea oil paulownia oil, canol oil, etc. And their thermal polymerization oils and oxidation polymerization oils.
- linseed oil fatty acid methyl ester As vegetable oil fatty acid esters, linseed oil fatty acid methyl ester, linseed oil fatty acid ethyl ester, linseed oil fatty acid propyl ester, linseed oil fatty acid butyl ester, soybean oil fatty acid methyl ester, soybean oil fatty acid ethyl ester, soybean oil fatty acid propyl ester, soybean oil fatty acid Butyl ester, Palm oil fatty acid methyl ester, Palm oil fatty acid ethyl ester, Palm oil fatty acid propyl ester, Palm oil fatty acid butyl ester, Castor oil fatty acid methyl ester, Castor oil fatty acid ethyl ester, Castor oil fatty acid propyl ester, Castor oil fatty acid butyl ester, South sea oil Tung oil Ester etc.
- Di-n-octyl ether, di-nonyl ether, dihexyl ether, nonyl hexyl ether, nonyl butyl ether, diheptyl ether, didecyl ether, nonyl octyl ether and the like can be used in the same manner as ethers made from vegetable oil.
- the vegetable oil component can be used even if it is a regenerated vegetable oil.
- Regenerated vegetable oil refers to vegetable oil that has been recovered by collecting oil used for cooking and the like.
- the regenerated vegetable oil is preferably an oil regenerated with a water content of 0.3% by mass or less, an iodine value of 90 or more, and an acid value of 3 or less, more preferably an iodine value of 100 or more.
- the water content 0.3% by mass or less, it becomes possible to remove impurities that affect the emulsification behavior of the ink, such as salt contained in moisture, and by regenerating with an iodine value of 90 or more, drying characteristics That is, it becomes possible to make it good in oxidative polymerizability, and it becomes possible to suppress over-emulsification of ink by selecting and regenerating vegetable oil having an acid value of 3 or less.
- Examples of the method for regenerating the recovered vegetable oil include methods such as filtration, removal of precipitates by standing, and decolorization by activated clay.
- Organic solvent used in the lithographic printing ink composition of the present invention, those generally used for printing inks can be used.
- the boiling range is preferably 230 to 320 ° C.
- examples of the organic solvent include AF Solvent Nos. 4, 5, 6, and 7 manufactured by JX Nippon Oil & Energy, ISU Chemical Co., Ltd.
- examples thereof include DSOL240, 260SP, 260C manufactured by LTD.
- auxiliary agents include dryers, compounds for adjusting viscosity, waxes, anti-drying agents, antifoaming agents, surfactants (emulsifiers) for adjusting emulsification suitability, preservatives, and bactericides.
- auxiliary agents include dryers, compounds for adjusting viscosity, waxes, anti-drying agents, antifoaming agents, surfactants (emulsifiers) for adjusting emulsification suitability, preservatives, and bactericides.
- the lithographic printing ink composition of the present invention contains a water-soluble polysaccharide described later as one of auxiliary agents.
- Wax is added to prevent the printing ink film from rubbing.
- a general wax used in printing ink can be used.
- a surfactant may be used together with the water-soluble polysaccharide described later.
- the emulsifier either water-soluble or water-insoluble can be used, and these may be used together.
- a water-insoluble emulsifier when used, its content is less than 1% by mass of the lithographic printing ink composition. It is preferable to set it as 0.6 mass% or less.
- the water-insoluble emulsifier remains in the printing ink without being eluted in the fountain solution, unlike the water-soluble emulsifier.
- the printing ink composition is excessively emulsified due to excessive dampening water, and the water rod There is a possibility that the stain resistance may be lowered by entanglement and inhibiting the transfer of dampening water.
- the content of the water-insoluble surfactant (emulsifier) in the above range, such a problem can be prevented.
- water-soluble emulsifier conventionally known emulsifiers can be used and are not particularly limited, and examples thereof include tridecanol, 2-hexyloctanol, 2-hexyldecanol, 2-octyldecanol, and hexyl diglycol.
- water-insoluble emulsifier include sorbitan monooleate, glycerin monooleate, polyoxyethylene cumylphenyl ether, and the like.
- Such emulsifiers are also available as commercial products, and examples thereof include Kao's Rheodor SP-010V and Rhedol SP-030V, and Nippon Emulsifier Newcol CMP-1.
- acids such as phosphoric acids and salts thereof, citric acid and salts thereof, and salts thereof are often added.
- One purpose of adding such inorganic acids, organic acids and salts thereof is to prevent the printing ink composition from adhering to the non-image area of the printing plate.
- acids or salts thereof are added to the lithographic printing ink composition of the present invention, the solubility of the water-soluble polysaccharide in water is decreased and insolubilized, and the storage stability and stain resistance may be decreased. is there.
- the total content of inorganic acids, organic acids and salts thereof in the printing ink composition of the present invention is preferably 0.2% by mass or less, and 0.1% by mass or less of the lithographic printing ink composition. More preferably, it is more preferable to set it as 0.05 mass% or less. Thereby, the above problems can be prevented.
- inorganic acids, organic acids and salts thereof include phosphoric acids such as phosphoric acid, pyrophosphoric acid, metaphosphoric acid, hexametaphosphoric acid, polyphosphoric acid, ammonium salts, alkali metal salts, alkaline earths of these phosphoric acids.
- phosphoric acids such as phosphoric acid, pyrophosphoric acid, metaphosphoric acid, hexametaphosphoric acid, polyphosphoric acid, ammonium salts, alkali metal salts, alkaline earths of these phosphoric acids.
- Metal dihydrogen salt, citric acid, ammonium salt of citric acid, alkali metal salt, magnesium salt and the like are examples of the above-mentioned inorganic acids, organic acids and salts thereof.
- the amount of water in the ink is preferably 1 to 30% in order to maintain good printability.
- the water content is more preferably 1 to 20%, still more preferably 1 to 15%.
- water-soluble polysaccharides used in the present invention include water-soluble cellulose derivatives, gum arabic, carrageenan, guar gum, pectin, tragacanth, cherry, spirrane, glucomannan, amylose, welan gum (gellan gum), tara gum (spin gum), locust bean gum , Pullulan, diyutan gum, xanthan gum, sodium chondroitin sulfate and the like.
- Water-soluble cellulose derivatives, xanthan gum, dieutan gum and carrageenan are preferred, and water-soluble cellulose derivatives are particularly preferred.
- water-soluble cellulose derivatives examples include methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and cationized cellulose obtained by adding a cationizing agent to these celluloses.
- sodium carboxymethyl cellulose hereinafter also referred to as CMC
- CMC sodium carboxymethyl cellulose
- the content of the water-soluble polysaccharide in the lithographic printing ink composition of the present invention is preferably 0.01 to 3%. If the water-soluble polysaccharide exceeds 3%, excessive moisture is taken into the ink during printing, and the transferability of the ink between the rollers of the printing press and the transferability of the ink from the blanket to the plate are reduced, resulting in uneven density. -Poor quality such as scraping is likely to occur, and printability is impaired. If the water-soluble polysaccharide is 0.01% or less, an appropriate water retention capacity cannot be obtained.
- the content of the water-soluble polysaccharide is more preferably 0.01 to 2%, still more preferably 0.01 to 1%.
- the viscosity of the water-soluble polysaccharide is preferably 2.5 to 1500 mPa ⁇ s for a 2% aqueous solution dissolved in distilled water, or 10 to 8000 mPa ⁇ s for the 1% aqueous solution. More preferably, the viscosity of a 1% aqueous solution of a water-soluble polysaccharide is 10 to 4000 mPa ⁇ s. More preferably, the viscosity of a 1% aqueous solution of the water-soluble polysaccharide is 10 to 2000 mPa ⁇ s.
- the viscosity of the aqueous solution of the water-soluble polysaccharide is measured using a Brookfield type rotational viscometer (hereinafter also referred to as B type rotational viscometer) described in JIS K7117-1.
- B type rotational viscometer is a Brookfield type rotational viscometer (model BM) manufactured by Tokyo Keiki Co., Ltd.
- the specific measurement procedure is as follows. 1) Measurement of water content in water-soluble polysaccharide Samples 1 to 2 g of water-soluble polysaccharide were accurately weighed in a weighing bottle, dried in a constant temperature dryer at 105 + -2 ° C for 4 hours, and cooled in a desiccator.
- Moisture content (%) (weight loss (g) / sample (g)) ⁇ 100 2)
- Moisture content (%) (weight loss (g) / sample (g)) ⁇ 100 2)
- Preparation of aqueous solution In a 300 mL (milliliter) Erlenmeyer flask with a stopper, weigh accurately about 4.4 g for a concentration of 2% and about 2.2 g for a concentration of 1%. Add the distilled water obtained and dissolve.
- Viscosity (mPa ⁇ s) reading scale ⁇ coefficient
- the coefficient of the previous equation is obtained from Table 1 based on the number of the rotor used and the number of rotations.
- the degree of etherification is preferably 0.45 to 1.00. If the degree of etherification is less than 0.45, the water solubility decreases, and if it exceeds 1.00, the printability of the ink decreases.
- the degree of etherification is more preferably 0.45 to 0.80, and further preferably 0.45 to 0.70.
- the degree of etherification refers to the number of carboxymethyl groups per unit of anhydrous glucose.
- the degree of etherification is 1.0.
- An example of a method for measuring the degree of etherification is as follows. A sample (anhydride) of 0.5 to 0.7 g is precisely weighed, wrapped in filter paper and incinerated in a magnetic crucible. After cooling, transfer this to a 500 mL (milliliter) beaker, add about 250 mL of water and 35 mL of 0.05 mol / L sulfuric acid with a pipette and boil for 30 minutes.
- the lithographic printing ink composition of the present invention is produced using a kneading disperser such as a three-roll mill by mixing the colorant, vehicle and auxiliary agent.
- Water and water-soluble polysaccharides can be added at any time during ink production. Each can be added separately, and water and CMC are mixed and stirred to make a uniform solution, which is added to printing ink (base ink) separately manufactured from raw materials other than CMC, and the whole is uniformly mixed It can also be finished as a printing ink.
- the lithographic printing ink composition of the present invention is prepared so that raw materials having the following composition are kneaded and dispersed by a known method using a three-roll mill or the like so that the particle size of coarse particles in the ink is 5 ⁇ m or less.
- the desired ink can be obtained.
- the particle size of the coarse particles in the ink refers to the kneading degree in the kneading degree test described in JIS K5701-1.
- the test method defined in 4.3 JIS K5701-1 (enacted on January 20, 2000) is as follows. Place a sample such as ink in a deep place on the grindometer gauge board where the groove depth (groove scale) varies linearly from 25 ⁇ m to 0 ⁇ m, and scrape with a scraper into the groove. Make a sample film. A scale indicating the depth of the groove is engraved on the gauge board.
- the particles When particles are present in the sample, the particles are scraped off and moved by a scraper, and a line is formed in a groove shallower than the size (diameter, etc.) of the particles.
- the line is observed, and the value of the scale where three or more continuous lines appear for 10 mm or more appear in one groove is A, and the position of the scale value where 10 or more lines appear is B.
- the particle diameter of the coarse particles in the ink is a scale value at the position A.
- the lithographic printing ink composition of the present invention can be suitably used for both lithographic printing using fountain solution and waterless lithographic printing without using fountain solution.
- F-8305 is a rosin-modified phenolic resin having a weight average molecular weight of 38,000, an acid value of 16.5, and an n-heptane tolerance of 400%.
- n-heptane tolerance was obtained by adding n-heptane dropwise while keeping 1 g of a rosin-modified phenolic resin and toluene mixed at a mass ratio of 1: 1 at 25 ° C. until the solution became cloudy. It is a value obtained by multiplying the amount (mL) by 100.
- the base ink, varnish and other components were blended according to the blending ratio shown in Table 2-4, and uniformly mixed and dispersed using a mixer or the like to produce the inks shown in Examples 1 to 20.
- inks of Comparative Examples 1 to 15 and Reference Example were prepared according to the blending ratios shown in Table 5-7.
- the water-soluble polysaccharide was added directly depending on the blending amount or added after making an aqueous solution.
- a reference example is a printing ink that is generally used in the past and does not contain water-soluble polysaccharides and water.
- the printability of this ink was set to 2 (standard level). A printability of 2 or more is good and less than 2 is bad. Since the printing inks of Comparative Example 9 and Reference Example do not contain water, the storage stability was not evaluated.
- water-soluble polysaccharides having the viscosity and the degree of etherification (in the case of CMC) shown in each example were used.
- HEC in the table is hydroxyethylcellulose
- HPC is hydroxypropylcellulose
- HPMC is hydroxypropylmethylcellulose.
- Examples of CMC manufacturers include Daicel Finechem Co., Ltd., Daiichi Kogyo Seiyaku Co., Ltd., Nichirin Chemical Co., Ltd., Nippon Paper Industries Co., Ltd., and CP kelco.
- the water-soluble polysaccharide viscosity (1%) in each table represents the viscosity of an aqueous solution having a water-soluble polysaccharide concentration of 1%.
- the water-soluble polysaccharide viscosity (2%) represents the viscosity of an aqueous solution having a water-soluble polysaccharide concentration of 2%.
- As the phosphoric acid an 85% aqueous solution (manufactured by Wako Pure Chemical Industries) was used.
- surface means the compounding quantity of 85% aqueous solution.
- the water-insoluble emulsifier glyceryl monooleate (Reodol SP-030V manufactured by Kao) was used.
- the inks of Examples and Comparative Examples prepared above were evaluated by the following evaluation methods.
- Storage stability evaluation method After the ink was prepared, the ink was stored at 25 ° C. and a relative humidity of 50% for 3 months, then 1.0 g of the ink was placed on a Hoover Maller, and the ink was kneaded 100 revolutions at a weight of 1.1 kg. The ink after kneading was scraped with an ink knife, and this ink was observed as follows. Water droplets separated from the ink are hardly seen ... 3 (good) Minute water droplets separated from ink can be seen ... 2 (no problem in practical use) Many water droplets separated from ink can be seen ... 1 (not practical)
- Printing machine Roland R700 printing machine (man Roland) Printing speed: 10,000 sheets / hour printing plate: Ex Thermo TP-W (manufactured by Kodak GK) Liquid H: Presert WD100 (manufactured by DIC Corporation) Paper: OK top coat + (US tsubo 104.7 g / m 2 manufactured by Oji Paper Co., Ltd.) Liquid H was diluted with water to a concentration of 1% and used as the fountain solution.
