Patent Publication Number: US-2009226616-A1

Title: Fountain solution composition for lithographic printing and heat-set offset rotary printing process

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to fountain solution compositions for lithographic printing, more specifically to fountain solution compositions for offset printing process, which are preferably used for a rotary heat-set offset printing process. 
     2. Description of the Related Art 
     Lithographic printing is a process of printing, which advantageously utilizes the property that water and oil are essentially not miscible with each other, and consists of two areas: one receives water and repels an oil based ink, and the other receives the oil based ink and repels water. The former one is the non-image area, and the latter is the image area. Wetting the non-image area with a fountain solution enlarges the surface chemical difference between the image and non-image areas, thereby enhancing the ink repellency of the non-image area and the ink receptivity of the image area. 
     Lithographic printing machines typically employ offset printing methods, in which ink and fountain solution are supplied onto the plate where ink attaches to the image area and fountain solution attaches to the non-image area to create an image, which image on the plate in turn becomes transferred to the blanket and then to the paper from the blanket, thereby achieving printing. During this procedure, when continuing printing for a long period of time, there causes a problem so-called “blanket piling”, where the ink component and paper component gradually pile up on the non-image areas on the blanket. Specifically, rotary lithographic offset (rotary offset) printing is characterized by its long-term and continuous operatability and high productivity, however, had a considerable problem of causing blanket piling. 
     In the blanket piling phenomena, the ink on the image area tends to be extruded and deposited on especially the back side of the rotation (the gripper end side), and said deposition inhibits ink transfer from the blanket to paper resulting in insufficient attachment of ink. In order to remove the deposit, printing operation has to be stopped for cleaning the blanket, giving rise remarkably to increase in paper waste and reduction of the productivity. Therefore, an improvement has been demanded. 
     Some solutions for blanket piling have been proposed such as an ink composition for rotary lithographic offset printing comprising lanoline with an acid value of less than 1.0 in an amount of 1-5% by weight (see Patent Document 1), and a pigment coated paper for offset printing characterized by being coated with a coating composition wherein a ratio between a particular adhesive agent and the pigment is defined (see Patent Document 2). 
     However, limitation to particular inks or printing papers cannot be satisfactory under circumstances where use of wide variety of inks or papers is desired. Therefore, improvement of blanket piling still remains as an important issue. 
     Commonly known fountain solutions include aqueous solutions containing alkali metal salt or ammonium salt of dichromic acid, phosphorus acid or salt thereof such as ammonium phosphate, gum Arabic, colloid substances such as carboxymethyl cellulose (CMC) and the like. However, fountain solution containing only these compounds has a drawback in that it shows a difficulty in wetting the non-image area of the plate evenly and often causes undesired stains on the printed matters. Also, there has been a problem that the control of fountain solution supply requires substantial training. 
     In order to improve the above drawback, Dahlgren system using an aqueous solution containing 20-25% of isopropyl alcohol has been proposed. This method is advantageous in many points, including operationality and quality of the printed matters, by improving wetting of the non-image area, reducing the required amount of fountain solution, facilitating balancing of the amounts of printing ink and water to be supplied, reducing the emulsifying amount of fountain solution into the printing ink and further by improving the transfer efficiency of the printing ink to the blanket. However, as isopropyl alcohol is volatile, a special apparatus is required in order to maintain a certain level of isopropyl alcohol in fountain solution, which leads to an increase of the cost. Further, isopropyl alcohol has a peculiar unpleasant odor, and a toxicity problem, therefore not favorable for the working environment. Application of a fountain solution containing isopropyl alcohol to offset printing where a common dampening roller is used has been problematic since isopropyl alcohol evaporates on the roller and on the plate surface and fails in exerting its effect. 
     Fountain solutions free from isopropyl alcohol have been proposed such as a fountain solution containing particular propylene glycol compounds (see Patent Document 3), a fountain solution containing compounds with ethylenediamine to which ethylene oxide and propylene oxide are attached (see Patent Documents 4 and 5), and a fountain solution containing compounds with ethylenetriamine to which ethylene oxide and propylene oxide are attached (see Patent Document 6). However, these still tended to cause blanket piling, and an improvement thereof has been demanded. 
     On the other hand, a technique using a water-soluble organic polymer for improving wettability of printing cylinder has been proposed and it utilizes a fountain solution containing naturally occurring collagen/elastin, which are soluble to a weak acid aqueous medium (see Patent Document 7). It is also disclosed therein that the wettability becomes further improved by inclusion of a long chain (n≧6) non-polymeric alcohol and/or alkane diol having a hydroxyl group at (1,2)- or (1,3)-position. However, a method for improving blanket piling is not explicitly mentioned in the above prior arts. 
     In addition, it has been proposed that a fountain solution containing a hydrophilic polymer compound, a pH adjusting agent, and 2-ethyl-1,3-hexanediol and/or an adduct compound of ethylene oxide and/or propylene oxide to 2-ethyl-1,3-hexanediol, and a cationic surfactant shows excellent printing property and does not impair image areas on a printing plate (see Patent Document 8). However, also in this document, improvement concerning blanket piling is not remarked.
     [Patent Document 1] JP 2006-328299 A   [Patent Document 2] JP 2006-322114 A   [Patent Document 3] JP 2001-138655 A   [Patent Document 4] JP 2007-50665 A   [Patent Document 5] JP 2007-168124 A   [Patent Document 6] JP 2007-55182 A   [Patent Document 7] JP S61-189997 A   [Patent Document 8] JP H4-363297 A   

     DISCLOSURE OF THE INVENTION 
     Problem to be solved by the Invention 
     An object of the present invention is to provide a method for improving blanket piling, and in particular to provide a method for improving blanket piling in terms of fountain solution compositions. An object of the present invention is also to provide fountain solution compositions that are excellent in printing properties, such as giving no damages to image areas on the printing plate, and suppressing ink-stain (ink feedback) on a dampening roller (a metering roller), as well as improving blanket piling. 
     Means to Solve the Problem 
     In order to achieve the objects described above, the present inventor extensively studied to discover that blanket piling is significantly improved and also other printing properties are excellent by adding particular diol compounds and particular cationic compounds to a fountain solution. 
     Accordingly, the present invention is a fountain solution composition for lithographic printing characterized by comprising at least one acyclic hydrocarbon diol compound, having 9 carbon atoms in total and two —OH groups, wherein the number of carbon atoms existing between said two —OH groups via minimal distance is from 2 to 6, and at least one cationic compound represented by the following formula (I) or (II): 
     
