JP2006069170A - Damping water composition for lithographic printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a damping water composition for lithographic printing which does not require any specialized skill in a printing operation and can perfectly substitute isopropyl alcohol in all printers of a differing mechanism, does not impair an image without dissolving an image portion, even when the remnant damping water on the plate surface becomes water droplets and the moisture vaporizes during the stoppage of the printer, and besides, inhibits the printing problems such as smudging, blinding and emulsification of a printing plate, does not involve safety, hygiene and fire defense problems, and ensures the availability of high-quality printed matter. <P>SOLUTION: The damping water composition for lithographic printing contains at least one kind of chemical compound selected from the group consisting of a chemical compound composed of ethylene oxide and propylene oxide added to diethylenetriamine, a chemical compound of bromonitro alcohol, a 1,2-benzisothiazolin-3-one compound, a p-hydroxy benzoic acid derivative, a chemical compound of azole and a heterocyclic alkyl ammonium salt. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  Lithographic printing is a printing method that skillfully utilizes the property that water and oil do not essentially mix, and the printing plate surface consists of an area that accepts water and repels oil-based ink, and an area that repels water and accepts 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 a drawback that it is difficult to uniformly wet the non-image area of the plate, and therefore, the printed matter sometimes gets dirty, and it is quite skilled to adjust the supply amount of the fountain solution. It has become a problem such as requiring. In recent years, the regulation of chromium ion emission in wastewater has become stricter and tends 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, the technique which substitutes for isopropyl alcohol has been proposed in recent years, and it is proposed to use a specific solvent (for example, refer to Patent Document 1). 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 2), and an ethylene oxide and propylene oxide adduct of alkylene diamine to be moistened. It has been proposed to be included in a water composition (see, for example, Patent Documents 3 and 4). 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.

JP 2002-192853 A JP 51-72507 A JP 2002-254852 A JP 2004-82593 A

  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 a further object of the present invention to suppress the occurrence of printing problems such as stains, blinding and water loss of printing plates, particularly using an electrochemically roughened and anodized support of an aluminum plate. It is an object of the present invention to provide a fountain solution for lithographic printing which can obtain a high-quality printed matter without causing problems on the top and fire safety.

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 relates to a compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine, a bromonitroalcohol compound, a 1,2-benzisothiazolin-3-one compound, a p-hydroxybenzoic acid derivative, an azole compound, and a heterocyclic alkyl. A fountain solution composition for lithographic printing, comprising at least one compound selected from the group consisting of ammonium salts.
In the embodiment of the present invention, the compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine to be used is preferably in the range of weight average molecular weight of 500 to 1500. In the embodiment of the present invention, preferably, the compound has an addition mole ratio of ethylene oxide to propylene oxide in the range of 5:95 to 50:50.
As another preferred embodiment of the fountain solution composition of the present invention, it is possible to further include polyvinylpyrrolidone. As a preferred embodiment of the present invention, it is also possible to further contain at least one selected from the group consisting of saccharides and glycerin. Therefore, as a more preferred embodiment of the present invention, polyvinylpyrrolidone and at least one selected from the group consisting of saccharides and glycerin are included.
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. Printability is good without causing problems such as stains on the printing plate, blinding and water loss. 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, 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.
The compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine used in the present invention preferably has a weight average molecular weight of 500 to 1500, more preferably 800 to 1200, and most suitable is a weight average molecular weight of around 1000. belongs to.
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.
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 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 with it. From this, a propylene oxide / ethylene oxide adduct of diethylenetriamine can be obtained.

（上記式中、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５００〜１５００となるような値であることが好ましい。
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 above 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 (It represents an integer above. Each copolymer chain may be a block structure or a random structure.)
In the formula, a to j are preferably values such that the molecular weight of the whole compound is 500 to 1500.
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.