- the evaluation of the smearing property was performed by magnifying and observing a 50% halftone dot portion of the paper surface when printing 10,000 copies with a microscope, and evaluating the degree of smearing in the non-image area in the following three stages. Dirt is hardly seen ... 3 (good) Slight dirt is seen but there is no practical problem ... 2 There is a lot of dirt and there are practical problems ... 1
- VOC reduction rate 100 ⁇ (VOC amount of each ink / VOC amount of reference example ink) ⁇ 100
- the amount of VOC in each ink is the total amount of AF Solvent No. 7 (AF-7).
- the total amount of AF-7 in the varnish and base ink and the AF-7 in the formulation shown in Table 2-7 are the total. And asked.
- the lithographic printing ink composition of the present invention By using the lithographic printing ink composition of the present invention, it is possible to reduce the amount of volatile organic compounds generated from the printing ink and printed matter when using the printing ink (during printing), and to reduce the burden on the environment. . Further, the lithographic printing ink composition of the present invention has excellent printability and can stably perform high-quality printing with little occurrence of stains.
Abstract
The present invention addresses the problem of providing a lithographic ink composition that has superior printability and reduces the volatile organic solvent (VOC) content in a printing ink. The lithographic ink composition satisfies all of the following conditions (a)-(d). (a) A water-soluble cellulose derivative is included at 0.01-3 mass%. (b) Water is included at 1-30 mass%. (c) A 2% aqueous solution of the cellulose derivative has a viscosity of 2.5 to 1500 mPa·s, or a 1% aqueous solution thereof has a viscosity of 10-8000 mPa·s. (d) The cellulose derivative has an etherification degree of 0.45-1.00. Additionally, the present invention is the lithographic ink composition to be used in a printing method wherein a dampening solution is used. Moreover, the present invention is a printed matter that has been printed using the lithographic ink composition.
Description
本発明はインキ中に水を安定して保持する平版印刷インキ組成物に関する。
The present invention relates to a lithographic printing ink composition that stably retains water in ink.
湿し水を用いた平版印刷は、水と油（インキは油に相当する）との反発を利用して印刷版上に画像を形成する。版面上の画線部（親油性部分）にはインキが付着し、非画線部（親水性部分）は表面が湿し水で被覆されてインキを反発する。そして版面から用紙等へインキが転移し、用紙上に画像が形成される。
Lithographic printing using fountain solution forms an image on the printing plate using the repulsion between water and oil (ink is equivalent to oil). Ink adheres to the image area (lipophilic area) on the printing plate, and the surface of the non-image area (hydrophilic area) is covered with dampening water to repel the ink. Then, the ink is transferred from the plate surface to the paper or the like, and an image is formed on the paper.
印刷インキの原料の一つとして石油系有機溶剤が用いられるが、この溶剤の大部分は揮発性有機化合物（ＶＯＣ）に属する。環境保全及び地球温暖化防止のために、温室効果ガスおよび揮発性有機化合物（ＶＯＣ）の排出量を削減することへの社会的要望が高まっている。
尚、本明細書において揮発性有機化合物（ＶＯＣ）とは、世界保健機構のＶＯＣ分類中のＶＶＯＣ及びＶＯＣを合わせたものをいう。これは印刷インキのエコマーク基準でもある。
ＶＶＯＣ・・・沸点範囲 ０℃～５０－１００℃
ＶＯＣ・・・・沸点範囲 ５０－１００℃～２４０－２６０℃ Petroleum organic solvents are used as one of the raw materials for printing inks, and most of these solvents belong to volatile organic compounds (VOC). In order to protect the environment and prevent global warming, there is an increasing social demand for reducing greenhouse gas and volatile organic compound (VOC) emissions.
In the present specification, the volatile organic compound (VOC) means a combination of VVOC and VOC in the World Health Organization VOC classification. This is also the Eco Mark standard for printing inks.
VVOC: Boiling range 0 ° C-50-100 ° C
VOC ··· Boiling range 50-100 ° C to 240-260 ° C
尚、本明細書において揮発性有機化合物（ＶＯＣ）とは、世界保健機構のＶＯＣ分類中のＶＶＯＣ及びＶＯＣを合わせたものをいう。これは印刷インキのエコマーク基準でもある。
ＶＶＯＣ・・・沸点範囲 ０℃～５０－１００℃
ＶＯＣ・・・・沸点範囲 ５０－１００℃～２４０－２６０℃ Petroleum organic solvents are used as one of the raw materials for printing inks, and most of these solvents belong to volatile organic compounds (VOC). In order to protect the environment and prevent global warming, there is an increasing social demand for reducing greenhouse gas and volatile organic compound (VOC) emissions.
In the present specification, the volatile organic compound (VOC) means a combination of VVOC and VOC in the World Health Organization VOC classification. This is also the Eco Mark standard for printing inks.
VVOC: Boiling range 0 ° C-50-100 ° C
VOC ··· Boiling range 50-100 ° C to 240-260 ° C
印刷インキに含まれるＶＯＣを削減する方策の一つとして、印刷インキの原料である石油系溶剤を水に置換することが挙げられる。本発明では水をインキ中に保持するために水溶性の多糖類を用いるが、関連する技術として特許文献１～４に記載された発明がある。
One way to reduce VOC contained in printing ink is to replace the petroleum solvent, which is the raw material of printing ink, with water. In the present invention, water-soluble polysaccharides are used to retain water in the ink. As related techniques, there are inventions described in Patent Documents 1 to 4.
特許文献１にはセルロースまたは非水溶性のセルロース誘導体を０．１～１５重量％含む平版印刷インキが記載されている。非画線部の感脂化を起こさず、印刷時に汚れの発生が無いとされている。但し本文献の印刷インキは水を含有しないため、ＶＯＣは削減されない。またセルロース誘導体は水溶性であることは好ましくないとされている。
Patent Document 1 describes a lithographic printing ink containing 0.1 to 15% by weight of cellulose or a water-insoluble cellulose derivative. It is said that the non-image area does not become sensitized and no smear occurs during printing. However, since the printing ink of this document does not contain water, VOC is not reduced. Moreover, it is said that it is not preferable that a cellulose derivative is water-soluble.
特許文献２には非水溶性の高吸水性樹脂からなる微粒子を含有し、その樹脂が自重の５０倍以下の量の水を吸収していることを特徴とするインキが記載されている。このインキは、湿し水の供給量が不足ぎみになったときでも汚れを発生させないで良好な印刷適性を保持できるとされている。
Patent Document 2 describes an ink characterized in that it contains fine particles made of a water-insoluble superabsorbent resin, and that the resin absorbs 50 times or less of its own weight of water. This ink is said to be able to maintain good printability without causing stain even when the supply amount of dampening water becomes insufficient.
特許文献３には自重の１００倍以上の水を吸収させた吸水性ポリマーをインキビヒクル中に分散せしめたことを特徴とする平版印刷インキが記載されている。このインキはインキの他の特性に影響を及ぼさずに、湿し水の適正供給量の幅を広げる（即ち湿し水が少な目でも多目でも広い範囲で適正に印刷が行える）ことができるとされている。この文献には該ポリマーの水溶性や、その水溶液の粘度に関する記載は無い。
Patent Document 3 describes a lithographic printing ink characterized in that a water-absorbing polymer that has absorbed water at least 100 times its own weight is dispersed in an ink vehicle. This ink can expand the range of the appropriate amount of fountain solution without affecting the other properties of the ink (that is, it can print properly over a wide range with less or more fountain solution). Has been. This document does not describe the water solubility of the polymer and the viscosity of the aqueous solution.
特許文献４には、ファウンテン溶液（湿し水）を用いない、オフセットリソグラフィー新聞印刷用の水性インクが記載されている。印刷インクからのＶＯＣ発生を減少させるために水及び水可溶性の樹脂や樹脂バインダーを含む。但し、本文献のインクは水なし印刷版でのみ印刷することができる。従来の湿し水を用いる平版印刷には用いることはできない。
Patent Document 4 describes a water-based ink for offset lithography newspaper printing that does not use a fountain solution (fountain solution). In order to reduce VOC generation from printing ink, water and water-soluble resin and resin binder are included. However, the ink of this document can be printed only with a waterless printing plate. It cannot be used for lithographic printing using a conventional fountain solution.
本発明は、印刷インキ中の揮発性有機溶剤（ＶＯＣ）の含有量を削減し、且つ優れた印刷適性を有する平版印刷インキ組成物を提供することを課題とする。
An object of the present invention is to provide a lithographic printing ink composition having a reduced volatile organic solvent (VOC) content in printing ink and having excellent printability.
発明者らは次に記載の平版印刷インキ組成物が前記の課題を解決することを見出した。
（１）即ち本発明は、次の（ａ）～（ｄ）の条件をすべて満足する平版印刷インキ組成物である。
（ａ）水溶性のセルロース誘導体を０．０１～３質量％含有する。
（ｂ）水を１～３０質量％含有する。
（ｃ）前記のセルロース誘導体の２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓである。
（ｄ）前記のセルロース誘導体のエーテル化度が０．４５～１．００である。 The inventors have found that the lithographic printing ink composition described below solves the above problems.
(1) That is, the present invention is a lithographic printing ink composition that satisfies all the following conditions (a) to (d).
(A) Contains 0.01 to 3% by mass of a water-soluble cellulose derivative.
(B) 1-30% by mass of water is contained.
(C) The viscosity of a 2% aqueous solution of the cellulose derivative is 2.5 to 1500 mPa · s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa · s.
(D) The degree of etherification of the cellulose derivative is 0.45 to 1.00.
（１）即ち本発明は、次の（ａ）～（ｄ）の条件をすべて満足する平版印刷インキ組成物である。
（ａ）水溶性のセルロース誘導体を０．０１～３質量％含有する。
（ｂ）水を１～３０質量％含有する。
（ｃ）前記のセルロース誘導体の２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓである。
（ｄ）前記のセルロース誘導体のエーテル化度が０．４５～１．００である。 The inventors have found that the lithographic printing ink composition described below solves the above problems.
(1) That is, the present invention is a lithographic printing ink composition that satisfies all the following conditions (a) to (d).
(A) Contains 0.01 to 3% by mass of a water-soluble cellulose derivative.
(B) 1-30% by mass of water is contained.
(C) The viscosity of a 2% aqueous solution of the cellulose derivative is 2.5 to 1500 mPa · s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa · s.
(D) The degree of etherification of the cellulose derivative is 0.45 to 1.00.
（２）また本発明は、さらに以下の条件を満足する前記（１）に記載の平版印刷インキ組成物である。
（ｅ）無機酸、無機酸の塩、有機酸、有機酸の塩の含有量の合計が０．２質量％以下である。 (2) Moreover, this invention is a lithographic printing ink composition as described in said (1) which further satisfies the following conditions.
(E) The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less.
（ｅ）無機酸、無機酸の塩、有機酸、有機酸の塩の含有量の合計が０．２質量％以下である。 (2) Moreover, this invention is a lithographic printing ink composition as described in said (1) which further satisfies the following conditions.
(E) The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less.
（３）あるいは本発明は、次の条件をすべて満足する平版印刷インキ組成物である。
（Ａ）水溶性多糖類を０．０１～３質量％含有する。
（ｂ）水を１～３０質量％含有する。
（ｃ）前記水溶性多糖類の２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓである。
（ｅ）無機酸、無機酸の塩、有機酸、有機酸の塩の含有量の合計が０．２質量％以下である。 (3) Or this invention is a lithographic printing ink composition which satisfies all the following conditions.
(A) It contains 0.01 to 3% by mass of a water-soluble polysaccharide.
(B) 1-30% by mass of water is contained.
(C) The viscosity of the 2% aqueous solution of the water-soluble polysaccharide is 2.5 to 1500 mPa · s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa · s.
(E) The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less.
（Ａ）水溶性多糖類を０．０１～３質量％含有する。
（ｂ）水を１～３０質量％含有する。
（ｃ）前記水溶性多糖類の２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓである。
（ｅ）無機酸、無機酸の塩、有機酸、有機酸の塩の含有量の合計が０．２質量％以下である。 (3) Or this invention is a lithographic printing ink composition which satisfies all the following conditions.
(A) It contains 0.01 to 3% by mass of a water-soluble polysaccharide.
(B) 1-30% by mass of water is contained.
(C) The viscosity of the 2% aqueous solution of the water-soluble polysaccharide is 2.5 to 1500 mPa · s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa · s.
(E) The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less.
（４）また本発明は、水溶性多糖類が、水溶性セルロース誘導体、キサンタンガム、ダイユータンガム、カラギーナンから選ばれる少なくとも一種である平版印刷インキ組成物である。
（５）また本発明は、非水溶性乳化剤の含有量が１．０質量％未満である前記（１）乃至（４）のいずれかに記載の平版印刷インキ組成物である。
（６）また本発明は、湿し水を用いた印刷方式に用いられる前記（１）乃至（５）のいずれかに記載の平版印刷インキ組成物である。
（７）また本発明は、前記（１）乃至（５）のいずれかに記載の平版印刷インキ組成物を用いて印刷された印刷物である。 (4) Moreover, this invention is a lithographic printing ink composition whose water-soluble polysaccharide is at least 1 type chosen from a water-soluble cellulose derivative, a xanthan gum, a diutane gum, and a carrageenan.
(5) Moreover, this invention is the lithographic printing ink composition in any one of said (1) thru | or (4) whose content of a water-insoluble emulsifier is less than 1.0 mass%.
(6) Moreover, this invention is a lithographic printing ink composition in any one of said (1) thru | or (5) used for the printing system using a dampening water.
(7) Moreover, this invention is the printed matter printed using the lithographic printing ink composition in any one of said (1) thru | or (5).
（５）また本発明は、非水溶性乳化剤の含有量が１．０質量％未満である前記（１）乃至（４）のいずれかに記載の平版印刷インキ組成物である。
（６）また本発明は、湿し水を用いた印刷方式に用いられる前記（１）乃至（５）のいずれかに記載の平版印刷インキ組成物である。
（７）また本発明は、前記（１）乃至（５）のいずれかに記載の平版印刷インキ組成物を用いて印刷された印刷物である。 (4) Moreover, this invention is a lithographic printing ink composition whose water-soluble polysaccharide is at least 1 type chosen from a water-soluble cellulose derivative, a xanthan gum, a diutane gum, and a carrageenan.
(5) Moreover, this invention is the lithographic printing ink composition in any one of said (1) thru | or (4) whose content of a water-insoluble emulsifier is less than 1.0 mass%.
(6) Moreover, this invention is a lithographic printing ink composition in any one of said (1) thru | or (5) used for the printing system using a dampening water.
(7) Moreover, this invention is the printed matter printed using the lithographic printing ink composition in any one of said (1) thru | or (5).
