JP4758219B2 - Dampening solution composition for lithographic printing - Google Patents

Description

  The present invention relates to a fountain solution 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. However, since these alternative technologies use volatile organic solvents, they cause discharge of VOC (volatile organic compounds), and improvements are required.
In addition to the above problems, there are problems of corrosion and rust generation on the metal parts of the printing press and the dampening water circulation device due to dampening water. As a printing machine, a printer in which a part of an ink kneading roller is made of a highly lipophilic copper or copper alloy roll is often used. When printing using such a printing machine, the non-image area of the lithographic printing plate is maintained in a hydrophilic state, ink is received only in the image area, and the ink is transferred to the paper through a rubber blanket. However, at this time, the impression cylinder (made of cast iron that is nickel-plated, chrome-plated, or polished) is brought into contact with the blanket. For this reason, when printing on a printing machine having a copper or copper alloy plating roll or impression cylinder, depending on the type and amount of the dampening water additive added to the dampening water, the copper or copper alloy plating is performed. In many cases, corrosion or rusting of the parts and the impression cylinder occurs.
Therefore, a fountain solution that can prevent corrosion and rust generation of these metals is required.

From the viewpoint of not using isopropyl alcohol, a technique for using a non-volatile or high boiling point compound as an isopropyl alcohol substitute compound has been developed. For example, it has been proposed that ethylene oxide and propylene oxide adducts of alkylene diamine are included in the fountain solution composition (see, for example, Patent Documents 1 and 2). 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.
Further, a fountain solution composition containing benzotriazoles has been proposed in order to suppress corrosion in metal parts such as printing presses (see, for example, Patent Document 3), and a dampening solution containing benzimidazole or a derivative thereof. A water composition has been proposed (for example, see Patent Document 4), and a lithographic printing plate surface treatment liquid containing a monothioether compound having succinic acid or a derivative thereof has been proposed (for example, see Patent Document 5).
Although various proposals have been made as described above, fountain solution that replaces isopropyl alcohol and has excellent fountain solution characteristics, and can suppress the corrosion and rust generation of metal parts of printing machines and fountain solution circulators. There is a further need for a composition. In particular, there is a need for a fountain solution composition that can suppress the corrosion and rust generation of metal parts such as iron, alloys thereof, steel, cast iron, and plating.

JP 2002-254852 A JP 2004-82593 A Japanese Patent Laid-Open No. 2-76793 JP-A-4-161387 JP-A-11-115341

  The object of the present invention is to eliminate the toxic and disadvantages of the conventional dampening water, and to completely replace isopropyl alcohol in a printing machine of any mechanism without requiring expert skill in printing. Another object of the present invention is to provide a fountain solution for lithographic printing. Specifically, the object of the present invention is a dampening for lithographic printing in which the dampening water remaining on the plate surface when the printing machine 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. It is also an object of the present invention to ensure the occurrence of corrosion and rust on metal parts used in printing presses and dampening water circulation devices such as copper and its alloys, iron and its alloys, steel, cast iron, and plated products thereof. An object of the present invention is to provide a fountain solution for lithographic printing that can be suppressed to a low level. The object of the present invention is further to suppress the occurrence of printing problems such as smearing, blinding and water loss of a printing plate using a support that has been electrochemically roughened and anodized, particularly an aluminum plate, and is stable. An object of the present invention is to provide a fountain solution composition for lithographic printing, which enables continuous printing, has no safety and health problems and fire safety problems, and can obtain a high-quality printed matter.

（式中、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈはそれぞれ、０〜５０の整数を表し、但しａ、ｃ、ｅ及びｇのうち少なくとも一つは１以上であり、及びｂ、ｄ、ｆ及びｈのうち少なくとも一つは１以上である。） As a result of intensive studies to achieve the above object, the present inventor has found that an excellent fountain solution for lithographic printing can be obtained by including a specific compound in the fountain solution composition. The present invention has been completed.
Accordingly, the present invention is a fountain solution composition for lithographic printing, comprising a compound represented by the following general formula (1) and a rust inhibitor.

(Wherein a, b, c, d, e, f, g and h each represents an integer of 0 to 50, provided that at least one of a, c, e and g is 1 or more, and (At least one of b, d, f, and h is 1 or more.)

