JP4684806B2 - Dampening solution composition for lithographic printing - Google Patents

Description

  The present invention relates to a fountain solution composition for lithographic printing.

  Lithographic printing is a printing method that skillfully uses the property that water and oil do not essentially mix, and the printing plate surface consists of an area that receives water and repels oil-based ink, and an area that repels water and receives oil-based ink. Thus, the former is a non-image area and the latter is an image area. The non-image area is moistened with the fountain solution to increase the interfacial chemical difference between the image area and the non-image area, thereby increasing the ink repellency of the non-image area and the ink receptivity of the image area. Made. Conventionally known fountain solutions include alkali metal salts or ammonium salts of dichromic acid, phosphoric acid or salts thereof such as colloidal substances such as ammonium salts, gum arabic, and carboxymethyl cellulose (CMC). There is an aqueous solution added. However, the fountain solution containing only these compounds has the disadvantage that it is difficult to uniformly wet the non-image area of the plate, so that the printed matter sometimes gets soiled, and considerable skill is required to adjust the supply amount of the fountain solution. It has become a problem such as requiring. In recent years, regulations on the release of chromium ions in wastewater have become stricter and tend to be regulated from the aspect of health and safety.

In order to remedy this drawback, a Dahlglen system using an aqueous solution to which about 20 to 25% of isopropyl alcohol is added as a fountain solution has been proposed and widely used. According to this method, wetting to non-image areas is improved, the amount of dampening water is small, the supply balance between printing ink and water is easy to adjust, and emulsification of dampening water into printing ink There are a number of advantages in terms of workability and accuracy of the printed matter obtained, such as a reduced amount and better transferability of the printing ink to the blanket.
However, since this isopropyl alcohol is different from water in easiness of evaporation, a special expensive apparatus for keeping the isopropyl alcohol concentration of the dampening solution constant is required. In addition, isopropyl alcohol has a peculiar unpleasant odor and has a problem in toxicity, and is an organic solvent poisoning prevention rule (organic law) type 2 organic solvent and is regulated. Furthermore, since it is a hazardous material class 4 alcohol and easily flammable, it requires handling and storage management, which is not preferable in the work environment. Moreover, even if this fountain solution to which isopropyl alcohol is added is applied to offset printing using a normal water rod, isopropyl alcohol evaporates on the roller and the plate surface, so that the effect cannot be exhibited. There was a problem.

For this reason, techniques for replacing isopropyl alcohol have been proposed in recent years (see, for example, Patent Documents 1 to 19).
However, since these alternative technologies use volatile organic solvents, they cause discharge of VOC (volatile organic compounds), and improvements are required.
On the other hand, a technique using a nonvolatile or high boiling point compound as an isopropyl alcohol substitute compound has been developed. For example, it has been proposed to include a specific alkylene oxide-based nonionic surfactant in the fountain solution (see, for example, Patent Document 20), and dampen the ethylene oxide and propylene oxide adducts of alkylene diamine. It is proposed to include in a water composition (for example, refer patent document 21). However, when such a fountain solution composition is used, when the fountain solution remaining on the plate surface when the printing machine is stopped becomes water droplets and the water is evaporated, these non-volatile or high boiling point compounds remain concentrated. There is a disadvantage that the image area of the lithographic printing plate is dissolved and the image is damaged.
Furthermore, with these isopropyl alcohol alternative technologies, printing with UV ink and printing machines equipped with an indirect water supply type water supply device such as Heidelberg make it easier for ink emulsification to proceed and printing for a long time. Ink emulsification causes a drop in transferability, causing problems such as water loss and poor inking, and isopropyl alcohol may have to be added to the fountain solution.