       
         
         
             
             
         
       
     
     wherein the above formulas, R 1  to R 10  each independently represent hydrogen atom, or an alkyl group, cyclic alkyl group, hydroxyalkyl group, substituted or unsubstituted benzyl group, or substituted or unsubstituted phenyl group, having 1 to 12 carbon atoms, Z 1  to Z 3  each represent N +  or P + , X 1  to X 3  each represent an anion, and n represents an integer of 1 to 5, excluding that two or more of R 1  to R 4  represent hydrogen atoms, two or more of R 5  to R 7  represent hydrogen atoms, or two or more of R 8  to R 10  represent hydrogen atoms. 
     As one embodiment of the invention, there is the fountain solution composition wherein the diol compound is 2,4-diethyl-1,5-pentanediol and/or 2-butyl-2-ethyl-1,3-propanediol. 
     In one embodiment of the invention, the fountain solution composition comprises as the above diol compound, 2-butyl-2-ethyl-1,3-propanediol. 
     Further embodiment of the invention is the fountain solution composition comprising two or more of said diol compounds, wherein 2-butyl-2-ethyl-1,3-propanediol represents at least 1% by weight of the total weight of diol compounds. As one example of the above fountain solution composition comprising two or more of said diol compounds, there is the fountain solution composition comprising 2,4-diethyl-1,5-pentanediol. 
     In another embodiment of the fountain solution composition of the invention, the fountain solution composition as described above further comprises at least one compound of formula (III) shown below, and at least one compound of formula (IV) shown below. 
       R 1 —O—(CH 2 CHR 2 O) m —H   (III) 
     where R 1  represents an alkyl group having 1 to 4 carbon atoms, R 2  represents a hydrogen atom or methyl group, and m represents an integer of 1 to 3. 
       HO—(CH 2 CH(CH 3 )O) n —H   (IV) 
     where n represents an integer of 1 to 5. 
     In yet another embodiment of the fountain solution composition of the invention, the fountain solution composition described above further comprises at least one compound selected from an adduct compound of ethylene oxide and propylene oxide to ethylenediamine and an adduct compound of ethylene oxide and propylene oxide to diethylenetriamine. 
     In yet another embodiment of the fountain solution composition of the invention, the fountain solution composition described above further comprises a pyrrolidone derivative represented by the following general formula (VIII): 
     
       
         
         
             
             
         
       
     
     wherein R 4  represents an alkyl group having 2 to 12 carbon atoms. 
     In yet another embodiment of the fountain solution composition of the invention, the fountain solution composition described above further comprises at least one selected from the group consisting of acetylene glycols, acetylene alcohols, and an adduct compound of ethylene oxide and/or propylene oxide thereto. As one specific embodiment thereof, there is the fountain solution composition comprising at least one compound selected from the group consisting of 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and an adduct compound of 4 to 10 ethylene oxides to 2,4,7,9-tetramethyl-5-decyne-4,7-diol. 
     The fountain solution composition of the invention can preferably be used for rotary heat-set offset printing, hence, the present invention is also directed to a rotary heat-set offset printing process using an ink for rotary offset of a heat-set type and the above fountain solution composition. 
     Effect of the Invention 
     The fountain solution composition of the invention represses the occurrence of blanket piling, almost does not damage image areas on a printing plate, and stably produces printings with high quality even through a continuous printing operation for a long period of time. In addition, the fountain solution composition of the invention does not require the use of volatile organic solvents such as isopropyl alcohol, which has been conventionally used for fountain solution. Therefore, by using the fountain solution composition of the invention, the amount of the fountain solution to be supplied can easily be controlled, and the ink-stain (ink feedback) on the dampening roller hardly deteriorates, so that an excellent printing performance would be provided. In addition, the fountain solution composition of the invention is more favorable for the operational environment. 
    
    
     MODE FOR CARRYING OUT THE INVENTION 
     The present invention will be described in its detail below. 
     A diol compound used for the present invention is an acyclic hydrocarbon diol compound, having 9 carbon atoms in total and two —OH groups, wherein the number of carbon atoms existing between said two —OH groups via minimal distance is from 2 to 6. Due to the total number of carbon atoms being 9, said compound shows favorable solubility, thereby an effect at which the present invention aims can be attained. 
     A compound such as 1,9-nonanediol that has 9 carbon atoms in total, but the number of carbon atoms existing between said two —OH groups via minimal distance being more than 6, does not seem to exhibit the effect of the present invention. Thus, it was observed that only compounds having hydrophilicity-hydrophobicity balances and molecular structures within narrow limits could exhibit the effect aimed by the invention. 
     In the diol compound used for the present invention, the number of carbon atoms existing between said two —OH groups via minimal distance is preferably in the range of from 3 to 5. 
     Examples of the diol compounds used for the present invention include specific compounds (1) to (16) shown below, however the present invention should not be limited thereto. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Among the above diol compounds, (7) 2-butyl-2-ethyl-1,3-propanediol and (10) 2,4-diethyl-1,5-pentanediol are excellent in the effect of reducing blanket piling. 
     The fountain solution composition of the invention can comprise one or more than one diol compounds. As one example of the fountain solution composition of the invention, there is the fountain solution comprising two or more diol compounds, wherein 2-butyl-2-ethyl-1,3-propanediol represents at least 1% by weight of the total weight of diol compounds. In this embodiment, 2-butyl-2-ethyl-1,3-propanediol represents preferably at least 3% by weight, and more preferably at least 10% by weight of the total weight of diol compounds. In the above fountain solution comprising two or more diol compounds, the diol compound to be used in combination with 2-butyl-2-ethyl-1,3-propanediol includes specifically 2,4-diethyl-1,5-pentanediol. 
     An appropriate amount of the diol compound of the invention to be added is suitably 0.001 to 2.0% by weight based on the total weight of the fountain solution composition when used, because within the above range, the composition would exhibit the effect of the invention sufficiently, while not displaying poor solubility or causing ink-stain (ink feedback) on the dampening roller. The amount to be added is preferably 0.05 to 1.0% by weight, more preferably 0.1 to 0.7% by weight, and further preferably 0.2 to 0.5% by weight. 
     The fountain solution composition according to present invention further comprises at least one cationic compound represented by the following formula (I) or (II): 
     