（式中、Ｒ¹及びＲ²はそれぞれ独立して−ＯＭを表し、該Ｍは水素原子、アルカリ金属又はアンモニウム基を表し、又はＲ¹及びＲ²は一緒になって−Ｏ−を表す。Ｒ³はアルキル基、アルケニル基、アリール基又はアラルキル基を表す。）
本発明の好ましい実施態様として、本発明の湿し水組成物にはさらに、ポリビニルピロリドンと、糖類から選ばれる少なくとも１種とを含有させる。本発明の湿し水組成物はまた、その好ましい実施態様として、実質的に揮発性有機溶剤を含まない湿し水組成物とする。 As an example of the rust inhibitor contained in the fountain solution composition of the present invention, at least one selected from benzotriazole and derivatives thereof and / or at least one succinic acid compound represented by the following general formula (2) Is mentioned.

(In the formula, R ¹ and R ² each independently represent —OM, and M represents a hydrogen atom, an alkali metal or an ammonium group, or R ¹ and R ² together represent —O—. R ³ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.)
As a preferred embodiment of the present invention, the fountain solution composition of the present invention further contains polyvinylpyrrolidone and at least one selected from saccharides. The fountain solution composition of the present invention is also a fountain solution composition substantially free of volatile organic solvents as a preferred embodiment thereof.

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 for lithographic printing of the present invention, metal parts used in printing presses and fountain solution circulation devices, such as copper and its alloys, iron and its alloys, steel, cast iron, and their plating processes Corrosion and rust generation of products can be suppressed. The fountain solution composition of the present invention can exhibit a particularly excellent rust prevention effect on iron, its alloys, steel, cast iron and the like.
According to the fountain solution composition of the present invention, isopropyl alcohol can be completely replaced without substantially containing a volatile organic solvent, 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.

（式中、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈはそれぞれ、０〜５０の整数を表し、但しａ、ｃ、ｅ及びｇのうち少なくとも一つは１以上であり、及びｂ、ｄ、ｆ及びｈのうち少なくとも一つは１以上である。） The compound represented by the following general formula (1) used in the present invention is obtained by adding propylene oxide to aminoethanolamine (H ₂ N—CH ₂ CH ₂ —NH—CH ₂ CH ₂ —OH) as a catalyst. It can be synthesized by reacting and then reacting with ethylene oxide.

(Wherein a, b, c, d, e, f, g and h each represents an integer of 0 to 50, provided that at least one of a, c, e and g is 1 or more, and (At least one of b, d, f, and h is 1 or more.)

The compound represented by the general formula (1) used in the present invention has an appropriate weight average molecular weight of 500 to 20000, preferably 500 to 5000, and more preferably 800. It is ˜1500, and the optimum is one having a weight average molecular weight of around 1000.
Such a compound does not damage the image area even when water droplets left on the plate when the printing press is stopped evaporates by water and are concentrated and remain. 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.

The molecular weight of the above compound and the ratio of ethylene oxide and propylene oxide can be determined by, for example, measurement of hydroxyl value and amine value, NMR measurement, and 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.

（式中、Ｒは水素原子又はアルキル基を表し、Ｒ¹及びＲ²は独立して水素原子、アルキル基、アルコキシ基、カルボキシル基、水酸基又はハロゲン原子を表す。）
Ｒで示されるアルキル基の例として炭素原子数１〜５の直鎖又は分岐鎖のアルキル基があり、これらのアルキル基は置換されていてもよく、該置換基として例えば、アミノ基、N-アルキルアミノ基、N,N-ジアルキルアミノ基などがある。
Ｒ¹又はＲ²で示されるアルキル基及びアルコキシ基の例として、炭素原子数１〜５の直鎖又は分岐鎖のアルキル基及びアルコキシ基が挙げられる。Ｒ¹又はＲ²で示されるハロゲン原子の例として塩素原子及び臭素原子などが挙げられる。 Specific examples of the rust inhibitor used in the present invention include at least one selected from benzotriazole and derivatives thereof.
Specific examples of the benzotriazole and derivatives thereof used in the present invention include those represented by the following general formula (3).

(In the formula, R represents a hydrogen atom or an alkyl group, and R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, or a halogen atom.)
Examples of the alkyl group represented by R include a linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups may be substituted, and examples of the substituent include an amino group, N- Examples include alkylamino groups and N, N-dialkylamino groups.
Examples of the alkyl group and alkoxy group represented by R ¹ or R ² include a linear or branched alkyl group and alkoxy group having 1 to 5 carbon atoms. Examples of the halogen atom represented by R ¹ or R ² include a chlorine atom and a bromine atom.