JP-A-5-92677 JP-A-5-318958 JP 2001-287476 A JP-A-2-269909 JP-A-3-63187 Japanese Patent Laid-Open No. 3-90389 Japanese Patent Laid-Open No. 3-90390 JP-A-4-363297 Japanese Patent Laid-Open No. 5-112085 JP-A-11-78281 JP-A-11-105449 JP 2001-130164 A JP 2001-138659 A JP 2001-180146 A JP 2001-18553 A JP 2001-71658 A JP 2002-187375 A JP 2002-187376 A JP 2002-192853 A JP 51-72507 A JP 2002-254852 A

The object of the present invention is that the conventional fountain solution does not have the toxicity and disadvantages, and can completely replace isopropyl alcohol in a printing machine of any mechanism without requiring expert skill in the printing operation. The object is to provide a fountain solution for lithographic printing. Another object of the present invention is to provide a fountain solution for lithographic printing which is free from safety and health and fire safety problems.
The object of the present invention is, in particular, a wet for lithographic printing, which can be printed stably even without continuous printing for a long time without causing problems such as smudges, blinding and water loss on the printing plate, and poor ink deposition on the plate. It is in providing a shimizu composition. Another object of the present invention is to provide a fountain solution composition that can maintain the ink on the ink roll in a state suitable for printing without excessively emulsifying the ink. Another object of the present invention is a dampening for lithographic printing in which the dampening water remaining on the plate surface when the printing press is stopped becomes water droplets, and even if the water evaporates, the image portion is not dissolved and the image is not damaged. It is to provide a water composition. Another object of the present invention is to provide a fountain solution for lithographic printing, which can obtain a high-quality printed matter.

As a result of intensive studies to achieve the above object, the present inventor can obtain an excellent fountain solution for lithographic printing by including a specific compound in the fountain solution composition. As a result, the present invention has been completed.
Therefore, the present invention provides a compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine,
The following (I) to (III):
(I) a starch-based water-soluble polymer compound modified with an alkyl group,
At least selected from the group consisting of (II) a cellulose-based water-soluble polymer compound modified with an alkyl group, and (III) a water-soluble polymer compound derived from vinyl polymerization of an unsaturated monomer containing a vinyl group. One water-soluble polymer compound;
Formula ^{(1): R 1 -O- (} CH 2 CHR 2 O) n-H (1)
A fountain solution for lithographic printing, comprising: a compound represented by (R ¹ represents an alkyl group having 4 carbon atoms, R ² represents hydrogen or a methyl group, and n is 1). It is a composition.
As a preferred embodiment of the present invention, the fountain solution composition further contains at least one selected from saccharides.

The fountain solution composition for lithographic printing according to the present invention substitutes isopropyl alcohol in the fountain solution composition in various continuous water supply type printers without the need for specialized skill in printing work, and at the time of printing. Stable continuous printing can be performed without causing problems such as smearing of the printing plate, blinding, and water loss, and the printability is good. According to the fountain solution composition for lithographic printing of the present invention, the dampening solution remaining on the plate surface when the printing machine is stopped, for example, during a lunch break, becomes water droplets and does not dissolve the image portion even if the water evaporates. The image is not damaged.
According to the fountain solution composition of the present invention, the amount of the volatile organic solvent can be made extremely small to completely replace isopropyl alcohol, and there is no problem in terms of occupational health and fire safety, and high quality. Prints can be obtained, and printing efficiency and productivity can be improved.

  Hereinafter, the present invention will be described in detail. The fountain solution is generally concentrated and commercialized when used on a commercial basis, and when used, such a concentrate is appropriately diluted and used as a fountain solution. In the present specification, the concentrated product is referred to as a fountain solution composition. The contents and addition amounts of various components mentioned below are based on the total mass of dampening water during use unless otherwise specified.

[Compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine]
The compound having ethylene oxide and propylene oxide added to diethylenetriamine used in the present invention has an appropriate weight average molecular weight in the range of 500 to 3,000, preferably 800 to 2,000, and most suitable is a weight average molecular weight of around 1000. Is.
The above-mentioned compound having such a molecular weight does not damage the image area even when water droplets remaining on the plate when the printing press is stopped are left by evaporation of water and concentration. The above compounds can also replace isopropyl alcohol without using in combination with a volatile organic solvent.