       
         
         
             
             
         
       
     
     wherein the above formulas, R 1  to R 10  each independently represent hydrogen atom, or an alkyl group, cyclic alkyl group, hydroxyalkyl group, substituted or unsubstituted benzyl group, or substituted or unsubstituted phenyl group, having 1 to 12 carbon atoms, Z 1  to Z 3  each represent N +  or P + , X 1  to X 3  each represent an anion, and n represents an integer of 1 to 5, excluding that two or more of R 1  to R 4  represent hydrogen atoms, two or more of R 5  to R 7  represent hydrogen atoms, or two or more of R 8  to R 10  represent hydrogen atoms. 
     The above cationic compound is explained in its detail below. 
     In the above formulas, R 1  to R 10  each independently represent hydrogen atom, or an alkyl group such as methyl group, ethyl group, n-propyl group and n-butyl group, cyclic alkyl group such as cyclohexyl group and 3-methyl cyclohexyl group, hydroxylalkyl group such as hydroxymethyl group and hydroxyethyl group, substituted or unsubstituted benzyl group such as benzyl group and alkyl benzyl group including isopropylbenzyl group, or substituted or unsubstituted phenyl group such as 2-methoxyphenyl group and 3,5-dichlorophenyl group, having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, Z 1  to Z 3  each represent N +  or P + , X 1  to X 3  each represent an anion such as halogen ion, nitrate ion, sulphate ion, phosphate ion, hydroxide ion, PF 6   − , or BF 4   − , and n represents an integer of 1 to 5, and preferably 1 to 3, excluding that two or more of R 1  to R 4  represent hydrogen atoms, two or more of R 5  to R 7  represent hydrogen atoms, or two or more of R 8  to R 10  represent hydrogen atoms. 
     Preferred are the cationic compounds wherein R 1  to R 10  each independently represent hydrogen atom, an alkyl group having 1 to 8 carbon atoms or benzyl group. 
     Examples of the above compounds include tetraphenyl phosphonium iodide, tetraphenyl phosphonium bromide, tetraphenyl phosphonium chloride, tetraphenyl phosphonium sulphate, tetraphenyl phosphonium nitrate, tetra n-butyl phosphonium iodide, tetra n-butyl phosphonium bromide, tetra n-butyl phosphonium chloride, tetra n-butyl phosphonium sulphate, tetra n-butyl phosphonium nitrate, tetrabutyl ammonium sulphate, tetrabutyl ammonium nitrate, ethyl triphenyl phosphonium chloride, benzyl triphenyl phosphonium chloride, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium phosphate, ethyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium bromide, tetratolyl phosphonium bromide, triethyl benzyl ammonium chloride, triethyl ammonium bromide, triethyl benzyl ammonium iodide, tributyl benzyl ammonium chloride, octyl dimethyl benzyl ammonium chloride, octyl dimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride, lauryl dimethyl ammonium bromide, 1,2-bis(diphenylphosphino)ethane bromide, and the like. 
     Among these, tetraphenyl phosphonium bromide, tetraphenyl phosphonium chloride, tributyl benzyl ammonium chloride, octyl dimethyl benzyl ammonium chloride and the like are preferable. 
     The cationic compound may be used alone or in combination of two or more. The amount of the cationic compound to be used is suitably 0.001 to 1% by weight based on the total weight of the fountain solution composition when used, preferably 0.01 to 0.5% by weight, more preferably 0.02 to 0.2% by weight. 
     It is preferable that the fountain solution composition would be generally used by diluting a concentrated solution before use in terms of transportation cost, storage space, and production cost including the cost of packaging materials. The dilution rate is preferably 10 to 200 fold, more preferably 20 to 150 fold, and the most preferably 30 to 100 fold. Therefore, the concentration of the composition in the concentrated solution is adjusted to a level that would give the above concentration of the fountain solution composition of use upon dilution. Higher concentration is preferred in respect of cost; however, excessive levels of concentration may cause some problems such as deposition or liquid separation, therefore being not favorable. 
     Upon preparation of the concentrated solution, as a solubilizing agent, it is preferred to use at least one compound of formula (III) below and at least one compound of formula (VI) below, and these compounds would enhance the effect of the invention in a synergistic manner. 
     Compound of Formula (III) 
       R 1 —O—(CH 2 CHR 2 O) m —H   (III) 
     where R 1  represents an alkyl group having 1 to 4 carbon atoms, R 2  represents a hydrogen atom or methyl group, and m represents an integer of 1 to 3. 
     In the compound of formula (I), in particular, R 1  represents a linear or branched alkyl group having 1 to 4 carbon atoms including, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, among which an n-butyl or t-butyl group is especially preferred because these increase solubility of diol compounds and repress blanket piling. R 2  represents a hydrogen atom or a methyl group, preferably a methyl group, and m represents an integer of 1 to 3, preferably 1. 
     Examples of the compound of formula (III) include ethylene glycol mono t-butyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene 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, propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoisobutyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t-butyl ether and tripropylene glycol mono t-butyl ether. 
     These compounds can be used either alone or in combination of more than one. 
     Among these, n-butyl or t-butyl ether of propylene glycol or ethylene glycol can be preferably used. An appropriate amount of the compound of formula (III) to be added is 0.05 to 5.0% by weight based on the total amount of the fountain solution composition when used, because within the above range, the composition would exhibit a sufficient effect of blanket piling repression, while not causing problems such as roller stripping or poor printing durability on a printing plate. More preferably, the amount to be added is 0.1 to 3.0% by weight. 
     Compound of Formula (IV) 
       HO—(CH 2 CH(CH 3 )O) n —H   (IV) 
     where n represents an integer of 1 to 5. 
     In the compound of formula (IV), in particular, n is preferably 1. 
     Accordingly, examples of the compound of formula (IV) include propylene glycol, dipropylene glycol, tripropyleneglycol, tetrapropylene glycol and pentapropylene glycol. These compounds can be used either alone or in combination of more than one. Among these compounds, propylene glycol, dipyropylene glycol, and tripropylene glycol are preferable, and propylene glycol is the most preferable in order to increase diol compound solubility. 
     An appropriate content of the compound of formula (IV) in a fountain solution composition is 0.05 to 5.0% by weight based on the total amount of the fountain solution composition when used, because within the above range, the solubility of the diol compound becomes sufficient, and the composition would exhibit a sufficient effect of blanket piling repression, while not causing roller stripping due to stabilized ink concentration. More preferably, the amount to be added is 0.1 to 3.0% by weight. 
     The fountain solution composition of the invention can further comprise at least one compound selected from an adduct compound of ethylene oxide and propylene oxide to ethylenediamine and an adduct compound of ethylene oxide and propylene oxide to diethylenetriamine. 
     These compounds will be described as follows. 
     [Adduct Compound of ethylene oxide and propylene oxide to ethylenediamine] 
     An adduct compound of ethylene oxide and propylene oxide to ethylenediamine used for the invention has an appropriate weight-average molecular weight of 500 to 20000, preferably 500 to 5000, more preferably 800 to 1500, and most preferably about 1000. 
     In the compound, a molar ratio of attachment of ethylene oxide and propylene oxide is suitably in the range of 5:95 to 50:50, and more preferably in the range of 20:80 to 35:65 in terms of sufficient printing performance. 
     Bond-structures of ethylene oxide and propylene oxide in the compound include a block structure in which ethylene oxide is added first followed by propylene oxide, block structure in which propylene oxide is added first followed by ethylene oxide, and random structure in which ethylene oxide and propylene oxide are added simultaneously, however, any of these structures displays almost the same effect. 
     The adduct compound of ethylene oxide and propylene oxide to ethylenediamine used for the invention can be produced by a conventional method, for example, by allowing ethylene oxide and/or propylene oxide to react with ethylenediamine in the presence of a catalyst. 
     The adduct compound of ethylene oxide and propylene oxide to ethylenediamine used for the invention is represented by formula (V) as follows. 
     