Specific examples of benzotriazole and derivatives thereof used in the present invention include benzotriazole (1,2,3-benzotriazole), methylbenzotriazole (4-methylbenzotriazole, 5-methylbenzotriazole, etc.), dimethylbenzotriazole (4,6-dimethylbenzotriazole, 5,7-dimethylbenzotriazole, etc.), carboxybenzotriazole, and 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole.
Of these, benzotriazole, methylbenzotriazole and dimethylbenzotriazole are preferably used.
Commercially available products can be used for benzotriazole and its derivatives used in the present invention.
The fountain solution composition of the present invention can be used singly or in combination of two or more selected from benzotriazole and its derivatives. By containing such a benzotriazole compound in the range of 0.0001 to 0.1 mass% in the fountain solution at the time of use, it is possible to exert an appropriate anticorrosion and rust prevention effect on the metal. More preferably, the benzotriazole compound is contained in the range of 0.001 to 0.02% by mass in the fountain solution used.

（式中、Ｒ¹及びＲ²はそれぞれ独立して−ＯＭを表し、該Ｍは水素原子、アルカリ金属又はアンモニウム基を表し、又はＲ¹及びＲ²は一緒になって−Ｏ−を表す。Ｒ³はアルキル基、アルケニル基、アリール基又はアラルキル基を表す。） Another specific example of the rust inhibitor used in the present invention includes at least one succinic acid compound represented by the following general formula (2).

(In the formula, R ¹ and R ² each independently represent —OM, and M represents a hydrogen atom, an alkali metal or an ammonium group, or R ¹ and R ² together represent —O—. R ³ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.)

In the formula, examples of the alkali metal atom represented by M include sodium, potassium, and lithium.
In the formula, the alkyl group represented by R ³ includes a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkenyl group includes a linear or branched alkenyl group having 1 to 18 carbon atoms. For example, a vinyl group, an allyl group, a butenyl group, a hexenyl group, a nonenyl group, a dodecenyl group, and the like are mentioned. As an aryl group, a phenyl group and a naphthyl group are mentioned. As an aralkyl group, a phenylmethyl group, a phenylethyl group are mentioned. Etc. These alkyl group, alkenyl group, aryl group and aralkyl group may have a substituent, for example, a hydroxyl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, and — (OC _m H _2m ) _n —OH (formula M represents 2 to 3, and n represents 1 to 20).
Among the succinic acid compounds, R ¹ and R ² in the general formula (I) are each —OM (where M is a hydrogen atom or an alkali metal), and R ³ has ³ to ³ carbon atoms. 12 represents an alkyl group, an alkenyl group having 3 to 12 carbon atoms, a phenyl group, and the like.

The succinic acid-based compound can be produced according to a conventional method. The said succinic-acid type compound can generally be obtained, and a commercial item can be used in this invention. For example, there are commercially available products such as nonenyl succinic acid, dodecenyl succinic acid, and phenyl succinic acid.
In the fountain solution composition of the present invention, the above succinic acid compounds can be used singly or in combination of two or more. By including such a succinic acid-based compound in the range of 0.0001 to 0.1% by mass in the fountain solution at the time of use, it is possible to exert an appropriate anticorrosion and rust prevention effect on the metal. More preferably, the succinic acid-based compound is contained in the range of 0.001 to 0.02 mass% in the fountain solution used.

  In the fountain solution composition of the present invention, at least one selected from benzotriazole and derivatives thereof and at least one of the above succinic compounds may be used in combination.

A water-soluble polymer compound may be further added to the fountain solution composition of the present invention.
Specific examples of such water-soluble polymer compounds include gum arabic, starch derivatives (eg, dextrin, enzymatically degraded dextrin, hydroxypropylated enzymatically degraded dextrin, carboxymethylated starch, phosphate starch, octenyl succinated starch), alginic acid. Natural products of salts, fiber derivatives (such as carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose, and their glyoxal modified products) and modified products thereof, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and Copolymers, polyacrylic acid and its copolymers, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, etc. Thing, and the like. These polymer compounds can be used alone or in combination, and the addition amount thereof is 0.0001 to 5% by mass, more preferably 0.003 to 1% by mass in dampening water.