The fountain solution composition of the present invention further includes a bromonitroalcohol compound, a 1,2-benzisothiazolin-3-one compound, a p-hydroxybenzoic acid derivative, an azole compound, and a heterocyclic alkylammonium salt. At least one selected compound is contained.
The bromonitroalcohol compound used in the present invention includes compounds represented by the following general formulas [A] to [C].

（式中、Ｒ₁〜Ｒ₁₃はそれぞれ独立に水素原子又はアルキル基を表す。）

(In the formula, R _{1 to} R ₁₃ each independently represents a hydrogen atom or an alkyl group.)

When R _{1 to} R ₁₃ in the general formulas [A] to [C] represent an alkyl group, a lower alkyl group is preferable, particularly an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, An isopropyl group or the like is suitable. One or more of these bromonitroalcohol compounds can be used.
Of the bromonitroalcohol compounds used in the present invention, particularly preferred are 2-bromo-2-nitropropane-1,3-diol (pronopol), 1,1-dibromo-1-nitro-2-ethanol (DBNE). ), 1,1-dibromo-1-nitro-2-propanol (DBNP), 3-bromo-3-nitropentane-2,4-diol, and the like. Many bromonitroalcohol compounds are poorly water-soluble substances, but can be used by dissolving in methanol or glycol organic solvents. Further, it can be used as a fountain solution by using an anionic, cationic or nonionic surfactant in combination without using an organic solvent.
The content of the bromonitroalcohol compound in the fountain solution is appropriately 0.001 to 5% by mass, and preferably 0.005 to 3% by mass.

  Next, the 1,2-benzisothiazolin-3-one compound will be described. Among the 1,2-benzisothiazolin-3-one compounds, 1,2-benzisothiazolin-3-one having the following structural formula is preferably used.

（式中、Ｒは水素原子又はアルキル基を表し、Ｘはアルキル基、アルコキシ基、又はハロゲン原子を表し、ｎは０又は１〜４の整数を表す。）
上記式中、Ｒがアルキル基を表すとき、低級アルキル基が好ましく、具体的に炭素原子数１〜４のアルキル基が好ましく、特にメチル基が挙げられる。Ｘがアルキル基を表すとき、低級アルキル基が好ましく、具体的に炭素原子数１〜４のアルキル基が好ましい。Ｘがアルコキシ基を表すとき、炭素原子数１〜４のアルコキシ基が好ましい。Ｘがハロゲン原子を表すとき、塩素原子、臭素原子が好ましい。

(In the formula, R represents a hydrogen atom or an alkyl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and n represents 0 or an integer of 1 to 4).
In the above formula, when R represents an alkyl group, a lower alkyl group is preferred, specifically an alkyl group having 1 to 4 carbon atoms, and particularly a methyl group. When X represents an alkyl group, a lower alkyl group is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. When X represents an alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. When X represents a halogen atom, a chlorine atom or a bromine atom is preferable.

In the fountain solution used in the present invention, one or more 1,2-benzisothiazolin-3-one compounds can be used.
Among the 1,2-benzisothiazolin-3-one compounds used in the present invention, the following are preferably used.

湿し水における１，２−ベンズイソチアゾリン−３−オン化合物の添加量は、０．００１〜５質量％が適当であり、好ましくは０．００５〜３質量％である。

The addition amount of the 1,2-benzisothiazolin-3-one compound in the fountain solution is suitably 0.001 to 5% by mass, preferably 0.005 to 3% by mass.

Examples of p-hydroxybenzoic acid derivatives used in the present invention include isobutyl p-hydroxybenzoate, isopropyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, propyl p-hydroxybenzoate, Examples include methyl p-hydroxybenzoate and vinyl p-hydroxybenzoate.
In the fountain solution used in the present invention, one or more p-hydroxybenzoic acid derivatives can be used.
0.001-5 mass% is suitable for the addition amount of the p-hydroxybenzoic acid derivative in dampening water, Preferably it is 0.005-3 mass%.