In the compound, the ratio of the number of added moles of ethylene oxide and propylene oxide is suitably in the range of 5:95 to 50:50, more preferably 20:80 to 35:65 from the viewpoint of obtaining sufficient printability. It is a range.
As the bond structure of ethylene oxide and propylene oxide, block structure in which ethylene oxide is added first and then propylene oxide is added, block structure in which propylene oxide is added first and then ethylene oxide is added, and simultaneously ethylene oxide and propylene There is a random structure to which oxide is added, but the same effect can be obtained with any structure.
The compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine used in the present invention can be produced according to a conventional method. For example, it can be produced by reacting diethylenetriamine with ethylene oxide and / or propylene oxide in the presence of a catalyst. Specifically, while cooling diethylenetriamine together with acetonitrile in an ice-water bath, propylene oxide was added dropwise to react therewith, and then ethylene oxide was further added dropwise to react, followed by filtration from this mixture and taking out the precipitate. From this, a propylene oxyad / ethylene oxide adduct of diethylenetriamine can be obtained.

（式中、Ａ及びＢはそれぞれ独立に−ＣＨ₂ＣＨ₂Ｏ−又は−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−を表し、Ａ及びＢは互いに異なる基であって、ａ〜ｊは各々１以上の整数を表す。各共重合鎖はブロック構造でも、ランダム構造でもよい。）
式中、ａ〜ｊは化合物全体の分子量が５００〜３０００となるような値であることが適当である。
なお、該化合物の分子量やエチレンオキサイドとプロピレンオキサイドの比率は、例えば水酸基価及びアミン価の測定、ＮＭＲ測定などにより決定することができる。 A compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine used in the present invention is specifically represented by the following formula.

(In the formula, A and B each independently represent —CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, wherein A and B are groups different from each other, and a to j are each 1 or more. (Each copolymer chain may be a block structure or a random structure.)
In the formula, a to j are suitably values such that the molecular weight of the whole compound is 500 to 3000.
The molecular weight of the compound and the ratio of ethylene oxide to propylene oxide can be determined by, for example, measurement of hydroxyl value and amine value, NMR measurement, or the like.

  By using a fountain solution containing 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass of the above compound, good printability is exhibited even if isopropyl alcohol is substituted. Further, after the fountain solution is applied, even if the water droplets remaining on the plate at the time of printing stop are left to evaporate and become concentrated, the image area of the plate is not affected.

[Water-soluble polymer compound]
The fountain solution composition of the present invention further contains at least one water-soluble polymer compound selected from the group consisting of the following (I) to (III).
(I) Starch-based water-soluble polymer compound modified by alkyl group (II) Cellulose-based water-soluble polymer compound modified by alkyl group (III) From vinyl polymerization of unsaturated monomer containing vinyl group Derived water-soluble polymer compound In the starch-based water-soluble polymer compound modified with the alkyl group of (I) above, specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples thereof include starch-based water-soluble polymer compounds modified with at least one selected from the above alkyl groups. Specific examples of the water-soluble polymer compound (I) include methyl starch, ethyl starch, hydroxyethyl starch, hydroxypropyl starch, carboxyethyl starch, hydroxypropylated enzymatically degraded dextrin, and octenyl succinated starch. Of these, starch-based water-soluble polymer compounds modified with a methyl group or a propyl group are preferable, and examples thereof include hydroxypropyl starch and hydroxypropylated enzyme-degraded dextrin.

  In the cellulose-based water-soluble polymer compound modified with the alkyl group (II) above, specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group, and at least one selected from these alkyl groups. Examples thereof include cellulose-based water-soluble polymer compounds modified by seeds. Specific examples of the water-soluble polymer compound (II) include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and carboxyethyl cellulose. Among these, a cellulose-based water-soluble polymer compound modified with a methyl group or a propyl group is preferable, and examples thereof include hydroxypropylcellulose and hydroxypropylmethylcellulose.