       
         
         
             
             
         
       
     
     where A and B each independently represents —CH 2 CH 2 O— or —CH 2 CH(CH 3 )O—, A and B are different groups from each other, a to h each represents an integer of 0 to 50, wherein at least one of a, c, e and g is not less than 1, and at least one of b, d, f and h is not less than 1. The symbols a to h take certain values so that the molecular weight of the compound in total would be 500 to 20000. Each copolymer chain may be in either a block or random structure. 
     The molecular weight of the compound and the ratio of ethylene oxide and propylene oxide can be determined, for example, by measuring a hydroxyl value and an amine value, or by NMR measurement. 
     The compound of formula (V) is preferably represented by formula (VI) as follows. 
     
       
         
         
             
             
         
       
     
     where a, b, c, d, e, f, g and h each represents an integer of 0 to 50, wherein at least one of a, c, e and g is not less than 1, and at least one of b, d, f and h is not less than 1. 
     The compound of above formula (VI) suitably has a weight-average molecular weight of 500 to 20000, preferably 500 to 5000, and more preferably 800 to 1500. The symbols a to h take certain values so that the molecular weight of the compound in total would be 500 to 20000, however, a to h are preferably 1 to 10, and in particular, 2 to 4. 
     Such compounds would not adversely affect image areas, even when the remaining water drops are left and becomes concentrated by evaporation during run-down time of the printing machine. These compounds can take the place of isopropyl alcohol without being combined with volatile organic solvents, however, tend to deteriorate blanket piling and ink-stain (ink feedback) on the dampening roller. By combining with the diol compound used for the invention, the above compound would be able to take place of isopropyl alcohol without aggravating blanket piling and ink-stain (ink feedback) on the dampening roller. 
     In the compound, a suitable molar ratio of added ethylene oxide and added propylene oxide is suitably in the range of 5:95 to 50:50, and more preferably in the range of 20:80 to 35:65 in terms of sufficient printing performance. 
     [Adduct Compound of ethylene oxide and propylene oxide to diethylenetriamine] 
     An adduct compound of ethylene oxide and propylene oxide to diethylenetriamine used for the invention has an appropriate weight-average molecular weight of 500 to 3000, preferably 800 to 2000, and most preferably about 1000. 
     Compounds having such molecular weights would not adversely affect image areas, even when the remaining water drops are left and becomes concentrated by evaporation during run-down time of the printing machine. These compounds can take place of isopropyl alcohol without being combined with volatile organic solvents. 
     In the compound, a suitable molar ratio of added ethylene oxide and added propylene oxide is suitably in the range of 5:95 to 50:50, and more preferably in the range of 20:80 to 35:65 in terms of sufficient printing performance. 
     Bond-structures of ethylene oxide and propylene oxide include a block structure in which ethylene oxide is attached first followed by propylene oxide, block structure in which propylene oxide is attached first followed by ethylene oxide, and random structure in which ethylene oxide and propylene oxide are attached simultaneously, however, any of these structures displays almost the same effect. 
     The adduct compound of ethylene oxide and propylene oxide to diethylenetriamine used for the invention can be produced by a conventional method, for example, by allowing ethylene oxide and/or propylene oxide to react with diethylenetriamine in the presence of a catalyst. Alternatively, one can cool diethylenetriamine along with acetonitrile in an ice bath and add propylene oxide thereto, and further add ethylene oxide thereto to allow to react, then remove the deposit from the mixture by filtration, whereby obtain the adduct compound of propylene oxide/ethylene oxide to diethylenetriamine. 
     The adduct compound of propylene oxide/ethylene oxide to diethylenetriamine used for the invention is specifically represented by formula (VII) as follows. 
     