In the present invention, among the above water-soluble polymer compounds, polyvinyl pyrrolidone can be particularly preferably used. The polyvinylpyrrolidone contained in the fountain solution composition means a homopolymer of vinylpyrrolidone. Polyvinylpyrrolidone having a molecular weight of 200 to 3,000,000 is appropriate, preferably having a molecular weight of 300 to 500,000, more preferably 300 to 100,000. Particularly preferred is 300 to 30,000.
These polyvinyl pyrrolidones can be used alone or in combination of two or more kinds having different molecular weights. Further, it can be combined with a low molecular weight polyvinyl pyrrolidone, for example, a vinyl pyrrolidone oligomer having a polymerization degree of 3 to 5.
As such polyvinyl pyrrolidone, a commercially available product can be used. For example, various great grades such as K-15, K-30, K-60, K-90, K-120 manufactured by ISP can be used.
The content of polyvinyl pyrrolidone in the fountain solution is suitably 0.001 to 0.3% by mass, preferably 0.005 to 0.2% by mass.

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, hyalbiouron, maltotriose, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-digit, D, L-talit, zulcit , Allozulcit, maltitol, reduced water candy, etc. It is. These saccharides may be used alone or in combination of two or more.
In the fountain solution, the content of at least one selected from saccharides is suitably 0.01 to 1% by mass, preferably 0.1 to 0.8% by mass.

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 other than those described above, 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.
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.

  Furthermore, the fountain solution composition of the present invention can contain glycols and / or alcohols as a wetting agent. Examples of such wetting agents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol. Monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, tetraethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether Tetraethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, tetraethylene glycol Monoisobutyl ether, ethylene glycol monotertiary butyl ether, diethylene glycol monotertiary butyl ether, triethylene glycol monotertiary butyl ether, tetraethylene glycol monotertiary butyl ether,

  Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrapropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tetrapropylene glycol monoethyl ether, Propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monopropyl ether, tetrapropylene glycol monopropyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether Tetrapropylene glycol monoisopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoisobutyl ether, Tetrapropylene glycol monoisobutyl ether, propylene glycol monotertiary butyl ether, dipropylene glycol monotertiary butyl ether, tripropylene glycol monotertiary butyl ether, tetrapropylene glycol monotertiary butyl ether, polypropylene group having a molecular weight of 200 to 1,000 Calls and their monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether and monobutyl ether,

Propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and pentapropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butylene glycol, hexylene glycol, ethyl alcohol, n-propyl alcohol, benzyl alcohol, ethylene Glycol monophenyl ether, 2-ethyl-1,3-hexanediol, 3-methoxy-3-methyl-1-butanol, 1-butoxy-2-propanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol , 3-methoxybutanol and the like.
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. It can melt | dissolve and the fountain solution composition which is a concentrate can be obtained. Such a concentrated solution is diluted about 10 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 can completely replace isopropyl alcohol without using it in combination with a volatile organic solvent. Therefore, the fountain solution composition of the present invention can be a fountain solution composition substantially free of volatile organic solvents. Here, “substantially free of volatile organic solvent” means that the amount of the volatile organic solvent is 10% or less in the fountain solution composition as a concentrate according to the measurement method of ASTM D 2369-95. means.
The measurement method of ASTM D 2369-95 is to determine the amount of volatile organic solvent by the following formula using a 3 ml sample in a hot air oven at 110 ° C. for 1 hour.
Formula: {(mass of sample−mass of heating residue−mass of moisture in sample) / (mass of sample)} × 100 = amount of volatile organic solvent (mass%)
Also, there is no problem in printing quality even when isopropyl alcohol up to about 15% by mass in dampening water during use 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 Table 1 below, various fountain solution compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared. In the table, the unit is gram, and water is finally added to make 1000 mL. Both are 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
^** エチレンジアミンにPOが付加して次にEOが付加している構造

^* EO: PO ratio = ratio of added moles of ethylene oxide and propylene oxide
^** Structure where PO is added to ethylenediamine, followed by EO

Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 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. Furthermore, Comparative Example 6 was prepared as a working solution by adding 8% isopropyl alcohol and 11% dampening water EU-3 manufactured by Fuji Photo Film Co., Ltd. to pseudo-hard water having a hardness of 400 ppm.
[Test method]
The printing machine uses Heidel MOV (Alcolor water supply device), Toyo Ink Co., Ltd. name High Unity process ink (black, indigo, red, yellow) ink and Fuji Photo Film Co., Ltd. positive Type PS plate VS is exposed to Ushio PS light using solid and 30% halftone dot film and Fuji Photo Film FQI chart film, then developed with Fuji Photo Film Developer DP-4 A printing test was carried out using the gumming process made with Fuji Photo Film's gum solution FP-2.