  The water-soluble polymer compound derived from the vinyl polymerization of the unsaturated monomer containing a vinyl group (III) may be a homopolymer or copolymer of an unsaturated monomer containing a vinyl group, Furthermore, what gave the neutralization process etc. may be used. Specific examples of the water-soluble polymer compound (III) include polyvinyl alcohol, polyvinyl alkyl ether, polyvinyl acetate, polyvinyl pyrrolidone, polyacrylic acid, polyacrylic acid soda, polyacrylamide, polyacrylic acid ester, and polymethacrylic acid ester. , Carboxyvinyl polymer, acrylamide / acrylate copolymer, alkylate polyvinyl pyrrolidone, and polyvinyl pyrrolidone / vinyl acetate copolymer. Among these, polyvinyl pyrrolidone, polyvinyl pyrrolidone / vinyl acetate copolymer, and alkylate polyvinyl pyrrolidone can be particularly preferably used.

The water-soluble polymer compound to be included in the fountain solution composition of the present invention may be one kind selected from the above (I) to (III), or may be used in combination of two or more kinds.
The water-soluble polymer compounds (I) to (III) used in the present invention preferably have a relatively low viscosity, and a 0.1% aqueous solution thereof is suitably 100 cps or less, more preferably a 1% aqueous solution. Is less than 100 cps.
The content of these water-soluble polymers in the fountain solution is suitably 0.001 to 0.3% by mass, preferably 0.005 to 0.2% by mass, from the viewpoint of improving printing performance.
The water-soluble polymer compounds (I) to (III) can be generally obtained on the market, and commercially available products can be used in the present invention. Examples of commercially available products include Metroze manufactured by Shin-Etsu Chemical Co., Ltd., and there are SM-4, SM-15, SM-25, SM-100, etc. as SM types of methylcellulose, and SH type of hydroxypropyl methylcellulose. There are 60SH-3, 60SH-6, 60SH-15, 60SH-50, 65SH-50 and so on.

[Compound represented by the general formula (1)]
The fountain solution composition of the present invention further contains a compound of the following general formula (1). By using this compound, the printing performance is improved and the phenomenon of ink over-emulsification is less likely to occur. Even in printing presses equipped with indirect water supply type water supply devices such as printing using UV ink and Heidelberg, Good printing performance can be exhibited without using isopropyl alcohol at all.
_{^{R 1 -O- (CH 2 CHR 2}} O) n-H (1)
(R ¹ represents an alkyl group having 4 carbon atoms, R ² represents hydrogen or a methyl group, and n is 1.)
In the formula, R ¹ is suitably an n-butyl group, an isobutyl group or a t-butyl group.
The compounds of general formula (1) are specifically ethylene glycol-n-butyl ether, ethylene glycol isobutyl ether, ethylene glycol-t-butyl ether, propylene glycol-n-butyl ether, propylene glycol isobutyl ether, and propylene glycol-t-butyl ether. It is.
From the viewpoint of occupational safety, a propylene glycol compound in which R ² is a methyl group is desirable.
0.001-1 mass% is suitable for content of the compound shown by General formula (1) in dampening water, Preferably it is 0.1-0.5 mass%.

[Sugar]
The fountain solution composition of the present invention preferably contains at least one selected from saccharides. The sugar to be used can be selected from monosaccharides, disaccharides, oligosaccharides, and the like, and includes sugar alcohols obtained by hydrogenation. Specific examples include D-erythrose, D-throse, D-arabinose, D-ribose, D-xylose, D-erythro-pentulose, D-allulose, D-galactose, D-glucose, D-mannose, D-talose, β -D-fructose, α-L-sorbose, 6-deoxy-D-glucose, D-glycero-D-galactose, α-D-allo-heptulose, β-D-alto-3-heptulose, saccharose, lactose, D Maltose, isomaltose, inulobiose, maltotriose, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, dulcit, allozulcit , Maltitol, and reduced water candy. These saccharides may be used alone or in combination of two or more. By including saccharides in the fountain solution composition, the printing performance can be further improved.
In the fountain solution, the content of at least one selected from saccharides is suitably 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass.