本発明の平版印刷インキ組成物を用いることにより、印刷インキの使用時（印刷時）において印刷インキ及び印刷物からの揮発性有機化合物の発生量を削減し、環境への負荷を低減することができる。
また本発明の平版印刷インキ組成物は優れた印刷適性を有し、汚れの発生等の少ない高品質の印刷を安定して行うことができる。 By using the lithographic printing ink composition of the present invention, it is possible to reduce the amount of volatile organic compounds generated from the printing ink and printed matter when using the printing ink (during printing), and to reduce the burden on the environment. .
Further, the lithographic printing ink composition of the present invention has excellent printability and can stably perform high-quality printing with little occurrence of stains.
また本発明の平版印刷インキ組成物は優れた印刷適性を有し、汚れの発生等の少ない高品質の印刷を安定して行うことができる。 By using the lithographic printing ink composition of the present invention, it is possible to reduce the amount of volatile organic compounds generated from the printing ink and printed matter when using the printing ink (during printing), and to reduce the burden on the environment. .
Further, the lithographic printing ink composition of the present invention has excellent printability and can stably perform high-quality printing with little occurrence of stains.
本明細書において、原料配合の組成割合、部、％等は特記しない限り質量基準である。
（インキ組成の概要説明）
本発明の平版印刷インキ組成物の主要な成分として、色料、ビヒクル及び助剤が挙げられる。 In the present specification, the composition ratio, part,%, etc. of the raw material blend are based on mass unless otherwise specified.
(Overview of ink composition)
The main components of the lithographic printing ink composition of the present invention include colorants, vehicles and auxiliaries.
（インキ組成の概要説明）
本発明の平版印刷インキ組成物の主要な成分として、色料、ビヒクル及び助剤が挙げられる。 In the present specification, the composition ratio, part,%, etc. of the raw material blend are based on mass unless otherwise specified.
(Overview of ink composition)
The main components of the lithographic printing ink composition of the present invention include colorants, vehicles and auxiliaries.
色料として顔料、染料等が挙げられるが、顔料にはほぼ無色の体質顔料と呼ばれるものが含まれる。
Colorants include pigments, dyes, etc., but pigments include those called almost colorless extender pigments.
（顔料）
本発明の平版印刷インキ組成物に用いられる顔料としては、任意の無機及び有機顔料が使用できる。無機顔料としては、黄鉛、亜鉛黄、紺青、カドミウムレッド、亜鉛華、弁柄、アルミナホワイト、群青、カーボンブラック、グラファイト、アルミニウム粉、ろう石クレー等のクレー、タルク、硫酸バリウム、炭酸カルシウム、重質炭酸カルシウム、炭酸バリウム、炭酸マグネシウム、シリカ、ベントナイト、酸化チタンなどがあげられる。 (Pigment)
Arbitrary inorganic and organic pigments can be used as the pigment used in the lithographic printing ink composition of the present invention. Inorganic pigments include yellow lead, zinc yellow, bitumen, cadmium red, zinc white, petal, alumina white, ultramarine, carbon black, graphite, aluminum powder, clay of clay, talc, barium sulfate, calcium carbonate, Examples include heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite, and titanium oxide.
本発明の平版印刷インキ組成物に用いられる顔料としては、任意の無機及び有機顔料が使用できる。無機顔料としては、黄鉛、亜鉛黄、紺青、カドミウムレッド、亜鉛華、弁柄、アルミナホワイト、群青、カーボンブラック、グラファイト、アルミニウム粉、ろう石クレー等のクレー、タルク、硫酸バリウム、炭酸カルシウム、重質炭酸カルシウム、炭酸バリウム、炭酸マグネシウム、シリカ、ベントナイト、酸化チタンなどがあげられる。 (Pigment)
Arbitrary inorganic and organic pigments can be used as the pigment used in the lithographic printing ink composition of the present invention. Inorganic pigments include yellow lead, zinc yellow, bitumen, cadmium red, zinc white, petal, alumina white, ultramarine, carbon black, graphite, aluminum powder, clay of clay, talc, barium sulfate, calcium carbonate, Examples include heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite, and titanium oxide.
有機顔料としては、アゾ系、フタロシアニン系、キナクリドン系、アントラキノン系、ジオキサジン系などオフセットインキに用いられる顔料が挙げられる。有機顔料に関しては、例えば、銅フタロシアニン系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５、１５：１、１５：２、１５：３、１５：４、１５：６、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７、３６）、モノアゾ系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３、４、５、２３、４８：１、４８：２、４８：３、４８：４、４９：１、４９：２、５３：１、５７：１）、ジスアゾ系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １２、１３、１４、１７、８３）、アントラキノン系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ１７７）、キナクリドン系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １９）、ジオキサジン系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ ２３）などが挙げられるが、これらに限定されるものではない。
Examples of organic pigments include pigments used for offset inks such as azo, phthalocyanine, quinacridone, anthraquinone, and dioxazine. Regarding organic pigments, for example, copper phthalocyanine pigments (CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, CI Pigment Green 7, 36) Monoazo pigments (CI Pigment Red 3, 4, 5, 23, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 53: 1, 57: 1 ), Disazo pigments (CI Pigment Yellow 12, 13, 14, 17, 83), anthraquinone pigments (CI Pigment Red 177), quinacridone pigments (CI Pigment Red 122, CI) Pigment Violet 19), dioxazine pigments (CI Pigment Violet 23), etc. It is, but not limited thereto.
（ビヒクルについて）
ビヒクルは植物油、植物油脂肪酸エステル、植物油を原料とするエーテル、鉱物油等の油、天然樹脂及び又は合成樹脂、可塑剤、ワックス及び溶剤等から成る。溶剤には有機溶剤等が含まれる。本発明の平版印刷インキ組成物は、溶剤を構成する成分の一つとして水を含有する。 (About vehicle)
The vehicle comprises vegetable oil, vegetable oil fatty acid ester, oil made from vegetable oil as a raw material, oil such as mineral oil, natural resin and / or synthetic resin, plasticizer, wax and solvent. The solvent includes an organic solvent. The lithographic printing ink composition of the present invention contains water as one of the components constituting the solvent.
ビヒクルは植物油、植物油脂肪酸エステル、植物油を原料とするエーテル、鉱物油等の油、天然樹脂及び又は合成樹脂、可塑剤、ワックス及び溶剤等から成る。溶剤には有機溶剤等が含まれる。本発明の平版印刷インキ組成物は、溶剤を構成する成分の一つとして水を含有する。 (About vehicle)
The vehicle comprises vegetable oil, vegetable oil fatty acid ester, oil made from vegetable oil as a raw material, oil such as mineral oil, natural resin and / or synthetic resin, plasticizer, wax and solvent. The solvent includes an organic solvent. The lithographic printing ink composition of the present invention contains water as one of the components constituting the solvent.
天然樹脂及び又は合成樹脂としては、少なくともロジン変性フェノール樹脂を含有し、それを用いたロジン変性フェノール樹脂ワニスを含有する。
The natural resin and / or synthetic resin contains at least a rosin-modified phenol resin, and a rosin-modified phenol resin varnish using the rosin-modified phenol resin.
ロジン変性フェノール樹脂以外のバインダー樹脂としては、石油樹脂、アルキッド樹脂、ロジン変性アルキッド樹脂、石油樹脂変性アルキッド樹脂、ロジンエステル等が挙げられる。
Examples of binder resins other than rosin-modified phenolic resins include petroleum resins, alkyd resins, rosin-modified alkyd resins, petroleum resin-modified alkyd resins, and rosin esters.
（ロジン変性フェノール樹脂ワニス）
本発明の平版印刷インキ組成物に使用されるロジン変性フェノール樹脂ワニスは、ｎ－ヘプタントレランス値が５～５０（ｍＬ／３ｇ）であることが好ましい。Ｌはリットルである。 (Rosin-modified phenolic resin varnish)
The rosin-modified phenolic resin varnish used in the lithographic printing ink composition of the present invention preferably has an n-heptane tolerance value of 5 to 50 (mL / 3 g). L is liters.
本発明の平版印刷インキ組成物に使用されるロジン変性フェノール樹脂ワニスは、ｎ－ヘプタントレランス値が５～５０（ｍＬ／３ｇ）であることが好ましい。Ｌはリットルである。 (Rosin-modified phenolic resin varnish)
The rosin-modified phenolic resin varnish used in the lithographic printing ink composition of the present invention preferably has an n-heptane tolerance value of 5 to 50 (mL / 3 g). L is liters.
トレランス値は一般的な方法で測定することができる。例えば、ワニス３ｇを２５℃に保ちながら、ｎ－ヘプタンを滴下してワニスと混合撹拌し、完全に白濁した時のｎ－へプタンの添加量（ｍＬ）がｎ－ヘプタントレランスである（単位はｍＬ／３ｇ）。
The tolerance value can be measured by a general method. For example, while maintaining 3 g of varnish at 25 ° C., n-heptane is dropped and mixed with the varnish and stirred, and the amount of n-heptane added (mL) when completely clouded is n-heptane tolerance (unit: mL / 3g).
本発明の平版印刷インキ組成物に用いるロジン変性フェノール樹脂ワニスは、公知の合成方法によって得られる。例えば公知のロジン変性フェノール樹脂に植物油、有機溶剤を添加して加熱溶解し、植物油成分とのエステル交換反応及び又はアルミキレートを用いたキレーション反応を行う方法である。
The rosin-modified phenolic resin varnish used in the lithographic printing ink composition of the present invention can be obtained by a known synthesis method. For example, it is a method of adding a vegetable oil or an organic solvent to a known rosin-modified phenolic resin and dissolving it by heating, and performing a transesterification reaction with a vegetable oil component and / or a chelation reaction using an aluminum chelate.
この際、分子量の異なるロジン変性フェノール樹脂を選定することや、その他のバインダー樹脂として、石油樹脂、アルキッド樹脂、ロジン変性アルキッド樹脂、石油樹脂変性アルキッド樹脂、ロジンエステル等を一緒に加熱溶解すること、エステル交換の温度を変更する手法などを用いることにより、所定のトレランス値への調整が可能になる。
At this time, selecting a rosin-modified phenolic resin having a different molecular weight, or as other binder resin, petroleum resin, alkyd resin, rosin-modified alkyd resin, petroleum resin-modified alkyd resin, rosin ester, etc. are heated and dissolved together. Adjustment to a predetermined tolerance value is possible by using a method for changing the temperature of transesterification.
（植物油）
本発明の平版印刷インキ組成物に使用される植物油成分としては、大豆油、亜麻仁油、米油、キリ油、ひまし油、脱水ひまし油、コーン油、サフラワー油、南洋油桐油、カノール油等の油類及びこれらの熱重合油、酸化重合油がある。 (Vegetable oil)
The vegetable oil component used in the lithographic printing ink composition of the present invention includes oils such as soybean oil, linseed oil, rice oil, giraffe oil, castor oil, dehydrated castor oil, corn oil, safflower oil, south sea oil paulownia oil, canol oil, etc. And their thermal polymerization oils and oxidation polymerization oils.
本発明の平版印刷インキ組成物に使用される植物油成分としては、大豆油、亜麻仁油、米油、キリ油、ひまし油、脱水ひまし油、コーン油、サフラワー油、南洋油桐油、カノール油等の油類及びこれらの熱重合油、酸化重合油がある。 (Vegetable oil)
The vegetable oil component used in the lithographic printing ink composition of the present invention includes oils such as soybean oil, linseed oil, rice oil, giraffe oil, castor oil, dehydrated castor oil, corn oil, safflower oil, south sea oil paulownia oil, canol oil, etc. And their thermal polymerization oils and oxidation polymerization oils.
植物油脂肪酸エステルとして、アマニ油脂肪酸メチルエステル、アマニ油脂肪酸エチルエステル、アマニ油脂肪酸プロピルエステル、アマニ油脂肪酸ブチルエステル、大豆油脂肪酸メチルエステル、大豆油脂肪酸エチルエステル、大豆油脂肪酸プロピルエステル、大豆油脂肪酸ブチルエステル、パーム油脂肪酸メチルエステル、パーム油脂肪酸エチルエステル、パーム油脂肪酸プロピルエステル、パーム油脂肪酸ブチルエステル、ひまし油脂肪酸メチルエステル、ひまし油脂肪酸エチルエステル、ひまし油脂肪酸プロピルエステル、ひまし油脂肪酸ブチルエステル、南洋油桐油のエステル等も同様に用いることができる。 植物油を原料とするエーテルとして、ジ－ｎ－オクチルエーテル、ジ－ノニルエーテル、ジヘキシルエーテル、ノニルヘキシルエーテル、ノニルブチルエーテル、ジヘプチルエーテル、ジデシルエーテル、ノニルオクチルエーテル等も同様に用いることができる。
As vegetable oil fatty acid esters, linseed oil fatty acid methyl ester, linseed oil fatty acid ethyl ester, linseed oil fatty acid propyl ester, linseed oil fatty acid butyl ester, soybean oil fatty acid methyl ester, soybean oil fatty acid ethyl ester, soybean oil fatty acid propyl ester, soybean oil fatty acid Butyl ester, Palm oil fatty acid methyl ester, Palm oil fatty acid ethyl ester, Palm oil fatty acid propyl ester, Palm oil fatty acid butyl ester, Castor oil fatty acid methyl ester, Castor oil fatty acid ethyl ester, Castor oil fatty acid propyl ester, Castor oil fatty acid butyl ester, South sea oil Tung oil Ester etc. can be used similarly. Di-n-octyl ether, di-nonyl ether, dihexyl ether, nonyl hexyl ether, nonyl butyl ether, diheptyl ether, didecyl ether, nonyl octyl ether and the like can be used in the same manner as ethers made from vegetable oil.
また前記の植物油成分は、再生植物油であっても使用することができる。再生植物油とは、調理等に使用された油を回収し、再生処理された植物油のことである。再生植物油としては、含水率を０．３質量％以下、ヨウ素価を９０以上、酸価を３以下として再生処理した油が好ましく、より好ましくはヨウ素価１００以上である。含水率を０．３質量％以下にすることにより水分に含まれる塩分等のインキの乳化挙動に影響を与える不純物を除去することが可能となり、ヨウ素価を９０以上として再生することにより、乾燥性、すなわち酸化重合性の良いものとすることが可能となり、さらに酸価が３以下の植物油を選別して再生することにより、インキの過乳化を抑制することが可能となる。回収植物油の再生処理方法としては、濾過、静置による沈殿物の除去、および活性白土等による脱色といった方法が例示される。
The vegetable oil component can be used even if it is a regenerated vegetable oil. Regenerated vegetable oil refers to vegetable oil that has been recovered by collecting oil used for cooking and the like. The regenerated vegetable oil is preferably an oil regenerated with a water content of 0.3% by mass or less, an iodine value of 90 or more, and an acid value of 3 or less, more preferably an iodine value of 100 or more. By making the water content 0.3% by mass or less, it becomes possible to remove impurities that affect the emulsification behavior of the ink, such as salt contained in moisture, and by regenerating with an iodine value of 90 or more, drying characteristics That is, it becomes possible to make it good in oxidative polymerizability, and it becomes possible to suppress over-emulsification of ink by selecting and regenerating vegetable oil having an acid value of 3 or less. Examples of the method for regenerating the recovered vegetable oil include methods such as filtration, removal of precipitates by standing, and decolorization by activated clay.