       
         
         
             
             
         
       
     
     where A and B each independently represents —CH 2 CH 2 O— or —CH 2 CH(CH 3 )O—, A and B are different groups from each other, a to j each represents an integer not less than 1. Each copolymer chain may be in either a block or random structure. In the formula, the symbols a to j take certain values so that the molecular weight of the compound in total would be 500 to 3000, however, a to h are preferably 1 to 6, and in particular, 2 to 3. 
     The molecular weight of the compound and the ratio of ethylene oxide and propylene oxide can be determined, for example, by measuring a hydroxyl value and an amine value or by NMR measurement. 
     Isopropyl alcohol can be replaced by the above compound contained in an amount of 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, in a fountain solution composition when used, and then an excellent printability would be displayed. Such compounds would not adversely affect image areas, even when the remaining water drops are left and becomes concentrated by evaporation during run-down time of the printing machine after using the fountain solution. However, these compounds tend to deteriorate blanket piling and ink-stain (ink feedback) on the dampening roller. By combining with the diol compound used for the invention, the above compound would be able to take the place of isopropyl alcohol without aggravating blanket piling and ink-stain (ink feedback) on the dampening roller. 
     The fountain solution composition of the invention may include other components as follows:
     (a) auxiliary agent for wettability improvement   (b) water-soluble polymer compound   (c) pH adjusting agent   (d) chelating agent   (e) odor masking agent   (f) others ((i) preservatives, (ii) colorant, (iii) anticorrosives, (iv) antifoaming agent, etc.)   

     As for (a) auxiliary agents for wettability improvement, surfactants and other solvents can be used. Among surfactants, for example, anionic surfactants include fatty acid salts, abietate, hydroxyalkanesulfonate, alkanesulfonate, dialkyl sulfosuccinate, linear alkylbenzene sulfonate, branched alkylbenzene sulfonate, alkylnaphthalenesulfonate, alkylphenoxy polyoxyethylene propylsulfonate, polyoxyethylene alkylsulfenyl ether salt, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonate, sulfated castor oil, sulfated beef tallow oil, sulfuric ester salt of fatty acid alkyl ester, alkyl sulfuric acid ester salt, polyoxyethylene alkyl ether sulfuric ester salt, fatty acid monoglyceride sulfuric ester salt, polyoxyethylene alkylphenyl ether sulfuric ester salt, polyoxyethylene styrylphenyl ether sulfuric ester salt, alkyl phosphoric ester salt, polyoxyethylene alkyl ether phosphoric ester salt, polyoxyethylene alkylphenyl ether phosphoric ester salt, partially saponified product of styrene-maleic anhydride copolymer, partially saponified product of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate and the like. Among these, dialkyl sulfosuccinate, alkyl sulfuric acid ester salt and alkylnaphthalenesulfonate are particularly preferably used. 
     Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polystyrylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerol fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylenated castor oil, polyoxyethylene glycerol fatty acid partial ester, fatty acid diethanol amide, N,N-bis-2-hydroxy alkylamine, polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide and the like. In addition, fluorochemical surfactants and silicon surfactants may be used. Among these, polyoxyethylene alkylphenyl ether and polyoxyethylene-polyoxypropylene block polymer are preferably used. In addition, there are surfactants of silicon derivatives and fluorine derivatives. In case of using a surfactant, an appropriate content thereof is not more than 1.0% by weight, preferably 0.001 to 0.5% by weight in the fountain solution composition when used, in view of foaming. In addition, combination of two or more surfactants can be employed. 
     As for another auxiliary agent or wetting solvent, 3-methoxy-3-methyl butanol, 3-methoxybutanol, ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol, hexylene glycol, glycerol, diglycerol, polyglycerin, trimethylolpropane and the like can be used. These solvents can be used either alone or in combination of more than one. These solvents are appropriately used in a range of 0.1 to 3% by weight based on the total weight of the fountain solution composition when used, and preferably 0.3 to 2% by weight. 
     As for another auxiliary agent, a pyrrolidone derivative represented by the following general formula (VIII) may be used. 
     
       
         
         
             
             
         
       
     