[Solubilization auxiliary solvent]
In actual use, the fountain solution is supplied as a fountain solution composition that is a concentrated solution, and is usually diluted to about 0.5 to 5% for use.
In blending the compound represented by the general formula (1), it is desirable to use a solubilizing auxiliary solvent together in order to maintain good liquid stability when preparing a fountain solution composition that is a concentrate.
Examples of the solubilizing auxiliary solvent include ethanol, propanol, butanol, isobutanol, t-butanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, propylene glycol methyl ether, propylene glycol ethyl Examples include ether, propylene glycol propyl ether, propylene glycol isopropyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, and 3-methoxy-3-methyl-1-butanol. Of these, 3-methoxy-3-methyl-1-butanol is preferably used.
Such a solubilizing auxiliary solvent is generally added in an amount of 3 to 30% by mass, preferably 5 to 20% by mass, in the fountain solution composition that is a concentrate. The solubilizing auxiliary solvent is generally contained in the dampening water at the time of use in an amount of about 0.1 to 1% by mass.

  In view of the amount used and the dilution rate in the fountain solution when using the various compounds described above, and in view of the stable solubilization of the compound represented by the general formula (1), the fountain solution composition that is a concentrated liquid As an example, 1 to 40% by mass of a compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine, 1 to 10% by mass of the above water-soluble polymer compound, and 4 to 40% by mass of the compound represented by the general formula (1) And a fountain solution composition containing 2 to 50% by mass of saccharide and 3 to 30% by mass of a solubilizing auxiliary solvent.

The fountain solution is generally desirably used in the acidic region, that is, in the range of pH around 3-6. When the pH is less than 3, the etching effect on the support becomes strong and the printing durability is lowered. In order to adjust the pH value to 3 to 6, generally, an organic acid and / or an inorganic acid or a salt thereof may be added. Preferred organic acids include, for example, citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, glycolic acid, gluconic acid, hydroxyacetic acid, succinic acid, malonic acid, levulinic acid, sulfanilic acid, p-toluenesulfonic acid, phytic acid And organic phosphonic acid. Examples of the inorganic acid include phosphoric acid, nitric acid, sulfuric acid, and polyphosphoric acid. Further, alkali metal salts, alkaline earth metal salts or ammonium salts of these organic acids and / or inorganic acids, and organic amine salts are also preferably used. These organic acids, inorganic acids and / or salts thereof can be used alone. Or you may use as a mixture of 2 or more types. The addition amount is generally 0.001 to 5% by mass in dampening water.
The fountain solution composition of the present invention can also contain an alkali metal hydroxide, an alkali metal phosphate, an alkali metal carbonate, a silicate and the like, and can be used in an alkaline region near pH 7-11.

In addition to the above components, a chelate compound can also be added to the fountain solution composition of the present invention. Usually, tap water, well water, etc. are added and diluted to the fountain solution composition which is a concentrated solution, and used as the fountain solution. At this time, calcium ions or the like contained in the tap water or well water to be diluted may affect the printing and cause the printed matter to be easily stained. In such a case, the above disadvantages can be eliminated by adding a chelate compound. Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, potassium salt thereof, sodium salt thereof; hydroxyethylethylenediaminetriacetic acid Nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2-propanoltetraacetic acid, its Aminopolycarboxylic acids such as potassium salt and sodium salt thereof, 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt and sodium salt thereof; 2-phosphonobutanetricarboxylic acid- , 3,4, its potassium salt, its sodium salt; 1-phosphonoethanetricarboxylic acid-1,2,2, its potassium salt, its sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt Organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri (methylenephosphonic acid), potassium salt, sodium salt, and the like.
Organic amine salts are also effective in place of the sodium or potassium salts of the above chelating agents.
These chelating agents are selected so that they are stably present in the dampening water and do not impair the printability. The amount to be added is 0.001 to 3% by mass, preferably 0.01 to 1% by mass in dampening water.

The fountain solution composition of the present invention may further contain a colorant, a rust inhibitor, an antifoaming agent, and the like. Food coloring agents and the like can be preferably used as the colorant. For example, CI No. 19140, 15985 as a yellow dye, CI No. 16185, 45430, 16255, 45380, 45100 as a red dye, CI No. 42640 as a purple dye, CI No. 42090, 73015 as a blue dye, CI No. 42095, and the like. Examples of the rust preventive include benzotriazole, 5-methylbenzotriazole, thiosalicylic acid, benzimidazole and derivatives thereof.
As the antifoaming agent, a silicon antifoaming agent is preferable, and any of an emulsified dispersion type and a solubilized type can be used.