（有機溶剤）
本発明の平版印刷インキ組成物に使用される有機溶剤は、一般に印刷インキに用いられるものを用いることができる。沸点範囲が２３０～３２０℃であることが好ましい。この有機溶剤として、ＪＸ日鉱日石エネルギー製ＡＦソルベント４号、５号、６号、７号、ＩＳＵケミカルＣｏ．ＬＴＤ製ＤＳＯＬ２４０、２６０ＳＰ、２６０Ｃなどが例示される。 (Organic solvent)
As the organic solvent used in the lithographic printing ink composition of the present invention, those generally used for printing inks can be used. The boiling range is preferably 230 to 320 ° C. Examples of the organic solvent include AF Solvent Nos. 4, 5, 6, and 7 manufactured by JX Nippon Oil & Energy, ISU Chemical Co., Ltd. Examples thereof include DSOL240, 260SP, 260C manufactured by LTD.
本発明の平版印刷インキ組成物に使用される有機溶剤は、一般に印刷インキに用いられるものを用いることができる。沸点範囲が２３０～３２０℃であることが好ましい。この有機溶剤として、ＪＸ日鉱日石エネルギー製ＡＦソルベント４号、５号、６号、７号、ＩＳＵケミカルＣｏ．ＬＴＤ製ＤＳＯＬ２４０、２６０ＳＰ、２６０Ｃなどが例示される。 (Organic solvent)
As the organic solvent used in the lithographic printing ink composition of the present invention, those generally used for printing inks can be used. The boiling range is preferably 230 to 320 ° C. Examples of the organic solvent include AF Solvent Nos. 4, 5, 6, and 7 manufactured by JX Nippon Oil & Energy, ISU Chemical Co., Ltd. Examples thereof include DSOL240, 260SP, 260C manufactured by LTD.
（助剤について）
助剤に属するものとして、ドライヤー、粘度調節のためのコンパウンド、ワックス、乾燥防止剤、消泡剤、乳化適性を調節するための界面活性剤（乳化剤）、防腐剤及び殺菌剤等が例示される。本発明の平版印刷インキ組成物は助剤の一つとして後述する水溶性多糖類を含有する。 (About auxiliary agents)
Examples of auxiliary agents include dryers, compounds for adjusting viscosity, waxes, anti-drying agents, antifoaming agents, surfactants (emulsifiers) for adjusting emulsification suitability, preservatives, and bactericides. . The lithographic printing ink composition of the present invention contains a water-soluble polysaccharide described later as one of auxiliary agents.
助剤に属するものとして、ドライヤー、粘度調節のためのコンパウンド、ワックス、乾燥防止剤、消泡剤、乳化適性を調節するための界面活性剤（乳化剤）、防腐剤及び殺菌剤等が例示される。本発明の平版印刷インキ組成物は助剤の一つとして後述する水溶性多糖類を含有する。 (About auxiliary agents)
Examples of auxiliary agents include dryers, compounds for adjusting viscosity, waxes, anti-drying agents, antifoaming agents, surfactants (emulsifiers) for adjusting emulsification suitability, preservatives, and bactericides. . The lithographic printing ink composition of the present invention contains a water-soluble polysaccharide described later as one of auxiliary agents.
ワックスは印刷インキ皮膜のこすれ防止等のために添加される。ワックスとしては、印刷インキに用いられている一般的なものを使用できる。例えば、カルナバワックス、みつろう、パラフィンワックス、マイクロクリスタリンワックス、ポリエチレンワックス、脂肪酸アマイド、ポリテトラフルオロエチレン等がある。
Wax is added to prevent the printing ink film from rubbing. As the wax, a general wax used in printing ink can be used. For example, carnauba wax, beeswax, paraffin wax, microcrystalline wax, polyethylene wax, fatty acid amide, polytetrafluoroethylene and the like.
乳化適性を調節するために、後述する水溶性多糖類とともに界面活性剤（乳化剤）を用いてもよい。乳化剤としては水溶性、非水溶性のいずれであっても用いることができこれらを併用してもよいが、非水溶性乳化剤を用いる場合はその含有量を平版印刷インキ組成物の１質量％未満とすることが好ましく、０．６質量％以下とすることがより好ましい。印刷時に、非水溶性乳化剤は水溶性乳化剤と異なり湿し水に溶出することなく印刷インキ中に残存する。水溶性多糖類と非水溶性乳化剤が本発明のように印刷前から水を含む印刷インキ組成物中で共存すると、湿し水を過剰に取り込んで印刷インキ組成物が過乳化し、水棒に絡んで湿し水の転移を阻害するなどして耐汚れ性が低下するおそれがある。非水溶性の界面活性剤（乳化剤）の含有量を上記の範囲とすることにより、このような不具合を防止することができる。
In order to adjust emulsification suitability, a surfactant (emulsifier) may be used together with the water-soluble polysaccharide described later. As the emulsifier, either water-soluble or water-insoluble can be used, and these may be used together. However, when a water-insoluble emulsifier is used, its content is less than 1% by mass of the lithographic printing ink composition. It is preferable to set it as 0.6 mass% or less. During printing, the water-insoluble emulsifier remains in the printing ink without being eluted in the fountain solution, unlike the water-soluble emulsifier. When the water-soluble polysaccharide and the water-insoluble emulsifier coexist in the printing ink composition containing water before printing as in the present invention, the printing ink composition is excessively emulsified due to excessive dampening water, and the water rod There is a possibility that the stain resistance may be lowered by entanglement and inhibiting the transfer of dampening water. By setting the content of the water-insoluble surfactant (emulsifier) in the above range, such a problem can be prevented.
水溶性の乳化剤としては、従来公知のものを用いることができ特に限定されないが、一例としてトリデカノール、２－ヘキシルオクタノール、２－ヘキシルデカノール、２－オクチルデカノール、又はヘキシルジグリコールなどが挙げられる。
非水溶性の乳化剤としては、モノオレイン酸ソルビタン、モノオレイン酸グリセリン、ポリオキシエチレンクミルフェニルエーテル等が例示される。このような乳化剤は市販品としても入手可能であり、例えば花王製レオドールＳＰ－０１０Ｖ、レオドールＳＰ－０３０Ｖや、日本乳化剤社製ニューコールＣＭＰ－１が挙げられる。 As the water-soluble emulsifier, conventionally known emulsifiers can be used and are not particularly limited, and examples thereof include tridecanol, 2-hexyloctanol, 2-hexyldecanol, 2-octyldecanol, and hexyl diglycol.
Examples of the water-insoluble emulsifier include sorbitan monooleate, glycerin monooleate, polyoxyethylene cumylphenyl ether, and the like. Such emulsifiers are also available as commercial products, and examples thereof include Kao's Rheodor SP-010V and Rhedol SP-030V, and Nippon Emulsifier Newcol CMP-1.
非水溶性の乳化剤としては、モノオレイン酸ソルビタン、モノオレイン酸グリセリン、ポリオキシエチレンクミルフェニルエーテル等が例示される。このような乳化剤は市販品としても入手可能であり、例えば花王製レオドールＳＰ－０１０Ｖ、レオドールＳＰ－０３０Ｖや、日本乳化剤社製ニューコールＣＭＰ－１が挙げられる。 As the water-soluble emulsifier, conventionally known emulsifiers can be used and are not particularly limited, and examples thereof include tridecanol, 2-hexyloctanol, 2-hexyldecanol, 2-octyldecanol, and hexyl diglycol.
Examples of the water-insoluble emulsifier include sorbitan monooleate, glycerin monooleate, polyoxyethylene cumylphenyl ether, and the like. Such emulsifiers are also available as commercial products, and examples thereof include Kao's Rheodor SP-010V and Rhedol SP-030V, and Nippon Emulsifier Newcol CMP-1.
平版印刷インキ組成物には、リン酸類やその塩、クエン酸やその塩といった酸類やその塩がしばしば添加される。このような無機酸、有機酸類やその塩を添加する目的の一つは印刷版の非画線部への印刷インキ組成物の付着を防止することにある。しかしながら本発明の平版印刷インキ組成物にこのような酸類やその塩類を添加すると、水溶性多糖類の水への溶解性が低下して不溶化し、保存安定性や耐汚れ性が低下するおそれがある。このため本発明の印刷インキ組成物における無機酸、有機酸類やその塩の含有量の合計は平版印刷インキ組成物の０．２質量％以下とすることが好ましく、０．１質量％以下とすることがより好ましく、０．０５質量％以下とすることがさらに好ましい。これにより上記のような不具合を防止することができる。
In the lithographic printing ink composition, acids such as phosphoric acids and salts thereof, citric acid and salts thereof, and salts thereof are often added. One purpose of adding such inorganic acids, organic acids and salts thereof is to prevent the printing ink composition from adhering to the non-image area of the printing plate. However, when such acids or salts thereof are added to the lithographic printing ink composition of the present invention, the solubility of the water-soluble polysaccharide in water is decreased and insolubilized, and the storage stability and stain resistance may be decreased. is there. Therefore, the total content of inorganic acids, organic acids and salts thereof in the printing ink composition of the present invention is preferably 0.2% by mass or less, and 0.1% by mass or less of the lithographic printing ink composition. More preferably, it is more preferable to set it as 0.05 mass% or less. Thereby, the above problems can be prevented.
なお、上述した無機酸、有機酸類やその塩の具体例としては、リン酸、ピロリン酸、メタリン酸、ヘキサメタリン酸、ポリリン酸等のリン酸類、これらリン酸類のアンモニウム塩、アルカリ金属塩、アルカリ土類金属二水素塩、クエン酸、クエン酸のアンモニウム塩、アルカリ金属塩、マグネシウム塩などが挙げられる。
Specific examples of the above-mentioned inorganic acids, organic acids and salts thereof include phosphoric acids such as phosphoric acid, pyrophosphoric acid, metaphosphoric acid, hexametaphosphoric acid, polyphosphoric acid, ammonium salts, alkali metal salts, alkaline earths of these phosphoric acids. Metal dihydrogen salt, citric acid, ammonium salt of citric acid, alkali metal salt, magnesium salt and the like.
（インキ中の水分量について）
インキ中の水分量は、良好な印刷適性を保持するために１～３０％が好ましい。水分量が３０％を超えると、印刷適性の悪化や後述するインキの保存安定性の悪化が見られる。
水分量が１％以下では印刷適性の改善効果が得られにくくなる。水分量は１～２０％がより好ましく、さらに好ましくは１～１５％である。 (About the amount of water in the ink)
The amount of water in the ink is preferably 1 to 30% in order to maintain good printability. When the water content exceeds 30%, the printability is deteriorated and the storage stability of the ink described later is deteriorated.
If the water content is 1% or less, it becomes difficult to obtain an improvement effect of printability. The water content is more preferably 1 to 20%, still more preferably 1 to 15%.
インキ中の水分量は、良好な印刷適性を保持するために１～３０％が好ましい。水分量が３０％を超えると、印刷適性の悪化や後述するインキの保存安定性の悪化が見られる。
水分量が１％以下では印刷適性の改善効果が得られにくくなる。水分量は１～２０％がより好ましく、さらに好ましくは１～１５％である。 (About the amount of water in the ink)
The amount of water in the ink is preferably 1 to 30% in order to maintain good printability. When the water content exceeds 30%, the printability is deteriorated and the storage stability of the ink described later is deteriorated.
If the water content is 1% or less, it becomes difficult to obtain an improvement effect of printability. The water content is more preferably 1 to 20%, still more preferably 1 to 15%.
（水溶性多糖類について）
水溶性多糖類は印刷インキ組成物中で安定的に水を保持する一方、印刷時には湿し水中に徐々に溶出するため印刷インキ組成物の過乳化や、これに起因する耐汚れ性の低下を抑制することができる。
本発明に使用される水溶性多糖類として、水溶性セルロース誘導体、アラビアガム、カラギーナン、グアガム、ペクチン、トラガント、サクラン、スピルラン、グルコマンナン、アミロース、ウェランガム（ジェランガム）、タラガム（スピノガム）、ローカストビーンガム、プルラン、ダイユータンガム、キサンタンガム、コンドロイチン硫酸ナトリウム等が挙げられる。水溶性セルロース誘導体、キサンタンガム、ダイユータンガム、カラギーナンが好ましく、水溶性セルロース誘導体が特に好ましい。 (About water-soluble polysaccharides)
While water-soluble polysaccharides stably retain water in the printing ink composition, the water-soluble polysaccharide elutes into the fountain solution gradually during printing, so over-emulsification of the printing ink composition and the resulting stain resistance decrease. Can be suppressed.
Examples of water-soluble polysaccharides used in the present invention include water-soluble cellulose derivatives, gum arabic, carrageenan, guar gum, pectin, tragacanth, cherry, spirrane, glucomannan, amylose, welan gum (gellan gum), tara gum (spin gum), locust bean gum , Pullulan, diyutan gum, xanthan gum, sodium chondroitin sulfate and the like. Water-soluble cellulose derivatives, xanthan gum, dieutan gum and carrageenan are preferred, and water-soluble cellulose derivatives are particularly preferred.
水溶性多糖類は印刷インキ組成物中で安定的に水を保持する一方、印刷時には湿し水中に徐々に溶出するため印刷インキ組成物の過乳化や、これに起因する耐汚れ性の低下を抑制することができる。
本発明に使用される水溶性多糖類として、水溶性セルロース誘導体、アラビアガム、カラギーナン、グアガム、ペクチン、トラガント、サクラン、スピルラン、グルコマンナン、アミロース、ウェランガム（ジェランガム）、タラガム（スピノガム）、ローカストビーンガム、プルラン、ダイユータンガム、キサンタンガム、コンドロイチン硫酸ナトリウム等が挙げられる。水溶性セルロース誘導体、キサンタンガム、ダイユータンガム、カラギーナンが好ましく、水溶性セルロース誘導体が特に好ましい。 (About water-soluble polysaccharides)
While water-soluble polysaccharides stably retain water in the printing ink composition, the water-soluble polysaccharide elutes into the fountain solution gradually during printing, so over-emulsification of the printing ink composition and the resulting stain resistance decrease. Can be suppressed.