Examples of azole compounds used in the present invention include α- (4-chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol (generic name: cyproconazole). , (±) α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (generic name: tebuconazole), and 1 -[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (generic name: propiconazole), etc. There is. One or more azole compounds can be used for the fountain solution.
0.001-5 mass% is suitable for the addition amount of the azole compound in dampening water, Preferably it is 0.005-3 mass%.

The heterocyclic alkyl ammonium salt used in the present invention is preferably one or more heterocyclic alkyl ammonium salts selected from the group consisting of alkyl-pyridinium salts, alkyl-quinolinium salts and alkyl-isoquinolinium salts. Among them, those having an alkyl group having 8 to 18 carbon atoms are preferable. For example, lauryl isoquinolinium chloride, cetyl pyridinium chloride and the like can be mentioned.
The addition amount of the heterocyclic alkyl ammonium salt in the fountain solution is appropriately 0.001 to 5% by mass, and preferably 0.005 to 3% by mass.

  In the fountain solution composition of the present invention, selected from the group consisting of bromonitroalcohol compounds, 1,2-benzisothiazolin-3-one compounds, p-hydroxybenzoic acid derivatives, azole compounds, and heterocyclic alkylammonium salts. When at least two or more compounds are included, the total content thereof is suitably in the range of 0.001 to 5 mass% in the fountain solution.

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 the group consisting of sugars and glycerin. 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.
Glycerin may be used alone or in combination with sugars.
In the fountain solution, the content of at least one selected from the group consisting of sugars and glycerin is suitably 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass.

  The fountain solution is generally desirably used in the acidic region, that is, in the range of pH around 3-7. If 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 7, generally, at least one selected from water-soluble organic acids, inorganic acids and salts thereof can be used. These compounds are effective in adjusting the pH of the fountain solution or buffering the pH, and appropriate etching or anticorrosion of the lithographic printing plate support. Preferred organic acids include, for example, citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, gluconic acid, hydroxyacetic acid, succinic acid, malonic acid, levulinic acid, sulfanilic acid, p-toluenesulfonic acid, phytic acid, and organic phosphones. An acid etc. are mentioned. 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, and one of these organic acids, inorganic acids and salts thereof is used alone. Or you may use it as a mixture of 2 or more types. The amount added to the fountain solution at the time of use is suitably in the range of 0.0002 to 0.1 mol / liter in combination with the organic acid, inorganic acid and salts thereof. The fountain solution composition of the present invention can also contain an alkali metal hydroxide, phosphoric acid, alkali metal salt, alkali metal carbonate, silicate and the like, and can be used in an alkaline region of 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 polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic 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 may contain glycols and / or alcohols as a wetting agent. Examples of such a wetting agent 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, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, methoxy Examples include ethanol, 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. 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%)
Further, there is no problem in printing quality even when 1 to 15% by mass of isopropyl alcohol 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 units or hydroxyethyl acrylate units 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.
Various fountain solution compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were prepared according to the compositions shown in Tables 1 and 2 below. The balance of the composition was water and finally 1000 ml. The unit of content of each component in the composition is mol / liter for primary ammonium phosphate, ammonium acetate, secondary ammonium citrate and their total, and gram for others. These are all concentrated types and are diluted at the time of use.

Each of the above fountain solution compositions is diluted 40 times with water, adjusted with NaOH / phosphoric acid (85%) so that the pH is around 4.8 to 5.3, and actually used. A dampening solution was used. These fountain solutions were subjected to the following tests.
[Test method]
The printing machine uses Heidel MOV (Alcolor water supply device), Toyo Ink Co., Ltd. name High Unity process four colors (black, indigo, red, yellow) ink and Fuji Photo Film Co., Ltd. as the plate used Using a film with a solid part and a 30% halftone dot part of a positive PS plate made by Fuji, using an FQI chart film made by Fuji Photo Film, exposing it with PS light made by Ushio, and developing solution DP-4 made by Fuji Photo Film A printing test was carried out using the one made by performing a developing process and making a plate by performing a gumming treatment with a gum solution FP-2 made by Fuji Photo Film.
(a) Continuous printing stability:
The amount of dampening water that does not cause stains and does not cause water loss (minimum water raising amount) is obtained, and the determination is made based on the number of printed sheets until the occurrence of stains on the printed matter or the loss of water makes it impossible to obtain a good printed matter.
10,000 sheets or more A
10000 to 3000 or more B
2999 sheets or less C