  The fountain solution composition of the present invention further includes corrosion inhibitors such as magnesium nitrate, zinc nitrate, calcium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, and ammonium nitrate, hardeners such as chromium compounds and aluminum compounds, and cyclic ethers. : For example, an organic solvent such as 4-butyrolactone, a water-soluble surface active organometallic compound described in JP-A No. 61-193893, and the like can be added in the range of 0.0001 to 1% by mass of dampening water.

  A small amount of a surfactant may be added to the fountain solution composition of the present invention. For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid salts, linear alkylbenzenesulfonic acid salts, branched alkylbenzenesulfonic acid salts, alkylnaphthalene. Sulfonates, alkylphenoxy polyoxyethylenepropyl sulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, Hydrogenated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride Acid ester salts, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene Examples thereof include partially saponified products of maleic anhydride copolymers, partially saponified products of olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates. Among these, dialkyl sulfosuccinates, alkyl sulfates and alkyl naphthalene sulfonates are particularly preferably used.

  Nonionic surfactants include polyoxyalkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial esters, sorbitan fatty acid moieties. Esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid partial esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyglycerin fatty acid partial esters, poly Oxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxy Alkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, such as trialkylamine oxides. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used.

Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, and the like. Examples of amphoteric surfactants include alkyl imidazolines. In addition, examples of the fluorine-based anionic surfactant include fluorine-based surfactants, such as perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, and fluorine-based nonionic surfactants. Examples of the perfluoroalkylethylene oxide adduct, perfluoroalkylpropylene oxide adduct, and fluorine-based cationic surfactant include perfluoroalkyltrimethylammonium salts.
The content of these surfactants is 10% by mass or less, preferably 0.01 to 3.0% by mass in dampening water in view of foaming.

  The fountain solution composition of the present invention may contain glycols and / or alcohols as a wetting agent. Examples of such wetting agents include diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, diethylene glycol monopropyl ether, triethylene glycol. Monopropyl ether, tetraethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, tetraethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol mono Chirueteru, diethylene glycol isobutyl ether, triethylene glycol monoisobutyl ether, tetraethylene glycol monoisobutyl ether, diethylene glycol mono t-butyl ether, triethylene glycol mono t-butyl ether, tetraethylene glycol mono t-butyl ether,

  Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrapropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tetrapropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol mono Propyl ether, tetrapropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether, tetrapropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol model Butyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoisobutyl ether, tetrapropylene glycol monoisobutyl ether, dipropylene glycol monotertiary butyl ether, tripropylene glycol monotertiary butyl ether, tetrapropylene glycol monotertiary butyl ether, molecular weight 200- 1000 polypropylene glycols and their monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether and monobutyl ether,

Tetrapropylene glycol and pentapropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butylene glycol, hexylene glycol, benzyl alcohol, ethylene glycol monophenyl ether, 2-ethyl-1,3-hexanediol, 1-butoxy Examples include 2-propanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, methoxyethanol, ethoxyethanol, butoxyethanol, and 3-methoxybutanol.
These wetting agents can be contained alone or in combination of two or more in an amount of about 0.01 to 1% by mass in dampening water.

The balance is water as a component of the fountain solution composition of the present invention.
Accordingly, in consideration of the content of the various components in the fountain solution and the dilution rate of the fountain solution composition, water, preferably demineralized water, i.e., pure water, is used to adjust the various components at appropriate concentrations. A fountain solution composition that is dissolved and a concentrated liquid can be prepared. Such a concentrated solution is diluted about 20 to 200 times with normal tap water, well water or the like at the time of use to obtain a dampening water at the time of use.