Examples of water-soluble polysaccharides used in the present invention include water-soluble cellulose derivatives, gum arabic, carrageenan, guar gum, pectin, tragacanth, cherry, spirrane, glucomannan, amylose, welan gum (gellan gum), tara gum (spin gum), locust bean gum , Pullulan, diyutan gum, xanthan gum, sodium chondroitin sulfate and the like. Water-soluble cellulose derivatives, xanthan gum, dieutan gum and carrageenan are preferred, and water-soluble cellulose derivatives are particularly preferred.
（水溶性セルロース誘導体について）
水溶性セルロース誘導体としてはメチルセルロース、エチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、これらセルロースにカチオン化剤を付加したカチオン化セルロース等が例示され、中でもカルボキシメチルセルロースナトリウム（以下ＣＭＣとも記載する）が好ましく用いられる。 (About water-soluble cellulose derivatives)
Examples of the water-soluble cellulose derivative include methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and cationized cellulose obtained by adding a cationizing agent to these celluloses. Among them, sodium carboxymethyl cellulose (hereinafter also referred to as CMC) Are preferably used.
水溶性セルロース誘導体としてはメチルセルロース、エチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、これらセルロースにカチオン化剤を付加したカチオン化セルロース等が例示され、中でもカルボキシメチルセルロースナトリウム（以下ＣＭＣとも記載する）が好ましく用いられる。 (About water-soluble cellulose derivatives)
Examples of the water-soluble cellulose derivative include methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and cationized cellulose obtained by adding a cationizing agent to these celluloses. Among them, sodium carboxymethyl cellulose (hereinafter also referred to as CMC) Are preferably used.
（インキ中の水溶性多糖類の量について）
良好な水保持能力及び良好な印刷適性を備えるために、本発明の平版印刷インキ組成物中の水溶性多糖類の含有量は０．０１～３％が好ましい。
水溶性多糖類が３％を超えると印刷中にインキ中に過剰の水分を取り込み、印刷機のローラー間でのインキの転移性や、ブランケットから版へのインキの転移性が低下し、濃度ムラ・カスレ等の品質不良が起きやすくなり、印刷適性が損なわれる。
水溶性多糖類が０．０１％以下では適切な水保持能力が得られない。
水溶性多糖類の含有量は、より好ましくは０．０１～２％であり、さらに好ましくは０．０１～１％である。 (About the amount of water-soluble polysaccharide in the ink)
In order to have a good water holding capacity and good printability, the content of the water-soluble polysaccharide in the lithographic printing ink composition of the present invention is preferably 0.01 to 3%.
If the water-soluble polysaccharide exceeds 3%, excessive moisture is taken into the ink during printing, and the transferability of the ink between the rollers of the printing press and the transferability of the ink from the blanket to the plate are reduced, resulting in uneven density. -Poor quality such as scraping is likely to occur, and printability is impaired.
If the water-soluble polysaccharide is 0.01% or less, an appropriate water retention capacity cannot be obtained.
The content of the water-soluble polysaccharide is more preferably 0.01 to 2%, still more preferably 0.01 to 1%.
良好な水保持能力及び良好な印刷適性を備えるために、本発明の平版印刷インキ組成物中の水溶性多糖類の含有量は０．０１～３％が好ましい。
水溶性多糖類が３％を超えると印刷中にインキ中に過剰の水分を取り込み、印刷機のローラー間でのインキの転移性や、ブランケットから版へのインキの転移性が低下し、濃度ムラ・カスレ等の品質不良が起きやすくなり、印刷適性が損なわれる。
水溶性多糖類が０．０１％以下では適切な水保持能力が得られない。
水溶性多糖類の含有量は、より好ましくは０．０１～２％であり、さらに好ましくは０．０１～１％である。 (About the amount of water-soluble polysaccharide in the ink)
In order to have a good water holding capacity and good printability, the content of the water-soluble polysaccharide in the lithographic printing ink composition of the present invention is preferably 0.01 to 3%.
If the water-soluble polysaccharide exceeds 3%, excessive moisture is taken into the ink during printing, and the transferability of the ink between the rollers of the printing press and the transferability of the ink from the blanket to the plate are reduced, resulting in uneven density. -Poor quality such as scraping is likely to occur, and printability is impaired.
If the water-soluble polysaccharide is 0.01% or less, an appropriate water retention capacity cannot be obtained.
The content of the water-soluble polysaccharide is more preferably 0.01 to 2%, still more preferably 0.01 to 1%.
（水溶性多糖類の粘度について）
水溶性多糖類の粘度は、蒸留水に溶解した２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓであることが好ましい。
より好ましくは、水溶性多糖類の１％水溶液の粘度が１０～４０００ｍＰａ・ｓである。
さらに好ましくは、水溶性多糖類の１％水溶液の粘度が１０～２０００ｍＰａ・ｓである。
水溶性多糖類の粘度が前記の範囲から外れる場合は印刷適性の悪化や後述するインキの保存安定性の悪化が見られる。 (Viscosity of water-soluble polysaccharides)
The viscosity of the water-soluble polysaccharide is preferably 2.5 to 1500 mPa · s for a 2% aqueous solution dissolved in distilled water, or 10 to 8000 mPa · s for the 1% aqueous solution.
More preferably, the viscosity of a 1% aqueous solution of a water-soluble polysaccharide is 10 to 4000 mPa · s.
More preferably, the viscosity of a 1% aqueous solution of the water-soluble polysaccharide is 10 to 2000 mPa · s.
When the viscosity of the water-soluble polysaccharide is out of the above range, the printability is deteriorated and the storage stability of the ink described later is deteriorated.
水溶性多糖類の粘度は、蒸留水に溶解した２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓであることが好ましい。
より好ましくは、水溶性多糖類の１％水溶液の粘度が１０～４０００ｍＰａ・ｓである。
さらに好ましくは、水溶性多糖類の１％水溶液の粘度が１０～２０００ｍＰａ・ｓである。
水溶性多糖類の粘度が前記の範囲から外れる場合は印刷適性の悪化や後述するインキの保存安定性の悪化が見られる。 (Viscosity of water-soluble polysaccharides)
The viscosity of the water-soluble polysaccharide is preferably 2.5 to 1500 mPa · s for a 2% aqueous solution dissolved in distilled water, or 10 to 8000 mPa · s for the 1% aqueous solution.
More preferably, the viscosity of a 1% aqueous solution of a water-soluble polysaccharide is 10 to 4000 mPa · s.
More preferably, the viscosity of a 1% aqueous solution of the water-soluble polysaccharide is 10 to 2000 mPa · s.
When the viscosity of the water-soluble polysaccharide is out of the above range, the printability is deteriorated and the storage stability of the ink described later is deteriorated.
水溶性多糖類の水溶液の粘度はＪＩＳ Ｋ７１１７－１に記載のブルックフィールド形回転粘度計（以下Ｂ形回転粘度計とも記載する）を用いて測定する。このタイプの粘度計として東京計器株式会社製Ｂ形回転粘度計（型式ＢＭ）が挙げられる。
具体的な測定手順は次の通りである。
１）水溶性多糖類中の水分量の測定
水溶性多糖類の試料１～２ｇを秤量ビンに精密にはかりとり、１０５＋－２℃の定温乾燥機中において４時間乾燥し、デシケーター中で冷却したのち重さを量り、その減量から次の式によって水分量（％）を算出する。
水分量（％）＝（減量（ｇ）／試料（ｇ））×１００
２）水溶液の調整
共栓付３００ｍＬ（ミリリットル）の三角フラスコに、濃度２％とする場合は約４．４ｇ、濃度１％の場合は約２．２ｇの試料を精密にはかりとり、次式で求めた蒸留水を加えて溶解する。
２％水溶液を作る場合：
加える蒸留水（ｇ）＝試料（ｇ）×（９８－水分量（％））／２
１％水溶液を作る場合：
加える蒸留水（ｇ）＝試料（ｇ）×（９９－水分量（％））
３）測定
前記の水溶液を一夜間放置後、マグネチックスターラーで約５分間かきまぜ、完全な溶液とする。
次にその溶液を口径約４５ｍｍ、高さ約１４５ｍｍのフタつき容器に移す。
次にその容器を２５＋－０．２℃に設定した恒温槽に３０分間入れる。
溶液が２５℃になればガラス棒でゆるくかきまぜて、Ｂ形回転粘度計の適当なローター（スピンドル）およびガードをとり付け、ローターを回転させてから３分後の目盛りを読み取る。ローターの回転数は粘度により、毎分３０回転又は６０回転とする。
粘度は次式により求める。
粘度（ｍＰａ・ｓ）＝読み取り目盛×係数
前式の係数は使用したローターの番号及び回転数に基づき表１から求める。 The viscosity of the aqueous solution of the water-soluble polysaccharide is measured using a Brookfield type rotational viscometer (hereinafter also referred to as B type rotational viscometer) described in JIS K7117-1. An example of this type of viscometer is a B-type rotational viscometer (model BM) manufactured by Tokyo Keiki Co., Ltd.
The specific measurement procedure is as follows.
1) Measurement of water content in water-soluble polysaccharide Samples 1 to 2 g of water-soluble polysaccharide were accurately weighed in a weighing bottle, dried in a constant temperature dryer at 105 + -2 ° C for 4 hours, and cooled in a desiccator. Then weigh and calculate the amount of water (%) from the weight loss by the following formula.
Moisture content (%) = (weight loss (g) / sample (g)) × 100
2) Preparation of aqueous solution In a 300 mL (milliliter) Erlenmeyer flask with a stopper, weigh accurately about 4.4 g for a concentration of 2% and about 2.2 g for a concentration of 1%. Add the distilled water obtained and dissolve.
When making a 2% aqueous solution:
Distilled water to be added (g) = sample (g) × (98−water content (%)) / 2
When making a 1% aqueous solution:
Distilled water to be added (g) = sample (g) × (99−water content (%))
3) Measurement After the above aqueous solution is left overnight, it is stirred with a magnetic stirrer for about 5 minutes to obtain a complete solution.
Next, the solution is transferred to a container with a lid having a diameter of about 45 mm and a height of about 145 mm.
The container is then placed in a thermostat set at 25 + -0.2 ° C. for 30 minutes.
When the solution reaches 25 ° C., gently stir with a glass rod, attach an appropriate rotor (spindle) and guard of a B-type rotational viscometer, and read the scale 3 minutes after rotating the rotor. The rotational speed of the rotor is 30 or 60 revolutions per minute depending on the viscosity.
The viscosity is determined by the following formula.
Viscosity (mPa · s) = reading scale × coefficient The coefficient of the previous equation is obtained from Table 1 based on the number of the rotor used and the number of rotations.
具体的な測定手順は次の通りである。
１）水溶性多糖類中の水分量の測定
水溶性多糖類の試料１～２ｇを秤量ビンに精密にはかりとり、１０５＋－２℃の定温乾燥機中において４時間乾燥し、デシケーター中で冷却したのち重さを量り、その減量から次の式によって水分量（％）を算出する。
水分量（％）＝（減量（ｇ）／試料（ｇ））×１００
２）水溶液の調整
共栓付３００ｍＬ（ミリリットル）の三角フラスコに、濃度２％とする場合は約４．４ｇ、濃度１％の場合は約２．２ｇの試料を精密にはかりとり、次式で求めた蒸留水を加えて溶解する。
２％水溶液を作る場合：
加える蒸留水（ｇ）＝試料（ｇ）×（９８－水分量（％））／２
１％水溶液を作る場合：
加える蒸留水（ｇ）＝試料（ｇ）×（９９－水分量（％））
３）測定
前記の水溶液を一夜間放置後、マグネチックスターラーで約５分間かきまぜ、完全な溶液とする。
次にその溶液を口径約４５ｍｍ、高さ約１４５ｍｍのフタつき容器に移す。
次にその容器を２５＋－０．２℃に設定した恒温槽に３０分間入れる。
溶液が２５℃になればガラス棒でゆるくかきまぜて、Ｂ形回転粘度計の適当なローター（スピンドル）およびガードをとり付け、ローターを回転させてから３分後の目盛りを読み取る。ローターの回転数は粘度により、毎分３０回転又は６０回転とする。
粘度は次式により求める。
粘度（ｍＰａ・ｓ）＝読み取り目盛×係数
前式の係数は使用したローターの番号及び回転数に基づき表１から求める。 The viscosity of the aqueous solution of the water-soluble polysaccharide is measured using a Brookfield type rotational viscometer (hereinafter also referred to as B type rotational viscometer) described in JIS K7117-1. An example of this type of viscometer is a B-type rotational viscometer (model BM) manufactured by Tokyo Keiki Co., Ltd.
The specific measurement procedure is as follows.
1) Measurement of water content in water-soluble polysaccharide Samples 1 to 2 g of water-soluble polysaccharide were accurately weighed in a weighing bottle, dried in a constant temperature dryer at 105 + -2 ° C for 4 hours, and cooled in a desiccator. Then weigh and calculate the amount of water (%) from the weight loss by the following formula.
Moisture content (%) = (weight loss (g) / sample (g)) × 100
2) Preparation of aqueous solution In a 300 mL (milliliter) Erlenmeyer flask with a stopper, weigh accurately about 4.4 g for a concentration of 2% and about 2.2 g for a concentration of 1%. Add the distilled water obtained and dissolve.
When making a 2% aqueous solution:
Distilled water to be added (g) = sample (g) × (98−water content (%)) / 2
When making a 1% aqueous solution:
Distilled water to be added (g) = sample (g) × (99−water content (%))
3) Measurement After the above aqueous solution is left overnight, it is stirred with a magnetic stirrer for about 5 minutes to obtain a complete solution.
Next, the solution is transferred to a container with a lid having a diameter of about 45 mm and a height of about 145 mm.
The container is then placed in a thermostat set at 25 + -0.2 ° C. for 30 minutes.
When the solution reaches 25 ° C., gently stir with a glass rod, attach an appropriate rotor (spindle) and guard of a B-type rotational viscometer, and read the scale 3 minutes after rotating the rotor. The rotational speed of the rotor is 30 or 60 revolutions per minute depending on the viscosity.
The viscosity is determined by the following formula.
Viscosity (mPa · s) = reading scale × coefficient The coefficient of the previous equation is obtained from Table 1 based on the number of the rotor used and the number of rotations.