     wherein R 4  represents an alkyl group having 2 to 12 carbon atoms. 
     Specific examples of the pyrrolidone derivative include ethyl pyrrolidone, butyl pyrrolidone, pentapyrrolidone, hexapyrrolidone, octylpyrrolidone, laurylpyrrolidone and the like. These compounds can be used either alone or in combination of more than one. Among these, those wherein R 4  represents an alkyl having 6 or more carbon atoms in the formula (VIII) are preferable, and octylpyrrolidone is particularly preferable. The compound represented by the general formula (VIII) are used appropriately in an amount of 0.0001 to 1.0% by weight on the basis of the total weight of the fountain solution composition when used, and more preferably 0.001 to 0.1% by weight. 
     The fountain solution composition of the invention can also comprise at least one selected from the group consisting of acetylene glycols, acetylene alcohols, and an adduct compound of ethylene oxide and/or propylene oxide thereto. Specific examples of said compounds include 3,5-dimethyl-1-hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2-butyne-1,4-diol, 3-methyl-1-butyne-3-ol, an adduct compound of ethylene oxide and/or propylene oxide to the above compound, and the like. Among these, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and an adduct compound of 4 to 10 ethylene oxides to 2,4,7,9-tetramethyl-5-decyne-4,7-diol are preferable. These compounds are used appropriately in an amount of 0.0001 to 1.0% by weight on the basis of the total weight of the fountain solution composition when used, and more preferably 0.001 to 0.1% by weight. 
     The following compounds can be added to the fountain solution composition, if desired, for the purpose of adjustment of dynamic surface tension, solubilization, control on a mix rate (emulsification rate) of printing ink into a proper range, or the like: 2-ethyl-1,3-hexanediol, an adduct compound of ethylene oxide and/or propylene oxide to 2-ethyl-1,3-hexanediol, an adduct compound of propylene oxide to trimethylolpropane, an adduct compound of propylene oxide to glycerin, an adduct compound of propylene oxide to sorbitol, tetrahydrofurfuryl alcohol, and the like. Among these, preferred as an auxiliary agent for adjustment of dynamic surface tension is 2-ethyl-1,3-hexanediol, and preferred as an agent for solubilization is tetrahydrofurfuryl alcohol. As an agent for controlling an ink emulsification rate, an adduct compound of ethylene oxide to 2-ethyl-1,3-hexanediol, an adduct compound of propylene oxide to trimethylolpropane and the like may be preferably used. These compounds can be used either alone or in combination of more than one. These compounds are used appropriately in an amount of 0.01 to 7% by weight on the basis of the total weight of the fountain solution composition when used, and more preferably 0.05 to 5% by weight. 
     The water-soluble polymer compounds (b) used for the fountain solution composition of the invention include natural products and denatured products thereof such as gum Arabic, starch derivatives (e.g. dextrin, enzymolysis dextrin, hydroxypropylated enzymolysis dextrin, carboxymethylated starch, phosphoric acid starch, octenylsuccinated starch), alginate, cellulose derivatives (e.g. carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hydroxyethyl cellulose) and the like, and synthetic products such as polyethylene glycol and copolymers thereof, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and copolymers thereof, polyacrylic acid and copolymers thereof, a vinyl methyl ether/maleic anhydride copolymer, a vinyl acetate/maleic anhydride copolymer, polystyrene sulfonic acid and copolymers thereof, and the like. The appropriate content of the water-soluble polymer is 0.0001 to 0.1% by weight, preferably 0.0005 to 0.05% by weight, based on the total weight of the fountain solution composition when used. 
     Among the water-soluble polymer compounds listed above, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropylmethyl cellulose are preferably used for the invention. 
     Polyvinylpyrrolidone contained in the fountain solution composition refers to a homopolymer of vinylpyrrolidone. Suitably, the molecular weight of polyvinylpyrrolidone is 200 to 3,000,000, preferably 300 to 500,000, and more preferably 300 to 100,000. The molecular weight of 300 to 30,000 is particularly preferred. 
     These polyvinylpyrrolidone can be used either alone or in combination of more than one with different molecular weights. In addition, they can be combined with polyvinylpyrrolidone of low molecular weight, such as vinylpyrrolidone oligomers with degree of polymerization of 3 to 5. 
     Such polyvinylpyrrolidone is commercially available. For example, polyvinylpyrrolidone in different grades, such as K-15, K-30, K-60, K-90, K-120 and the like from ISP Co., Ltd. can be usefully employed. 
     The appropriate polyvinylpyrrolidone content in the fountain solution composition when used is 0.001 to 0.3% by weight, and preferably 0.005 to 0.2% by weight. 
     The fountain solution composition of the invention preferably comprises at least one compound selected from sugars. The sugar for use can be selected from monosaccharide, disaccharide, oligosaccharide and sugar alcohols thereof obtainable by hydrogenation. Examples of sugars include D-erythrose, D-threose, 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-allulo-heptulose, β-D-altro-3-heptulose, saccharose, lactose, D-maltose, isomaltose, inulobiose, maltotriose, D,L-arabite, ribitol, xylitol, D,L-sorbitol, D,L-mannite, D,L-idit, D,L-talite, dulcite, allodulcite, maltitol, reduced starch syrup and the like. These sugars can be used either alone or in combination of more than one. 
     The appropriate content of at least one compound selected from sugars is 0.01 to 1% by weight, and preferably 0.1 to 0.8% by weight, in the fountain solution composition when used. 
     Water-soluble organic and/or inorganic acids and/or salts thereof can be used as pH adjusting agents (c) used for the fountain solution composition of the invention. These compounds act as a pH adjusting agent or buffer in the fountain solution and can be effectively used for adequate etching or anticorrosive treatment. Preferable organic acid includes, for example, citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, gluconic acid, acetic acid, hydroxyacetic acid, oxalic acid, malonic acid, levulinic acid, sulfanilic acid, p-toluenesulfonic acid, phytic acid, an organic phosphonic acid and the like. Inorganic acid includes phosphoric acid, nitric acid, sulfuric acid, polyphosphoric acid and the like. In addition, alkali metal salts, alkaline earth metal salts, ammonium salts or organic amine salts of these organic and/or inorganic acids can be preferably used, and such organic and inorganic acids and salts thereof can be used either alone or in combination of more than one. The amount of such a pH adjusting agent to be added to the fountain solution composition of the invention is preferably in the range of 0.001 to 0.3% by weight. Although the pH adjusting agent is preferably used within an acidic condition of pH 3-7 in the fountain solution composition, it can also be used within alkali condition of pH 7-11 in the presence of alkali metal hydroxide, phosphoric acid, alkali metal salt, alkali metal salt of carbonic acid, silicate and the like. 
     The fountain solution composition of the invention may further comprise a chelating agent (d). A fountain solution composition is usually prepared by diluting the concentrated solution with tap water, well water or the like, and components of tap water or well water such as calcium ion may adversely affect printing and make printing matter stain-prone. Under such condition, addition of a chelating agent may solve the above problem. Examples of preferred chelating agents include ethylenediaminetetraacetic acid and potassium salts and sodium salts thereof; diethylenetriaminepentaacetic acid and potassium salts and sodium salts thereof; triethylenetetraminehexaacetic acid and potassium salts and sodium salts thereof; hydroxyethylethylenediaminetriacetic acid and potassium salts and sodium salts thereof; nitrilotriacetic acid and sodium salts thereof; organic phosphonic acids such as 1-hydroxy ethane-1,1-diphosphonic acid and potassium salts and sodium salts thereof; aminotri (methylenephosphonic acid) and potassium salts and sodium salts thereof, and phosphonoalkanetricarboxylic acids. Organic amine salts are also effective instead of the sodium salts or potassium salts of the chelating agents above. Among these, chelating agents which are stable in the fountain solution composition when used and do not inhibit printing property are selected. The appropriate content of the chelating agent is 0.001 to 0.5% by weight, and preferably 0.002 to 0.25% by weight in the fountain solution composition when used. 