The fountain solution composition of the present invention greatly reduces the amount of organic solvent used to discharge VOC (volatile organic compounds), while printing using UV ink without using isopropyl alcohol. It can suppress the ink over-emulsification phenomenon that tends to occur in a printer equipped with an indirect water supply type water supply device, and can exhibit good printing performance.
Further, there is no problem in printing quality even when isopropyl alcohol up to about 15% by mass in dampening water is used in combination.

  The fountain solution composition of the present invention can be used for various lithographic printing plates. In particular, a photosensitive lithographic printing plate having an aluminum plate as a support and a photosensitive layer thereon (previously photosensitive). The applied printing plate is called a PS plate) and can be suitably used for a lithographic printing plate obtained by image exposure and development. A preferable example of such PS plate is a photosensitive layer comprising a mixture of a diazo resin (a salt of a condensate of p-diazodiphenylamine and paraformaldehyde) and a shellac as described in British Patent 1,350,521. On the aluminum plate, polymers having diazo resin and hydroxyethyl methacrylate unit or hydroxyethyl acrylate unit as main repeating units as described in British Patent Nos. 1,460,978 and 1,505,739 And a photosensitive polymer system containing a dimethylmaleimide group described in JP-A-2-236552 and JP-A-4-274429 was provided on an aluminum plate. A negative PS plate such as the one disclosed in JP-A-50-125806 It includes positive PS plate provided on an aluminum plate and a photosensitive layer comprising a mixture of O- Kinonjiado photosensitive material and a novolac-type phenolic resins as described in. It can also be used for a positive PS plate that has been burned.

In the composition forming the photosensitive layer, an alkali-soluble resin other than the alkali-soluble novolak resin can be blended as necessary. For example, styrene-acrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer, alkali-soluble polyurethane resin, alkali-soluble vinyl resin described in JP-B-52-28401, alkali-soluble polybutyral resin, and the like. it can. Further, a PS plate having a photosensitive layer of a photopolymerizable photopolymer composition as described in US Pat. Nos. 4,072,528 and 4,072,527 on an aluminum plate, British Patent Nos. 1,235,281 and A PS plate having a photosensitive layer made of a mixture of an azide and a water-soluble polymer on an aluminum plate as described in each specification of No. 1,495,861 is also preferable.
Furthermore, it can be suitably used for a CTP plate that is directly exposed with a visible or infrared laser. Specific examples include a photopolymer type digital plate (for example, LP-NX manufactured by Fuji Photo Film Co., Ltd.), a thermal positive type digital plate (for example, LH-PI manufactured by Fuji Photo Film Co., Ltd.), and a thermal negative type digital plate (for example, Fuji Photo Film Co., Ltd. LH-NI).

Next, the present invention will be described more specifically with reference to examples. % Indicates mass% unless otherwise specified.
According to the composition of the following Tables 1-2, the various fountain solution compositions of Examples 1-8 and Comparative Examples 1-4 were prepared. In the table, the unit is gram, and water is finally added to make 1000 ml. These are all concentrated types and are diluted at the time of use.

^*EO:PO比：エチレンオキサイドとプロピレンオキサイドとの付加モル数比率
^*1 商品名：メトローズ SM-4（信越化学工業（株）製）
^*2 商品名：HPC L（日本曹達（株）製）
^*3 商品名：KL-506（（株）クラレ製）
^*4 商品名：アロン A-10（東亜合成（株）製）
^*5 商品名：K-15（ＩＳＰ社製）
^*6 商品名：GANEX P（ＩＳＰ社製）
^*7 商品名：クリームデキストリン（松谷化学工業（株）製）

^* EO: PO ratio: Ratio of added moles of ethylene oxide and propylene oxide
^{* 1} Product name: Metroz SM-4 (manufactured by Shin-Etsu Chemical Co., Ltd.)
^{* 2} Product name: HPC L (Nippon Soda Co., Ltd.)
^{* 3} Product name: KL-506 (Kuraray Co., Ltd.)
^{* 4} Product name: Aaron A-10 (manufactured by Toa Gosei Co., Ltd.)
^{* 5} Product name: K-15 (made by ISP)
^{* 6} Product name: GANEX P (made by ISP)
^{* 7} Product name: Cream dextrin (Matsuya Chemical Co., Ltd.)