（ＣＭＣのエーテル化度について）
水溶性多糖類としてＣＭＣを用いる場合は、エーテル化度は０．４５～１．００であることが好ましい。エーテル化度が０．４５より小さいと水溶性が低下し、１．００を超えるとインキの印刷適性が低下する。エーテル化度はより好ましくは０．４５～０．８０であり、さらに好ましくは０．４５～０．７０である。 (About the degree of etherification of CMC)
When CMC is used as the water-soluble polysaccharide, the degree of etherification is preferably 0.45 to 1.00. If the degree of etherification is less than 0.45, the water solubility decreases, and if it exceeds 1.00, the printability of the ink decreases. The degree of etherification is more preferably 0.45 to 0.80, and further preferably 0.45 to 0.70.
水溶性多糖類としてＣＭＣを用いる場合は、エーテル化度は０．４５～１．００であることが好ましい。エーテル化度が０．４５より小さいと水溶性が低下し、１．００を超えるとインキの印刷適性が低下する。エーテル化度はより好ましくは０．４５～０．８０であり、さらに好ましくは０．４５～０．７０である。 (About the degree of etherification of CMC)
When CMC is used as the water-soluble polysaccharide, the degree of etherification is preferably 0.45 to 1.00. If the degree of etherification is less than 0.45, the water solubility decreases, and if it exceeds 1.00, the printability of the ink decreases. The degree of etherification is more preferably 0.45 to 0.80, and further preferably 0.45 to 0.70.
ここでエーテル化度とは、無水グルコース１単位当たりのカルボキシメチル基の数をいう。無水グルコース１単位当たりのカルボキシメチル基の数が１個の場合、エーテル化度は１．０である。
エーテル化度の測定方法の一例は次の通りである。
試料（無水物）０．５～０．７ｇを精密にはかり、ろ紙に包んで磁製ルツボ中で灰化する。冷却したのち、これを５００ｍＬ（ミリリットル）ビーカーに移し、水を約２５０ｍＬ、さらにピペットで０．０５モル／Ｌ硫酸３５ｍＬを加えて３０分間煮沸する。
これを冷却し、フェノールフタレイン指示薬を加えて、過剰の酸を０．１モル／Ｌ水酸化カリウムで逆滴定して、次の式によってエーテル化度を算出する。
Ａ＝（ａｆ－ｂｇ）／試料（無水物）（ｇ）－アルカリ度（または＋酸度）
エーテル化度＝１６２×Ａ／（１００００－８０Ａ）
（記号の説明）
Ａ：試料１ｇ中の結合アルカリに消費された０．０５モル／Ｌ硫酸のｍＬ
ａ：０．０５モル／Ｌ硫酸の使用ｍＬ
ｆ：０．０５モル／Ｌ硫酸の力価
ｂ：０．１モル／Ｌ水酸化カリウムの滴定ｍＬ
ｇ：０．１モル／Ｌ水酸化カリウムの力価
１６２：グルコースの分子量
８０：ＣＨ２ＣＯＯＮａ－Ｈの分子量
（アルカリ度または酸度の求め方）
試料（無水物）約１ｇを３００ｍＬ三角フラスコに精密にはかりとり、水を約２００ｍＬ加えて溶かす。
これに０．０５モル／Ｌ硫酸５ｍＬをピペットで加え、１０分間煮沸したのち冷却して、フェノールフタレイン指示薬を加え、０．１モル／Ｌ水酸化カリウムで滴定する（ＳｍＬ）。同時に空試験を行い（ＢｍＬ）、次の式によって算出する。
アルカリ度＝（Ｂ－Ｓ）ｈ／試料無水物（ｇ）
ｈ：０．１モル／Ｌ水酸化カリウムの力価
なお（Ｂ－Ｓ）ｈの値が負のときにはアルカリ度を酸度と読み替える。 Here, the degree of etherification refers to the number of carboxymethyl groups per unit of anhydrous glucose. When the number of carboxymethyl groups per anhydroglucose unit is 1, the degree of etherification is 1.0.
An example of a method for measuring the degree of etherification is as follows.
A sample (anhydride) of 0.5 to 0.7 g is precisely weighed, wrapped in filter paper and incinerated in a magnetic crucible. After cooling, transfer this to a 500 mL (milliliter) beaker, add about 250 mL of water and 35 mL of 0.05 mol / L sulfuric acid with a pipette and boil for 30 minutes.
This is cooled, phenolphthalein indicator is added, excess acid is back titrated with 0.1 mol / L potassium hydroxide, and the degree of etherification is calculated by the following formula.
A = (af−bg) / sample (anhydride) (g) −alkalinity (or + acidity)
Degree of etherification = 162 × A / (10000-80A)
(Explanation of symbols)
A: mL of 0.05 mol / L sulfuric acid consumed by bound alkali in 1 g of sample
a: Use of 0.05 mol / L sulfuric acid mL
f: 0.05 mol / L sulfuric acid titer b: 0.1 mol / L potassium hydroxide titration mL
g: Potency of 0.1 mol / L potassium hydroxide 162: Molecular weight of glucose 80: Molecular weight of CH2COONa-H (How to determine alkalinity or acidity)
About 1 g of sample (anhydride) is accurately weighed into a 300 mL Erlenmeyer flask, and about 200 mL of water is added and dissolved.
Add 0.05 mL of 0.05 mol / L sulfuric acid with a pipette, boil for 10 minutes, cool, add phenolphthalein indicator, and titrate with 0.1 mol / L potassium hydroxide (SmL). At the same time, a blank test is performed (BmL), and the following formula is used.
Alkalinity = (B−S) h / sample anhydride (g)
h: Potency of 0.1 mol / L potassium hydroxide When the value of (B−S) h is negative, alkalinity is read as acidity.
エーテル化度の測定方法の一例は次の通りである。
試料（無水物）０．５～０．７ｇを精密にはかり、ろ紙に包んで磁製ルツボ中で灰化する。冷却したのち、これを５００ｍＬ（ミリリットル）ビーカーに移し、水を約２５０ｍＬ、さらにピペットで０．０５モル／Ｌ硫酸３５ｍＬを加えて３０分間煮沸する。
これを冷却し、フェノールフタレイン指示薬を加えて、過剰の酸を０．１モル／Ｌ水酸化カリウムで逆滴定して、次の式によってエーテル化度を算出する。
Ａ＝（ａｆ－ｂｇ）／試料（無水物）（ｇ）－アルカリ度（または＋酸度）
エーテル化度＝１６２×Ａ／（１００００－８０Ａ）
（記号の説明）
Ａ：試料１ｇ中の結合アルカリに消費された０．０５モル／Ｌ硫酸のｍＬ
ａ：０．０５モル／Ｌ硫酸の使用ｍＬ
ｆ：０．０５モル／Ｌ硫酸の力価
ｂ：０．１モル／Ｌ水酸化カリウムの滴定ｍＬ
ｇ：０．１モル／Ｌ水酸化カリウムの力価
１６２：グルコースの分子量
８０：ＣＨ２ＣＯＯＮａ－Ｈの分子量
（アルカリ度または酸度の求め方）
試料（無水物）約１ｇを３００ｍＬ三角フラスコに精密にはかりとり、水を約２００ｍＬ加えて溶かす。
これに０．０５モル／Ｌ硫酸５ｍＬをピペットで加え、１０分間煮沸したのち冷却して、フェノールフタレイン指示薬を加え、０．１モル／Ｌ水酸化カリウムで滴定する（ＳｍＬ）。同時に空試験を行い（ＢｍＬ）、次の式によって算出する。
アルカリ度＝（Ｂ－Ｓ）ｈ／試料無水物（ｇ）
ｈ：０．１モル／Ｌ水酸化カリウムの力価
なお（Ｂ－Ｓ）ｈの値が負のときにはアルカリ度を酸度と読み替える。 Here, the degree of etherification refers to the number of carboxymethyl groups per unit of anhydrous glucose. When the number of carboxymethyl groups per anhydroglucose unit is 1, the degree of etherification is 1.0.
An example of a method for measuring the degree of etherification is as follows.
A sample (anhydride) of 0.5 to 0.7 g is precisely weighed, wrapped in filter paper and incinerated in a magnetic crucible. After cooling, transfer this to a 500 mL (milliliter) beaker, add about 250 mL of water and 35 mL of 0.05 mol / L sulfuric acid with a pipette and boil for 30 minutes.
This is cooled, phenolphthalein indicator is added, excess acid is back titrated with 0.1 mol / L potassium hydroxide, and the degree of etherification is calculated by the following formula.
A = (af−bg) / sample (anhydride) (g) −alkalinity (or + acidity)
Degree of etherification = 162 × A / (10000-80A)
(Explanation of symbols)
A: mL of 0.05 mol / L sulfuric acid consumed by bound alkali in 1 g of sample
a: Use of 0.05 mol / L sulfuric acid mL
f: 0.05 mol / L sulfuric acid titer b: 0.1 mol / L potassium hydroxide titration mL
g: Potency of 0.1 mol / L potassium hydroxide 162: Molecular weight of glucose 80: Molecular weight of CH2COONa-H (How to determine alkalinity or acidity)
About 1 g of sample (anhydride) is accurately weighed into a 300 mL Erlenmeyer flask, and about 200 mL of water is added and dissolved.
Add 0.05 mL of 0.05 mol / L sulfuric acid with a pipette, boil for 10 minutes, cool, add phenolphthalein indicator, and titrate with 0.1 mol / L potassium hydroxide (SmL). At the same time, a blank test is performed (BmL), and the following formula is used.
Alkalinity = (B−S) h / sample anhydride (g)
h: Potency of 0.1 mol / L potassium hydroxide When the value of (B−S) h is negative, alkalinity is read as acidity.
（インキの製造方法について）
本発明の平版印刷インキ組成物は、前記の色料、ビヒクル及び助剤を混合し、三本ロールミル等の練肉分散機を用いて製造される。 (About ink manufacturing method)
The lithographic printing ink composition of the present invention is produced using a kneading disperser such as a three-roll mill by mixing the colorant, vehicle and auxiliary agent.
本発明の平版印刷インキ組成物は、前記の色料、ビヒクル及び助剤を混合し、三本ロールミル等の練肉分散機を用いて製造される。 (About ink manufacturing method)
The lithographic printing ink composition of the present invention is produced using a kneading disperser such as a three-roll mill by mixing the colorant, vehicle and auxiliary agent.
水及び水溶性多糖類はインキ製造時の任意のタイミングで添加する事ができる。それぞれ別個に添加することができ、また水及びＣＭＣを混合撹拌して均一な溶液とし、これをＣＭＣ以外の原料で別途製造した印刷インキ（ベースインキ）に添加して、全体を均一に混合することにより印刷インキとして仕上げることもできる。
Water and water-soluble polysaccharides can be added at any time during ink production. Each can be added separately, and water and CMC are mixed and stirred to make a uniform solution, which is added to printing ink (base ink) separately manufactured from raw materials other than CMC, and the whole is uniformly mixed It can also be finished as a printing ink.
本発明の平版印刷インキ組成物は、下記に配合を示す原料を三本ロールミル等を用いて公知の方法で練肉分散してインキ中の粗大粒子の粒径が５μｍ以下になるように調製し、目的とするインキを得ることができる。
前記のインキ中の粗大粒子の粒径とは、ＪＩＳ Ｋ５７０１－１に記載の練和度試験における練和度を指す。 The lithographic printing ink composition of the present invention is prepared so that raw materials having the following composition are kneaded and dispersed by a known method using a three-roll mill or the like so that the particle size of coarse particles in the ink is 5 μm or less. The desired ink can be obtained.
The particle size of the coarse particles in the ink refers to the kneading degree in the kneading degree test described in JIS K5701-1.
前記のインキ中の粗大粒子の粒径とは、ＪＩＳ Ｋ５７０１－１に記載の練和度試験における練和度を指す。 The lithographic printing ink composition of the present invention is prepared so that raw materials having the following composition are kneaded and dispersed by a known method using a three-roll mill or the like so that the particle size of coarse particles in the ink is 5 μm or less. The desired ink can be obtained.
The particle size of the coarse particles in the ink refers to the kneading degree in the kneading degree test described in JIS K5701-1.
ＪＩＳ Ｋ５７０１－１（平成１２年１月２０日制定）の４．３練和度に規定された試験方法は次の通りである。
溝の深さ（溝の目盛）が２５μｍから０μｍまで直線的に変化しているグラインドメータのゲージ盤上の深いところにインキ等の試料を置き、スクレーパーを用いて掻き取るようにして溝内に試料の膜を作る。ゲージ盤上には溝の深さを示す目盛が刻まれている。 The test method defined in 4.3 JIS K5701-1 (enacted on January 20, 2000) is as follows.
Place a sample such as ink in a deep place on the grindometer gauge board where the groove depth (groove scale) varies linearly from 25 μm to 0 μm, and scrape with a scraper into the groove. Make a sample film. A scale indicating the depth of the groove is engraved on the gauge board.
溝の深さ（溝の目盛）が２５μｍから０μｍまで直線的に変化しているグラインドメータのゲージ盤上の深いところにインキ等の試料を置き、スクレーパーを用いて掻き取るようにして溝内に試料の膜を作る。ゲージ盤上には溝の深さを示す目盛が刻まれている。 The test method defined in 4.3 JIS K5701-1 (enacted on January 20, 2000) is as follows.
Place a sample such as ink in a deep place on the grindometer gauge board where the groove depth (groove scale) varies linearly from 25 μm to 0 μm, and scrape with a scraper into the groove. Make a sample film. A scale indicating the depth of the groove is engraved on the gauge board.
試料中に粒子が存在すると、その粒子がスクレーパーで掻き取られて移動することにより、その粒子の大きさ（直径等）より浅い溝内に線が生じる。その線を観察し、１０ｍｍ以上連続した線が、一つの溝について３本以上現れたところの目盛の値をＡとし、１０本以上現れたところの目盛の値の位置をＢとする。
前記のインキ中の粗大粒子の粒径とは、前記位置Ａにおける目盛の値である。 When particles are present in the sample, the particles are scraped off and moved by a scraper, and a line is formed in a groove shallower than the size (diameter, etc.) of the particles. The line is observed, and the value of the scale where three or more continuous lines appear for 10 mm or more appear in one groove is A, and the position of the scale value where 10 or more lines appear is B.
The particle diameter of the coarse particles in the ink is a scale value at the position A.
前記のインキ中の粗大粒子の粒径とは、前記位置Ａにおける目盛の値である。 When particles are present in the sample, the particles are scraped off and moved by a scraper, and a line is formed in a groove shallower than the size (diameter, etc.) of the particles. The line is observed, and the value of the scale where three or more continuous lines appear for 10 mm or more appear in one groove is A, and the position of the scale value where 10 or more lines appear is B.