     Odor masking agents (e) include esters which is conventionally known to be used as flavors. Examples of odor masking agents include those represented by formula (IX) as follows. 
       R 2 —COOR 3    (IX) 
     In the compound of formula (IX), R 2  is a C 1 -C 15  alkyl, alkenyl or aralkyl group or phenyl group; in case where R 2  is alkyl or alkenyl, the number of carbon atoms therein is preferably 4 to 8; in case where R 2  represents an alkyl, alkenyl or aralkyl group, the group may be either linear or branched. Note that a suitable alkenyl group has one double bond. Aralkyl groups include a benzyl group, phenylethyl group and the like. One or more of hydrogen atoms of alkyl, alkenyl or aralkyl group or phenyl group represented by R 2  may optionally be substituted by hydroxy or acetyl groups. R 3  is a C 3 -C 10  alkyl, aralkyl or phenyl group, and may be either linear or branched; in case where R 3  is an alkyl group, the number of carbon atoms therein is preferably from 3 to 9. Aralkyl groups include a benzyl group, phenylethyl group and the like. 
     Specific examples of odor masking agents (e) which may be used include esters of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid, hexanoic acid (caproic acid), 4-methylpentanoic acid (isohexane acid), 2-hexenoic acid, 4-pentene acid, heptanoic acid, 2-methylheptane acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), 2-decenoic acid, lauric acid or myristic acid. In addition, odor masking agents also includes acetoacetic esters such as benzyl phenylacetate, ethyl acetoacetate and 2-hexyl acetoacetate. Among these, n-pentyl acetate, isopentyl acetate, n-butyl butyrate, n-pentyl butyrate and isopentyl butyrate are preferred and, in particular, n-butyl butyrate, n-pentyl butyrate and isopentyl butyrate are preferred. The appropriate content of such acid ester in the fountain solution composition is 0.0001 to 10% by weight, and preferably 0.001 to 1% by weight, based on the total weight of the fountain solution composition when used. Such odor masking agents may improve the working environment, and be used in combination with vanillin, ethyl vanillin and the like. 
     Preservatives (f)(i) used for the fountain solution composition of the invention include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benztriazole derivatives, derivatives of amidine or guanidine, quaternary ammonium salt, pyridine, derivatives of quinoline or guanidine, derivatives of diazine or triazole, derivatives of oxazol or oxazin, bromonitro alcohols such as bromonitro propanol, 2,2-dibromo-2-nitro ethanol, 3-bromo-3-nitro pentane 2,4-diol, and the like. Preferable amount of the preservative to be added is such that stably exhibit its effect on bacteria, fungi, yeasts and the like, and varies with the types of the bacteria, fungi and yeasts, however, it is preferably 0.001 to 1.0% by weight relative to the fountain solution composition when used. It is also preferable to use preservatives in combination of more than one which are potent against a variety of bacteria, fungi and yeasts. 
     Food colorings and the like can be preferably used for invention as colorants (f)(ii). Examples of colorants include CI No. 19140 and 15985 for yellow pigments; CI No. 16185, 45430, 16255, 45380, and 45100 for red pigments; CI No. 42640 for purple pigment; CI No. 42090 and 73015 for blue pigment; CI No. 42095 for green pigment; and the like. Anticorrosives (f)(iii) which may be used for the invention include benzotriazole, 5-methylbenzotriazol, thiosalicylic acid, benzimidazole and derivatives thereof and the like. Silicone antifoaming agents are preferable for antifoaming agents (f)(iv) which may be used for the invention. Among these, either emulsion-dispersing type or solubilized type may be used. 
     The balance of the fountain solution composition according to the invention is water. Fountain solution compositions are generally concentrated in commercial products on a commercial basis. Accordingly, the concentrated solution can be obtained as an aqueous solution with the above components dissolved therein by using water, preferably desalted water, i.e. pure water. The concentrated solution is used by diluting about 10-200 fold with tap water, well water or the like thereby making the fountain solution composition when used. 
     The fountain solution composition of the invention can be used for a variety of lithographic printing plates, and, in particular, can be preferably used for lithographic printing plates which can be obtained by imagewise exposure and development of a photo-sensitive lithographic printing plate (a printing plate which is preliminarily photosensitized and referred to as PS plate) onto the surface of an aluminum plate support. Preferable examples of such PS plates include a plate in which a photo-sensitive layer consisting of a mixture with diazo resin (salt of a condensation product of p-diazodiphenylamine and paraformaldehyde) and shellac is prepared on an aluminium plate as described in GB Patent No. 1,350,521, a plate in which a photo-sensitive layer consisting of a mixture with diazo resin and a polymer containing hydroxyethylmethacrylate unit or hydroxyethyl acrylate unit as the primary recurring unit is prepared on an aluminium plate as described in GB Patent Nos. 1,460,978 and 1,505,739, a negative-working PS plate in which a photo-sensitive polymer containing dimethylmaleimide group is prepared on an aluminium plate as described in JP H2-236552 A and JP H4-274429 A, and a positive-working PS plate in which a photo-sensitive polymer consisting of a mixture with o-quinonediazido photosensitive product and novolac phenol resin is prepared on an aluminium plate as described in JP S50-125806 A. Furthermore, the fountain solution composition can be used for burning-treated positive-working PS plates. 
     In the composition forming the above photosensitive layer, an alkali-soluble resin other than the alkali-soluble novolac resin may be incorporated, if necessary. Such an alkali-soluble resin includes for example, styrene-acrylic acid copolymer, methylmethacrylate-mathacrylic acid copolymer, alkali-soluble polyurethane resin, alkali-soluble vinyl resin as disclosed in J.P. KOKOKU (publication of examined application) No. Sho 52-28401, and alkali-soluble polybutyral resin. Further, a PS plate wherein a photosensitive layer of photopolymerizable photopolymer composition is provided on an aluminum plate as disclosed in U.S. Pat. Nos. 4,072,528 and 4,072,527, and a PS plate wherein a photosensitive layer comprising a mixture of an azide compound and a water-soluble polymer is provided on an aluminum plate as disclosed in GB Patent Nos. 1,235,281 and 1,495,861 are preferable. 
     Furthermore, the fountain solution composition of the present invention can be preferably applied to a CTP plate, which has been directly exposed by a visible or infrared laser, and examples thereof include a photopolymer type digital plate such as LP-NX manufactured by FUJI FILM Corporation, a thermal positive type digital plate such as LH-PI manufactured by FUJI FILM Corporation, a plate of on press processing type to be developed by a fountain solution and an ink, such as ET-S manufactured by FUJI FILM Corporation, and a thermal negative type digital plate such as LH-NI manufactured by FUJI FILM Corporation, and the like. 
     EXAMPLES 
     The present invention will now be described more in detail by way of examples thereof. It should be noted that % used herein indicates % by weight unless otherwise mentioned. 
     Examples 1-11 and Comparative Examples 1-11 
     A variety of fountain solution compositions were prepared according to the following preparation in the same manner, except for changing diol compounds and cationic compounds as shown in Table 1 below, but using the equal weight thereof. The units used in the preparation is in grams, and each value represents an amount added when water was finally added up to 100 grams, therefore consistent with % by weight. 
     Formulation of the Fountain Solution Composition (Working Solution) of Use 
       
