JP2007062068A - Lithographic printing dampening water composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing dampening water composition, which has neither toxicity nor defect of the conventional dampening water, requires no technical skill at printing work and can thoroughly substitute for isopropyl alcohol in printing machines with all possible mechanisms, which suppress the development of printing problematic points such as the scumming, blinding and emulsifying of a printing plate and realizes stable printing and which neither dissolve an image part nor mar an image even when the dampening water left on the surface of the printing plate at the stoppage of a printing machine turns into waterdrops and the moisture of the waterdrops evaporates. <P>SOLUTION: This lithographic printing dampening water composition includes a compound obtained by adding elthylene oxide and propylene oxide to diethylenetriamine under the condition that its weight average molecular weight is >1,500 and ≤10,000 and at least one kind of saccharide selected from the group consisting of monosaccharide, disaccharide and oligosaccharide. <P>COPYRIGHT: (C)2007,JPO&INPIT

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 substituting isopropyl alcohol have been proposed in recent years, and the use of a specific solvent has been proposed (see, for example, 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 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 fountain solution composition for lithographic printing that can suppress printing problems such as smearing, blinding, and water loss of printing plates, and can stably print even after continuous printing for a long time. Is to provide. 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.

Therefore, the present invention is a compound in which ethylene oxide and propylene oxide are added to diethylenetriamine, the weight average molecular weight being greater than 1500 and 10,000 or less, and at least one saccharide selected from monosaccharides, disaccharides and oligosaccharides A fountain solution for lithographic printing, comprising:
As a preferable embodiment of the fountain solution composition of the present invention, at least one compound selected from an isothiazoline derivative and a bromonitroalcohol compound is further 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, continuous printing can be carried out stably for a long time, and the fountain solution composition for lithographic printing of the present invention has good stability over time.
Furthermore, according to the fountain solution composition for lithographic printing of the present invention, even if the dampening water remaining on the plate surface becomes water droplets when the printing machine is stopped, for example, during a lunch break, the image area is dissolved. The image will not be 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.

A compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine used in the present invention has a weight average molecular weight of more than 1500 and not more than 10,000, preferably 1600 to 5000, and most suitable is a weight average molecular weight of around 3000. 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.
A 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, diethylenetriamine is reacted with ethylene oxide and / or propylene oxide in the presence of a catalyst.

（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１５００より大きく１００００以下となるような値である。
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 values such that the molecular weight of the whole compound is greater than 1500 and 10000 or less.
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, 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.

The fountain solution composition of the present invention further contains at least one saccharide selected from monosaccharides, disaccharides and oligosaccharides. The sugar includes a sugar alcohol 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.
In the fountain solution, the saccharide content is suitably 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass.

（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。 The fountain solution composition of the present invention preferably further contains at least one compound selected from isothiazoline derivatives and bromonitroalcohol compounds.
Typical isothiazoline derivatives include 4-isothiazolin-3-one compounds and 1,2-benzisothiazolin-3-one compounds. Among these, a 1,2-benzisothiazolin-3-one compound represented by the following structural formula is preferably used.

(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.

湿し水におけるイソチアゾリン誘導体の添加量は、０．００１〜５質量％が適当であり、好ましくは０．００５〜３質量％である。 One or more isothiazoline derivatives can be used in the fountain solution composition.
Of the above 1,2-benzisothiazolin-3-one compounds, the following are particularly preferably used.

The addition amount of the isothiazoline derivative in the fountain solution is suitably 0.001 to 5% by mass, preferably 0.005 to 3% by mass.

（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。） The bromonitroalcohol compound used in the present invention includes compounds represented by the following general formulas [A] to [C].

(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.
Among 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 together without using an organic solvent.
The content of the bromonitroalcohol compound in the fountain solution is suitably 0.001 to 5 mass%, preferably 0.005 to 3 mass%.

  In the fountain solution composition of the present invention, an isothiazoline derivative and a bromonitroalcohol compound may be used in combination, and when two or more compounds are included, the total content thereof is 0.001 to 0.001 in the fountain solution. It is appropriate to be in the range of 5% by mass.

  The fountain solution composition of the present invention preferably further contains a silicon antifoaming agent represented by polydimethylsiloxane. As the silicon antifoaming agent, any of an emulsified dispersion type and a solubilized type can be used.

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 succinylated starch), alginic acid. Natural products of salts, fibrous derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose, glyoxal derivatives thereof) 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.

  It is desirable that the fountain solution is generally used in the acidic region, that is, in the range of around pH 3-7. 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 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. 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, 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.

  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, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts, alkyl naphthalene. 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 oil, 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 wetting agents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol momethyl 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, Traethylene 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 1000 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 , Methoxyethanol, ethoxyethanol, butoxyethanol, 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 tap water, well water or the like during normal use to obtain a dampening water during 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
= Volatile organic solvent amount (% by 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. The preferred 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, for example. 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- quinonediazide 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 concentration compositions of Examples 1-6 and Comparative Examples 1-8 were prepared. The balance of the composition was water and finally made up to 1 liter. In the table, the unit of the content of each component in the composition is mol / liter for primary ammonium phosphate, ammonium nitrate and secondary ammonium citrate, and the other is mass%.
The fountain solution composition prepared here is diluted at the time of use to obtain a fountain solution.

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:
Obtain the amount of dampening water (minimum water raising amount) that does not cause stains and does not cause water loss, and prints with this minimum amount of water dampening using various dampening waters. Judgment is made based on the number of printed sheets until a good print cannot be obtained due to losing.
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. Judgment is made based on 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
The test results are shown in Table 1 and Table 2 below.

^*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 composition of the present invention is different from isopropyl alcohol in that there is no problem in terms of occupational safety and fire safety, and an organic solvent contained in an existing isopropyl alcohol alternative fountain solution is used. This is not necessary, and the amount of the volatile organic solvent can be extremely reduced, which is very preferable from the viewpoint of the environment.

Claims (6)

  A compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine, the weight average molecular weight being greater than 1500 and 10,000 or less, and at least one saccharide selected from monosaccharides, disaccharides and oligosaccharides A fountain solution composition for lithographic printing.   The fountain solution composition for lithographic printing according to claim 1, wherein the weight average molecular weight of a compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine is 1600-5000.   The fountain solution for lithographic printing according to claim 1 or 2, further comprising at least one compound selected from isothiazoline derivatives and bromonitroalcohol compounds. The fountain solution composition for lithographic printing according to claim 3, wherein the isothiazoline derivative is a 1,2-benzisothiazolin-3-one 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).   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 3, which is a compound selected from -bromo-3-nitropentane-2,4-diol.   The fountain solution composition for lithographic printing according to any one of claims 1 to 5, further comprising a silicon antifoaming agent.