The particle diameter of the coarse particles in the ink is a scale value at the position A.
本発明の平版印刷インキ組成物は、湿し水を用いる平版印刷、及び湿し水を用いない、水なし平版印刷のいずれにも好適に用いることができる。
The lithographic printing ink composition of the present invention can be suitably used for both lithographic printing using fountain solution and waterless lithographic printing without using fountain solution.
以下、実施例及び比較例により、本発明をより詳細に説明する。
（インキの調製のために用いるワニスの調製）
ロジン変性フェノール樹脂Ｆ－８３０５（ＤＩＣ（株）製）・・・３０部
大豆油（日清オイリオ（株）製）・・・２４部
石油樹脂（東ソー（株）製）ペトコール１２０・・・１０部
ＡＦソルベント７号（ＪＸ日鉱日石エネルギー（株）製）・・・３５部
以上の合計９９部を加熱して溶解し、その後ＡＬＣＨ（アルミニウムエチルアセトアセテート・ジイソプロピレート、川研ファインケミカル（株）製）１部を添加してキレーションを行って、トレランスが１０（ｍＬ／３ｇ）であるワニスを調製した。
なお、Ｆ－８３０５の重量平均分子量は３８，０００、酸価は１６．５、ｎ－ヘプタントレランスが４００％のロジン変性フェノール樹脂である。ｎ－ヘプタントレランスはロジン変性フェノール樹脂とトルエンとを質量比が１：１で混合した溶液１ｇを２５℃に保ちながらｎ－ヘプタンを滴下し、溶液が白濁するまでに添加されたｎ－ヘプタンの量（ｍＬ）に１００を乗じた値である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
(Preparation of varnish used for ink preparation)
Rosin modified phenolic resin F-8305 (manufactured by DIC Corporation) ... 30 parts soybean oil (manufactured by Nisshin Oilio Co., Ltd.) ... 24 parts petroleum resin (manufactured by Tosoh Corporation) Petcoal 120 ... 10 Part AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation): 35 parts A total of 99 parts is heated and dissolved, and then ALCH (aluminum ethyl acetoacetate diisopropylate, Kawaken Fine Chemicals Co., Ltd.) 1) 1 part was added and chelated to prepare a varnish having a tolerance of 10 (mL / 3 g).
F-8305 is a rosin-modified phenolic resin having a weight average molecular weight of 38,000, an acid value of 16.5, and an n-heptane tolerance of 400%. The n-heptane tolerance was obtained by adding n-heptane dropwise while keeping 1 g of a rosin-modified phenolic resin and toluene mixed at a mass ratio of 1: 1 at 25 ° C. until the solution became cloudy. It is a value obtained by multiplying the amount (mL) by 100.
（インキの調製のために用いるワニスの調製）
ロジン変性フェノール樹脂Ｆ－８３０５（ＤＩＣ（株）製）・・・３０部
大豆油（日清オイリオ（株）製）・・・２４部
石油樹脂（東ソー（株）製）ペトコール１２０・・・１０部
ＡＦソルベント７号（ＪＸ日鉱日石エネルギー（株）製）・・・３５部
以上の合計９９部を加熱して溶解し、その後ＡＬＣＨ（アルミニウムエチルアセトアセテート・ジイソプロピレート、川研ファインケミカル（株）製）１部を添加してキレーションを行って、トレランスが１０（ｍＬ／３ｇ）であるワニスを調製した。
なお、Ｆ－８３０５の重量平均分子量は３８，０００、酸価は１６．５、ｎ－ヘプタントレランスが４００％のロジン変性フェノール樹脂である。ｎ－ヘプタントレランスはロジン変性フェノール樹脂とトルエンとを質量比が１：１で混合した溶液１ｇを２５℃に保ちながらｎ－ヘプタンを滴下し、溶液が白濁するまでに添加されたｎ－ヘプタンの量（ｍＬ）に１００を乗じた値である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
(Preparation of varnish used for ink preparation)
Rosin modified phenolic resin F-8305 (manufactured by DIC Corporation) ... 30 parts soybean oil (manufactured by Nisshin Oilio Co., Ltd.) ... 24 parts petroleum resin (manufactured by Tosoh Corporation) Petcoal 120 ... 10 Part AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation): 35 parts A total of 99 parts is heated and dissolved, and then ALCH (aluminum ethyl acetoacetate diisopropylate, Kawaken Fine Chemicals Co., Ltd.) 1) 1 part was added and chelated to prepare a varnish having a tolerance of 10 (mL / 3 g).
F-8305 is a rosin-modified phenolic resin having a weight average molecular weight of 38,000, an acid value of 16.5, and an n-heptane tolerance of 400%. The n-heptane tolerance was obtained by adding n-heptane dropwise while keeping 1 g of a rosin-modified phenolic resin and toluene mixed at a mass ratio of 1: 1 at 25 ° C. until the solution became cloudy. It is a value obtained by multiplying the amount (mL) by 100.
（ベースインキの調製）
有機顔料ＦＡＳＴＯＧＥＮＢｌｕｅ ＦＡ５３７５（ＤＩＣ（株）製）・・１３部
炭酸カルシウム白艶華Ｔ－ＤＤ（白石工業（株）製）・・・３部
前記ワニス・・・４０部
ワックスコンパウンド・・・１部
ＡＦソルベント７号（ＪＸ日鉱日石エネルギー(株)製）・・・３部
以上合計６０部を混合し、三本ロールミルを用いて練肉分散して実施例及び比較例で用いるベースインキを調製した。
尚、上記のワックスコンパウンドは、ポリテトラフルオロエチレンワックスを前記ワニス中に濃度３０％で分散したものである。 (Preparation of base ink)
Organic pigment FASTOGENBlue FA5375 (manufactured by DIC Corporation) ··· 13 parts Calcium carbonate white gloss T-DD (manufactured by Shiroishi Kogyo Co., Ltd.) · · · 3 parts said varnish · 40 parts wax compound · · 1 part AF solvent No. 7 (manufactured by JX Nippon Oil & Energy Co., Ltd.) 3 parts A total of 60 parts was mixed, and kneaded with a three-roll mill to prepare base inks used in Examples and Comparative Examples.
The above wax compound is obtained by dispersing polytetrafluoroethylene wax in the varnish at a concentration of 30%.
有機顔料ＦＡＳＴＯＧＥＮＢｌｕｅ ＦＡ５３７５（ＤＩＣ（株）製）・・１３部
炭酸カルシウム白艶華Ｔ－ＤＤ（白石工業（株）製）・・・３部
前記ワニス・・・４０部
ワックスコンパウンド・・・１部
ＡＦソルベント７号（ＪＸ日鉱日石エネルギー(株)製）・・・３部
以上合計６０部を混合し、三本ロールミルを用いて練肉分散して実施例及び比較例で用いるベースインキを調製した。
尚、上記のワックスコンパウンドは、ポリテトラフルオロエチレンワックスを前記ワニス中に濃度３０％で分散したものである。 (Preparation of base ink)
Organic pigment FASTOGENBlue FA5375 (manufactured by DIC Corporation) ··· 13 parts Calcium carbonate white gloss T-DD (manufactured by Shiroishi Kogyo Co., Ltd.) · · · 3 parts said varnish · 40 parts wax compound · · 1 part AF solvent No. 7 (manufactured by JX Nippon Oil & Energy Co., Ltd.) 3 parts A total of 60 parts was mixed, and kneaded with a three-roll mill to prepare base inks used in Examples and Comparative Examples.
The above wax compound is obtained by dispersing polytetrafluoroethylene wax in the varnish at a concentration of 30%.
さらに表２－４に示す配合割合に従ってベースインキ、ワニス及びその他の成分を配合し、ミキサー等を用いて均一に混合分散して実施例１～２０に示すインキを作成した。
また同様に表５－７に示す配合割合に従って比較例１～１５及び参考例のインキを作成した。
水溶性多糖類は配合量により、直接添加するか、又は水溶液を作ってから添加した。
参考例は、水溶性多糖類及び水を含有しない、従来一般に使われている印刷インキであり、このインキの印刷適性を２（標準レベル）とした。印刷適性が２以上を良とし、２未満は不良である。
比較例９及び参考例の印刷インキは水を含有しないため、保存安定性の評価は行っていない。 Further, the base ink, varnish and other components were blended according to the blending ratio shown in Table 2-4, and uniformly mixed and dispersed using a mixer or the like to produce the inks shown in Examples 1 to 20.
Similarly, inks of Comparative Examples 1 to 15 and Reference Example were prepared according to the blending ratios shown in Table 5-7.
The water-soluble polysaccharide was added directly depending on the blending amount or added after making an aqueous solution.
A reference example is a printing ink that is generally used in the past and does not contain water-soluble polysaccharides and water. The printability of this ink was set to 2 (standard level). A printability of 2 or more is good and less than 2 is bad.
Since the printing inks of Comparative Example 9 and Reference Example do not contain water, the storage stability was not evaluated.
また同様に表５－７に示す配合割合に従って比較例１～１５及び参考例のインキを作成した。
水溶性多糖類は配合量により、直接添加するか、又は水溶液を作ってから添加した。
参考例は、水溶性多糖類及び水を含有しない、従来一般に使われている印刷インキであり、このインキの印刷適性を２（標準レベル）とした。印刷適性が２以上を良とし、２未満は不良である。
比較例９及び参考例の印刷インキは水を含有しないため、保存安定性の評価は行っていない。 Further, the base ink, varnish and other components were blended according to the blending ratio shown in Table 2-4, and uniformly mixed and dispersed using a mixer or the like to produce the inks shown in Examples 1 to 20.
Similarly, inks of Comparative Examples 1 to 15 and Reference Example were prepared according to the blending ratios shown in Table 5-7.
The water-soluble polysaccharide was added directly depending on the blending amount or added after making an aqueous solution.
A reference example is a printing ink that is generally used in the past and does not contain water-soluble polysaccharides and water. The printability of this ink was set to 2 (standard level). A printability of 2 or more is good and less than 2 is bad.
Since the printing inks of Comparative Example 9 and Reference Example do not contain water, the storage stability was not evaluated.
尚、表２－７に示す実施例及び比較例では、水溶性多糖類として各例に示す粘度及びエーテル化度（ＣＭＣの場合）のものを用いた。表中のＨＥＣはヒドロキシエチルセルロースであり、ＨＰＣはヒドロキシプロピルセルロースであり、ＨＰＭＣはヒドロキシプロピルメチルセルロースである。ＣＭＣのメーカーとしてダイセルファインケム株式会社、第一工業製薬株式会社、ニチリン化学工業株式会社、日本製紙株式会社、ＣＰ ｋｅｌｃｏ社等が挙げられる。
各表の水溶性多糖類粘度（１％）は、水溶性多糖類濃度１％の水溶液の粘度を表す。水溶性多糖類粘度（２％）は、水溶性多糖類濃度２％の水溶液の粘度を表す。
リン酸は８５％濃度の水溶液（和光純薬製）を使用した。また、表中のリン酸の配合量は、８５％水溶液の配合量を意味する。
非水溶性乳化剤は、モノオレイン酸グリセリン（花王製 レオドール ＳＰ－０３０Ｖ）を用いた。 In Examples and Comparative Examples shown in Table 2-7, water-soluble polysaccharides having the viscosity and the degree of etherification (in the case of CMC) shown in each example were used. HEC in the table is hydroxyethylcellulose, HPC is hydroxypropylcellulose, and HPMC is hydroxypropylmethylcellulose. Examples of CMC manufacturers include Daicel Finechem Co., Ltd., Daiichi Kogyo Seiyaku Co., Ltd., Nichirin Chemical Co., Ltd., Nippon Paper Industries Co., Ltd., and CP kelco.
The water-soluble polysaccharide viscosity (1%) in each table represents the viscosity of an aqueous solution having a water-soluble polysaccharide concentration of 1%. The water-soluble polysaccharide viscosity (2%) represents the viscosity of an aqueous solution having a water-soluble polysaccharide concentration of 2%.
As the phosphoric acid, an 85% aqueous solution (manufactured by Wako Pure Chemical Industries) was used. Moreover, the compounding quantity of the phosphoric acid in a table | surface means the compounding quantity of 85% aqueous solution.
As the water-insoluble emulsifier, glyceryl monooleate (Reodol SP-030V manufactured by Kao) was used.
各表の水溶性多糖類粘度（１％）は、水溶性多糖類濃度１％の水溶液の粘度を表す。水溶性多糖類粘度（２％）は、水溶性多糖類濃度２％の水溶液の粘度を表す。
リン酸は８５％濃度の水溶液（和光純薬製）を使用した。また、表中のリン酸の配合量は、８５％水溶液の配合量を意味する。
非水溶性乳化剤は、モノオレイン酸グリセリン（花王製 レオドール ＳＰ－０３０Ｖ）を用いた。 In Examples and Comparative Examples shown in Table 2-7, water-soluble polysaccharides having the viscosity and the degree of etherification (in the case of CMC) shown in each example were used. HEC in the table is hydroxyethylcellulose, HPC is hydroxypropylcellulose, and HPMC is hydroxypropylmethylcellulose. Examples of CMC manufacturers include Daicel Finechem Co., Ltd., Daiichi Kogyo Seiyaku Co., Ltd., Nichirin Chemical Co., Ltd., Nippon Paper Industries Co., Ltd., and CP kelco.
The water-soluble polysaccharide viscosity (1%) in each table represents the viscosity of an aqueous solution having a water-soluble polysaccharide concentration of 1%. The water-soluble polysaccharide viscosity (2%) represents the viscosity of an aqueous solution having a water-soluble polysaccharide concentration of 2%.
As the phosphoric acid, an 85% aqueous solution (manufactured by Wako Pure Chemical Industries) was used. Moreover, the compounding quantity of the phosphoric acid in a table | surface means the compounding quantity of 85% aqueous solution.
As the water-insoluble emulsifier, glyceryl monooleate (Reodol SP-030V manufactured by Kao) was used.
上記で調製した実施例及び比較例のインキを下記の評価法により評価を行った。
（保存安定性の評価方法）
インキの調製後、２５℃、相対湿度５０％でインキを３カ月間保管した後、そのインキ１．０ｇをフーバーマラーに置き、１．１ｋｇの重量でインキを１００回転練肉した。練肉後のインキをインキナイフでこすり取り、このインキを以下のように観察した。
インキから分離した水滴はほとんど見られない・・・３（良好）
インキから分離した微小な水滴が見られる・・・２（実用上問題は無い）
インキから分離した水滴が多く見られる・・・１（実用できない） The inks of Examples and Comparative Examples prepared above were evaluated by the following evaluation methods.