^*EO:PO比：エチレンオキサイドとプロピレンオキサイドとの付加モル数比率
^*1 〜^*7は表１の注記と同様である。

^* EO: PO ratio: Ratio of added moles of ethylene oxide and propylene oxide
^{* 1} to ^{* 7} are the same as the notes in Table 1.

  Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 4 prepared as described above was diluted 40 times with pseudo-hard water having a hardness of 400 ppm, and the pH became around 4.8 to 5.3. In this way, it was adjusted with NaOH / phosphoric acid (85%) to obtain a dampening solution that was actually used. Further, 8% isopropyl alcohol and 11% dampening water EU-3 manufactured by Fuji Photo Film Co., Ltd. were added to pseudo-hard water having a hardness of 400 ppm to prepare Comparative Example 5 as a working solution.

[Test method]
The printing machine uses Heidelberg MOV, Toyo Ink Co., Ltd. name FD Carton ACE process four colors (black, indigo, red, yellow) ink, and Fuji Photo Film Co., Ltd. thermal type After writing with Creo platesetter using CTP-PS HP-S, develop with Fuji Photo Film Developer DT-2, and with Fuji Photo Film Finisher Liquid FG-1 A printing test was carried out using what was made and made.
(a) Continuous printing stability:
Obtain the minimum amount of dampening water that does not cause stains and does not cause water loss, and perform printing with this minimum amount of water using various types of dampening water. Thus, the determination is made based on the number of printed sheets until a satisfactory printed matter cannot be obtained.
10,000 sheets or more A
10000 to 3000 or more B
2999-1 sheets C
None D

(b) Emulsification:
The state of emulsification of the ink on the ink kneading roller when 10,000 sheets are printed is examined.
Good A
Slightly bad B
Bad C
(c) Image portion deterioration:
The printing machine is stopped, and 5 μl, 10 μl, 20 μl and 50 μl of dampening water are dropped onto the solid portion of the PS plate and the image portion of the 30% halftone dot portion using a syringe, and left for 60 minutes. Thereafter, printing is resumed, and image area deterioration is evaluated.
No problem A
There is some deterioration (there is ring-shaped trace) B
Degradation C
The test results are shown in Table 3 below.

From the above results, the fountain solution according to the embodiment of the present invention is excellent in any of continuous printing stability, emulsifiability, and image portion deterioration even in printing using UV ink that easily causes over-emulsification. A printed matter is obtained, and the continuous printing stability is remarkably excellent as compared with the dampening water of Comparative Examples 1 to 4 and the dampening water of Comparative Example 5 using isopropyl alcohol.
Further, the fountain solution compositions of Examples 1 to 8 are different from isopropyl alcohol, have no problems in occupational safety and fire safety, and are different from existing isopropyl alcohol alternative fountain solutions in that UV ink is used. Even in difficult conditions such as time and printing machines such as Heidelberg, good printing performance can be exhibited without using isopropyl alcohol together, and this is environmentally preferable.

Claims (2)

A compound in which ethylene oxide and propylene oxide are added to diethylenetriamine , the weight average molecular weight is in the range of 800 to 2000, and the added mole ratio of ethylene oxide and propylene oxide is in the range of 20:80 to 35:65. A compound ,
The following (II) to (III):
At least selected from the group consisting of (II) a cellulose-based water-soluble polymer compound modified with an alkyl group, and (III) a water-soluble polymer compound derived from vinyl polymerization of an unsaturated monomer containing a vinyl group. One water-soluble polymer compound;
Formula ^{(1): R 1 -O- (} CH 2 CHR 2 O) n-H
(Wherein R ¹ represents an alkyl group having 4 carbon atoms, R ² represents hydrogen or a methyl group, and n is 1) ,
At least one selected from sugars;
A fountain solution for lithographic printing, comprising 3-methoxy-3-methyl-1-butanol . The fountain solution composition for lithographic printing according to claim 1, wherein the saccharide is at least one selected from monosaccharides, disaccharides, oligosaccharides and sugar alcohols.