(b) Aging property: The dampening water after printing 10,000 sheets is collected, and after aged for 3 days at 25 ° C., the dampening solution is set again on the water supply tray of the printing press, and the same evaluation as in the above (a) is repeated. As in (a), the amount of dampening water that does not cause stains and does not cause water loss (minimum water raising amount) is obtained, and until a good printed matter cannot be obtained due to occurrence of stains on the printed matter or water loss. Judged by the number of printed sheets.
10,000 sheets or more A
10000 to 3000 or more B
2999 sheets or less C
(c) Image part deterioration The printing machine is stopped, and 5 μl, 10 μl, 20 μl and 50 μl of each dampening water are dropped into the solid part of the PS plate and the image part of the 30% halftone dot part using a syringe. Leave for a minute. 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
A test result is combined with the following Tables 1-2, and is shown.

^* 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

^* EO: PO ratio: Ratio of added moles of ethylene oxide and propylene oxide

^* 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

^* EO: PO ratio: Ratio of added moles of ethylene oxide and propylene oxide

  From the above results, it can be seen that the fountain solution according to the example of the present invention is excellent in all of the continuous printing stability, aging and image portion deterioration, and a good printed matter can be obtained. Further, the fountain solution compositions of Examples 1 to 7 are different from isopropyl alcohol, have no problems in terms of occupational safety and fire safety, and are organic solvents that are included in existing isopropyl alcohol alternative fountain solutions. Is not used, and the amount of the volatile organic solvent can be extremely reduced, which is very preferable from the viewpoint of the environment.

Claims (8)

  A group consisting of a compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine, a bromonitroalcohol compound, a 1,2-benzisothiazolin-3-one compound, a p-hydroxybenzoic acid derivative, an azole compound, and a heterocyclic alkylammonium salt A fountain solution for lithographic printing, comprising at least one compound selected from the group consisting of:   The fountain solution composition for lithographic printing according to claim 1, further comprising polyvinylpyrrolidone.   Bromonitroalcohol compounds are 2-bromo-2-nitropropane-1,3-diol, 1,1-dibromo-1-nitro-2-ethanol, 1,1-dibromo-1-nitro-2-propanol and 3 The fountain solution composition for lithographic printing according to claim 1 or 2, which is selected from -bromo-3-nitropentane-2,4-diol. The fountain solution composition for lithographic printing according to claim 1 or 2, wherein the 1,2-benzisothiazolin-3-one compound is a compound represented by the following general formula.

(In the formula, R represents a hydrogen atom or an alkyl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and n represents 0 or an integer of 1 to 4).   p-hydroxybenzoic acid derivatives are isobutyl p-hydroxybenzoate, isopropyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, propyl p-hydroxybenzoate, methyl p-hydroxybenzoate, And a fountain solution for lithographic printing according to claim 1 or 2, which is selected from vinyl p-hydroxybenzoate.   The azole compound is α- (4-chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol, α- [2- (4-chlorophenyl) ethyl]- α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, and 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3- The fountain solution for lithographic printing according to claim 1 or 2, selected from dioxolan-2-yl] methyl] -1H-1,2,4-triazole.   The fountain solution composition for lithographic printing according to claim 1 or 2, wherein the alkyl group of the heterocyclic alkylammonium salt is an alkyl group having 8 to 18 carbon atoms.   The fountain solution composition for lithographic printing according to any one of claims 1 to 7, which is substantially free of a volatile organic solvent.