(Storage stability evaluation method)
After the ink was prepared, the ink was stored at 25 ° C. and a relative humidity of 50% for 3 months, then 1.0 g of the ink was placed on a Hoover Maller, and the ink was kneaded 100 revolutions at a weight of 1.1 kg. The ink after kneading was scraped with an ink knife, and this ink was observed as follows.
Water droplets separated from the ink are hardly seen ... 3 (good)
Minute water droplets separated from ink can be seen ... 2 (no problem in practical use)
Many water droplets separated from ink can be seen ... 1 (not practical)
（保存安定性の評価方法）
インキの調製後、２５℃、相対湿度５０％でインキを３カ月間保管した後、そのインキ１．０ｇをフーバーマラーに置き、１．１ｋｇの重量でインキを１００回転練肉した。練肉後のインキをインキナイフでこすり取り、このインキを以下のように観察した。
インキから分離した水滴はほとんど見られない・・・３（良好）
インキから分離した微小な水滴が見られる・・・２（実用上問題は無い）
インキから分離した水滴が多く見られる・・・１（実用できない） The inks of Examples and Comparative Examples prepared above were evaluated by the following evaluation methods.
(Storage stability evaluation method)
After the ink was prepared, the ink was stored at 25 ° C. and a relative humidity of 50% for 3 months, then 1.0 g of the ink was placed on a Hoover Maller, and the ink was kneaded 100 revolutions at a weight of 1.1 kg. The ink after kneading was scraped with an ink knife, and this ink was observed as follows.
Water droplets separated from the ink are hardly seen ... 3 (good)
Minute water droplets separated from ink can be seen ... 2 (no problem in practical use)
Many water droplets separated from ink can be seen ... 1 (not practical)
（印刷適性の評価方法）
印刷機・・・ローランドＲ７００印刷機（マンローランド社製）
印刷速度・・・１００００枚／時
印刷版・・・ＥｘＴｈｅｒｍｏ ＴＰ－Ｗ（コダック合同会社製）
Ｈ液・・・プレサートＷＤ１００（ＤＩＣ株式会社製）
用紙・・・ＯＫトップコート＋（米坪 １０４．７ｇ／ｍ２ 王子製紙株式会社製）
Ｈ液は水で濃度１％に希釈したものを湿し水として用いた。
汚れ性の評価は、１万部印刷時の紙面の５０％網点部分を顕微鏡で拡大観察して、非画線部の汚れ度合いを次の３段階で評価した。
汚れはほとんど見られない・・・３（良好）
汚れは僅かに見られるが実用上問題は無い・・・２
汚れがかなり発生しており、実用上問題がある・・・１ (Evaluation method for printability)
Printing machine: Roland R700 printing machine (man Roland)
Printing speed: 10,000 sheets / hour printing plate: Ex Thermo TP-W (manufactured by Kodak GK)
Liquid H: Presert WD100 (manufactured by DIC Corporation)
Paper: OK top coat + (US tsubo 104.7 g / m 2 manufactured by Oji Paper Co., Ltd.)
Liquid H was diluted with water to a concentration of 1% and used as the fountain solution.
The evaluation of the smearing property was performed by magnifying and observing a 50% halftone dot portion of the paper surface when printing 10,000 copies with a microscope, and evaluating the degree of smearing in the non-image area in the following three stages.
Dirt is hardly seen ... 3 (good)
Slight dirt is seen but there is no practical problem ... 2
There is a lot of dirt and there are practical problems ... 1
印刷機・・・ローランドＲ７００印刷機（マンローランド社製）
印刷速度・・・１００００枚／時
印刷版・・・ＥｘＴｈｅｒｍｏ ＴＰ－Ｗ（コダック合同会社製）
Ｈ液・・・プレサートＷＤ１００（ＤＩＣ株式会社製）
用紙・・・ＯＫトップコート＋（米坪 １０４．７ｇ／ｍ２ 王子製紙株式会社製）
Ｈ液は水で濃度１％に希釈したものを湿し水として用いた。
汚れ性の評価は、１万部印刷時の紙面の５０％網点部分を顕微鏡で拡大観察して、非画線部の汚れ度合いを次の３段階で評価した。
汚れはほとんど見られない・・・３（良好）
汚れは僅かに見られるが実用上問題は無い・・・２
汚れがかなり発生しており、実用上問題がある・・・１ (Evaluation method for printability)
Printing machine: Roland R700 printing machine (man Roland)
Printing speed: 10,000 sheets / hour printing plate: Ex Thermo TP-W (manufactured by Kodak GK)
Liquid H: Presert WD100 (manufactured by DIC Corporation)
Paper: OK top coat + (US tsubo 104.7 g / m 2 manufactured by Oji Paper Co., Ltd.)
Liquid H was diluted with water to a concentration of 1% and used as the fountain solution.
The evaluation of the smearing property was performed by magnifying and observing a 50% halftone dot portion of the paper surface when printing 10,000 copies with a microscope, and evaluating the degree of smearing in the non-image area in the following three stages.
Dirt is hardly seen ... 3 (good)
Slight dirt is seen but there is no practical problem ... 2
There is a lot of dirt and there are practical problems ... 1
（ＶＯＣ削減率）
次の式によってＶＯＣ削減率（％）を計算した。
ＶＯＣ削減率＝１００－（各インキのＶＯＣ量／参考例インキのＶＯＣ量）×１００
各インキ中のＶＯＣ量はＡＦソルベント７号（ＡＦ－７）の合計量であり、ワニス及びベースインキ中のＡＦ－７の量と、表２－７に示す配合中のＡＦ－７とを合計して求めた。 (VOC reduction rate)
The VOC reduction rate (%) was calculated by the following formula.
VOC reduction rate = 100− (VOC amount of each ink / VOC amount of reference example ink) × 100
The amount of VOC in each ink is the total amount of AF Solvent No. 7 (AF-7). The total amount of AF-7 in the varnish and base ink and the AF-7 in the formulation shown in Table 2-7 are the total. And asked.
次の式によってＶＯＣ削減率（％）を計算した。
ＶＯＣ削減率＝１００－（各インキのＶＯＣ量／参考例インキのＶＯＣ量）×１００
各インキ中のＶＯＣ量はＡＦソルベント７号（ＡＦ－７）の合計量であり、ワニス及びベースインキ中のＡＦ－７の量と、表２－７に示す配合中のＡＦ－７とを合計して求めた。 (VOC reduction rate)
The VOC reduction rate (%) was calculated by the following formula.
VOC reduction rate = 100− (VOC amount of each ink / VOC amount of reference example ink) × 100
The amount of VOC in each ink is the total amount of AF Solvent No. 7 (AF-7). The total amount of AF-7 in the varnish and base ink and the AF-7 in the formulation shown in Table 2-7 are the total. And asked.
以上の実施例、比較例の結果から、本発明を構成する要件から外れたインキでは、発明
の課題を解決することはできず、本発明の構成をもって初めて課題解決に至ることが明ら
かである。 From the results of the examples and comparative examples described above, it is clear that inks that do not satisfy the requirements of the present invention cannot solve the problems of the invention, and that the problems can be solved only with the structure of the present invention.
の課題を解決することはできず、本発明の構成をもって初めて課題解決に至ることが明ら
かである。 From the results of the examples and comparative examples described above, it is clear that inks that do not satisfy the requirements of the present invention cannot solve the problems of the invention, and that the problems can be solved only with the structure of the present invention.
本発明の平版印刷インキ組成物を用いることにより、印刷インキの使用時（印刷時）において印刷インキ及び印刷物からの揮発性有機化合物の発生量を削減し、環境への負荷を低減することができる。
また本発明の平版印刷インキ組成物は優れた印刷適性を有し、汚れの発生等の少ない高品質の印刷を安定して行うことができる。 By using the lithographic printing ink composition of the present invention, it is possible to reduce the amount of volatile organic compounds generated from the printing ink and printed matter when using the printing ink (during printing), and to reduce the burden on the environment. .
Further, the lithographic printing ink composition of the present invention has excellent printability and can stably perform high-quality printing with little occurrence of stains.
また本発明の平版印刷インキ組成物は優れた印刷適性を有し、汚れの発生等の少ない高品質の印刷を安定して行うことができる。 By using the lithographic printing ink composition of the present invention, it is possible to reduce the amount of volatile organic compounds generated from the printing ink and printed matter when using the printing ink (during printing), and to reduce the burden on the environment. .
Further, the lithographic printing ink composition of the present invention has excellent printability and can stably perform high-quality printing with little occurrence of stains.
Claims (7)
- 次の（ａ）～（ｄ）の条件をすべて満足する平版印刷インキ組成物。
（ａ）水溶性のセルロース誘導体を０．０１～３質量％含有する。
（ｂ）水を１～３０質量％含有する。
（ｃ）前記のセルロース誘導体の２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓである。
（ｄ）前記のセルロース誘導体のエーテル化度が０．４５～１．００である。 A lithographic printing ink composition satisfying all of the following conditions (a) to (d):
(A) Contains 0.01 to 3% by mass of a water-soluble cellulose derivative.
(B) 1-30% by mass of water is contained.
(C) The viscosity of a 2% aqueous solution of the cellulose derivative is 2.5 to 1500 mPa · s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa · s.
(D) The degree of etherification of the cellulose derivative is 0.45 to 1.00. - さらに以下の条件を満足する請求項１に記載の平版印刷インキ組成物。
（ｅ）無機酸、無機酸の塩、有機酸、有機酸の塩の含有量の合計が０．２質量％以下である。 The lithographic printing ink composition according to claim 1, further satisfying the following conditions.
(E) The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less. - 次の条件を全て満足する平版印刷インキ組成物。
（Ａ）水溶性多糖類を０．０１～３質量％含有する。
（ｂ）水を１～３０質量％含有する。
（ｃ）前記水溶性多糖類の２％水溶液の粘度が２．５から１５００ｍＰａ・ｓであるか、若しくはその１％水溶液の粘度が１０～８０００ｍＰａ・ｓである。
（ｅ）無機酸、無機酸の塩、有機酸、有機酸の塩の含有量の合計が０．２質量％以下である。 A lithographic printing ink composition that satisfies all of the following conditions.
(A) It contains 0.01 to 3% by mass of a water-soluble polysaccharide.
(B) 1-30% by mass of water is contained.
(C) The viscosity of the 2% aqueous solution of the water-soluble polysaccharide is 2.5 to 1500 mPa · s, or the viscosity of the 1% aqueous solution is 10 to 8000 mPa · s.
(E) The total content of inorganic acid, inorganic acid salt, organic acid, and organic acid salt is 0.2% by mass or less. - 前記水溶性多糖類が、水溶性セルロース誘導体、キサンタンガム、ダイユータンガム、カラギーナンから選ばれる少なくとも一種であることを特徴とする請求項３に記載の平版印刷インキ組成物。 The lithographic printing ink composition according to claim 3, wherein the water-soluble polysaccharide is at least one selected from a water-soluble cellulose derivative, xanthan gum, diyutan gum, and carrageenan.
- 非水溶性乳化剤の含有量が１．０質量％未満であることを特徴とする請求項１乃至４のいずれか一項に記載の平版印刷インキ組成物。 The lithographic printing ink composition according to any one of claims 1 to 4, wherein the content of the water-insoluble emulsifier is less than 1.0% by mass.
- 湿し水を用いた印刷方法に用いられる請求項１乃至５のいずれか一項に記載の平版印刷インキ組成物。 The lithographic printing ink composition according to any one of claims 1 to 5, which is used in a printing method using fountain solution.
- 請求項１乃至５のいずれか一項に記載の平版印刷インキ組成物を用いて印刷された印刷物。 Printed matter printed using the planographic printing ink composition according to any one of claims 1 to 5.
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| JP2016540058A JP6018350B1 (en) | 2014-12-22 | 2015-12-16 | Lithographic printing ink composition |
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|---|---|---|---|
| JP2014258704 | 2014-12-22 | ||
| JP2014-258704 | 2014-12-22 |
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| WO2016104283A1 true WO2016104283A1 (en) | 2016-06-30 |
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| PCT/JP2015/085216 WO2016104283A1 (en) | 2014-12-22 | 2015-12-16 | Lithographic ink composition |
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| WO (1) | WO2016104283A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50124715A (en) * | 1974-03-15 | 1975-10-01 | ||
| JPS5562980A (en) * | 1978-11-06 | 1980-05-12 | Daicel Chem Ind Ltd | Aqueous ink composition |
| JPS62250083A (en) * | 1986-04-23 | 1987-10-30 | Toyo Ink Mfg Co Ltd | Ink for lithography |
| JPH0952463A (en) * | 1995-08-10 | 1997-02-25 | Riso Kagaku Corp | Fixing method of printing water base ink and water base ink |
| JPH11323216A (en) * | 1998-05-14 | 1999-11-26 | Nisshin Oil Mills Ltd:The | Ink containing high-viscosity xanthan gum |
| JP2000351944A (en) * | 1999-06-14 | 2000-12-19 | Dainippon Ink & Chem Inc | Drier for printing ink, production of the same drier and printing ink composition comprising the same drier |
| JP2002265838A (en) * | 2001-02-28 | 2002-09-18 | Sun Chemical Corp | Water-based offset lithography ink for printing newspaper |
-
2015
- 2015-12-16 WO PCT/JP2015/085216 patent/WO2016104283A1/en active Application Filing
- 2015-12-16 JP JP2016540058A patent/JP6018350B1/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50124715A (en) * | 1974-03-15 | 1975-10-01 | ||
| JPS5562980A (en) * | 1978-11-06 | 1980-05-12 | Daicel Chem Ind Ltd | Aqueous ink composition |
| JPS62250083A (en) * | 1986-04-23 | 1987-10-30 | Toyo Ink Mfg Co Ltd | Ink for lithography |
| JPH0952463A (en) * | 1995-08-10 | 1997-02-25 | Riso Kagaku Corp | Fixing method of printing water base ink and water base ink |
| JPH11323216A (en) * | 1998-05-14 | 1999-11-26 | Nisshin Oil Mills Ltd:The | Ink containing high-viscosity xanthan gum |
| JP2000351944A (en) * | 1999-06-14 | 2000-12-19 | Dainippon Ink & Chem Inc | Drier for printing ink, production of the same drier and printing ink composition comprising the same drier |
| JP2002265838A (en) * | 2001-02-28 | 2002-09-18 | Sun Chemical Corp | Water-based offset lithography ink for printing newspaper |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6018350B1 (en) | 2016-11-02 |
| JPWO2016104283A1 (en) | 2017-04-27 |
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