(a) Continuous printing stability:
The amount of dampening water that does not cause smudges and does not cause water loss (minimum water raising amount) is obtained, and continuous printing is performed under the conditions. Judgment is made based on the number of printed sheets until a good printed matter cannot be obtained due to the occurrence of stains on the printed matter or water loss.
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

(d) Preventing the occurrence of rust:
As test equipment, test equipment for immersion corrosion test shown in Fig. 5 on page 7 of Testing Method for the Corrosion Test of Fountain Concentrates, Version 12/2004 by FOGRA Forschungsgesellschaft Druck eV (Fig. 5). 5: Using a device similar to the scheme of the permanent total-immersion test, rust generation was tested on iron and copper.
The test piece of iron used for evaluation was made of high carbon chrome bearing steel and was processed into a size: diameter 19 mm, length 65 mm, and surface roughness Ra 1.5 μm. As the copper test piece, a copper plate having a size of 28 mm × 60 mm and a thickness of 2 mm was used.
The amount of dampening water was 650 mL. Air Flow was 150 mL / min. The immersion was carried out for 7 days at a temperature of 22 ° C.
In the evaluation method of rust prevention, in the case of iron, the amount of dissolution was measured by an atomic absorption method, and in the case of copper, the change in appearance was visually determined.

[Evaluation of iron rust prevention]
Take 650 ml of each of the dampening solutions of Examples 1 to 5 and Comparative Examples 1 to 6, and immerse two iron test pieces (high carbon chromium bearing steel) in a test apparatus for immersion test. Air Flow is 150 mL / min. The immersion was carried out for 7 days at a temperature of 22 ° C. The degree of rust generation at this time and the amount of iron dissolved in the fountain solution composition (measured with an atomic absorption spectrometer) were used for determination.
No rust generation (iron elution amount less than 5ppm) A
Rust is generated (iron elution amount 5ppm or more and less than 20ppm) B
Rust is remarkably generated (iron elution amount 20ppm or more) C
[Evaluation of copper rust prevention]
650 ml of each of the dampening waters of Examples 1 to 5 and Comparative Examples 1 to 6 were taken, two copper test pieces were immersed in a test apparatus for test, Air Flow was 150 mL / min, and the temperature was 22 ° C. Soaked for 7 days. In the case of copper, the change in appearance was visually determined.
There is no rusting (change in appearance is not recognized A
Rust has occurred but is slight (there is slight change in hue and gloss) B
Rust has occurred (changes in hue and gloss are large) C

The test results are shown in Table 2 below.

From the results shown in Table 2, especially from the comparison of the results of Examples 1-5 and Comparative Examples 1-4, the combined use of the compound of the general formula (1) according to the present invention and the rust inhibitor synergizes with the rust preventive effect. It turns out that the effect is demonstrated. Generally, a rust inhibitor alone has a high effect on copper and brass, but a sufficient effect on iron is often not obtained. According to the combined use of the compound of the general formula (1) and the rust inhibitor, the effect on copper and brass is increased, and a sufficient effect can be obtained also on iron.
The fountain solution according to the embodiment of the present invention is good in all of continuous printing stability, emulsification property, and image portion deterioration. In the fountain solution according to the example of the present invention, a good printed matter similar to the fountain solution using isopropyl alcohol of Comparative Example 6 was obtained. Unlike the isopropyl alcohol, the fountain solution composition of the above example has no occupational safety and fire safety problems, and uses an organic solvent that is included in the existing isopropyl alcohol alternative fountain solution. In addition, the amount of volatile organic solvent can be extremely reduced, which is very preferable from the viewpoint of the environment.

Claims (4)

A fountain solution for lithographic printing, comprising a compound represented by the following general formula (1) and a rust inhibitor.

(Wherein a, b, c, d, e, f, g and h each represents an integer of 0 to 50, provided that at least one of a, c, e and g is 1 or more, and (At least one of b, d, f, and h is 1 or more.) The dampening for lithographic printing according to claim 1, wherein the rust inhibitor is at least one selected from benzotriazole and derivatives thereof and / or at least one succinic acid compound represented by the following general formula (2). Water composition.

(In the formula, R ¹ and R ² each independently represent —OM, and M represents a hydrogen atom, an alkali metal or an ammonium group, or R ¹ and R ² together represent —O—. R ³ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.)   The fountain solution composition for lithographic printing according to claim 1 or 2, further comprising polyvinylpyrrolidone and at least one selected from saccharides.   The fountain solution composition for lithographic printing according to any one of claims 1 to 3, which does not substantially contain a volatile organic solvent.