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Ingredients 
                 Additive amount 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Ethylene glycol mono-t-butyl ether 
                 0.5 
                 g 
               
               
                   
                 Propylene glycol 
                 0.5 
                 g 
               
               
                   
                 Diol compounds shown in Table 1 
                 0.3 
                 g 
               
               
                   
                 Cationic compounds shown in Table 1 
                 0.05 
                 g 
               
               
                   
                 Hydroxypropyl cellulose 
                 0.001 
                 g 
               
               
                   
                 Ammonium nitrate 
                 0.05 
                 g 
               
               
                   
                 Citric acid 
                 0.02 
                 g 
               
               
                   
                 2,2-Dibromo-2-nitroethanol 
                 0.002 
                 g 
               
               
                   
                 2-Methyl-5-chloro-4-isothiazolin-3-one 
                 0.002 
                 g 
               
               
                   
                 Benzotriazole 
                 0.001 
                 g 
               
               
                   
                 Water 
                 up to 100 
                 g in total 
               
               
                   
                   
               
            
           
         
       
     
     The following assays were conducted for each fountain solution composition after printing 20000 sheets using Lithron26 printing machine from KOMORI Corporation with an ink: Super LeoEcoo SOY Black L, TOYO INK MFG CO., LTD., ultra lightweight coat papers: OK topcoat+ from OJI Paper Co., Ltd., and a plate: VS from FUJI FILM Corporation. 
     (1) Evaluation of Blanket Piling 
     After above printing, the blanket was removed and the height of deposit on a non-image area was measured with a stylus surface roughness meter (SURFCORDER) to evaluate blanket piling as a relative value to a fountain solution free from the diol compound and the cationic compound. The smaller the value is, the smaller the height of piling is, therefore preferable. 
     (2) Ink-Stain (Ink Feedback) on the Dampening Roller 
     After completion of the printing, ink-stain on the dampening roller were visually observed and ranked as follows
     ◯ . . . little ink-stain   Δ . . . slight ink-stain   × . . . obvious ink-stain   

     (3) Evaluation of Plate Damage 
     In a printing plate that has been exposed and developed, but before printing, each fountain solution composition for use in printing was dropped in amounts of 1 μl, 5 μl and 20 μl, on image areas of 50% dot portion and the solid portion on the plate and the plate was left for 60 minutes. Then, the printing plate was mounted on the printing press and printing was performed as described above, and damage to the image area was evaluated as follows, on printed matter obtained.
     ◯ . . . no damage to the image areas   Δ . . . slightly observed a trace of droplet and a little damage   × . . . apparent damage to image areas of 50% dot portion or the solid portion   

                     TABLE 1                  (Symbols of diol compounds used in the examples correspond to those       attached to the exemplified compounds described above.)                                                     Ink-stain                           on       Exam-   Diol   Cationic   Blanket   dampening   Plate       ples   compound   compound   piling   roller   damage                                             Example                            1   (7)   Tetraphenyl   52   ◯   ◯               phosphonium bromide        2   (7)   Tetraphenyl   52   ◯   ◯               phosphonium chloride        3   (7)   Triethylbenzyl   54   ◯   ◯               ammonium chloride        4   (7)   Tributylbenzyl   50   ◯   ◯               ammonium chloride        5   (7)   Octyldimethylbenzyl   50   ◯   ◯               ammonium chloride        6   (10)   Tetraphenyl   50   ◯   ◯               phosphonium bromide        7   (10)   Tributylbenzyl   48   ◯   ◯               ammonium chloride        8   (10)   Octyldimethylbenzyl   48   ◯   ◯               ammonium chloride        9   (1)   Tetraphenyl   72   Δ   ◯               phosphonium bromide       10   (6)   Tetraphenyl   65   Δ   ◯               phosphonium bromide       11   (14)   Tetraphenyl   61   Δ   ◯               phosphonium bromide       Comparative       Example       1   No additive   No additive   100   Δ   ◯       2   2-ethyl-1,3-   No additive   96   Δ   X           hexanediol       3   1,9-nonanediol   No additive   96   Δ   X       4   Comparative   No additive   98   X   Δ           compound (1)       5   (7)   No additive   52   ◯   X       6   (10)   No additive   50   ◯   X       7   No additive   Tetraphenyl   105   X   ◯               phosphonium bromide       8   2-ethyl-1,3-   Tetraphenyl   98   X   Δ           hexanediol   phosphonium bromide       9   1,9-nonanediol   Tetraphenyl   98   X   Δ               phosphonium bromide       10   Comparative   Tetraphenyl   98   X   Δ           compound (1)   phosphonium bromide       11   2-ethyl-1,3-   Tributylbenzyl   96   X   Δ           hexanediol   ammonium chloride                         Comparative compound (1):                                      
that is the compound wherein ethylene oxide is added to a diol described in JP H02-48996 A.
 
     The result shown in Table 1 indicates that the combination use of diol compounds and cationic compounds according to the invention remarkably inhibits blanket piling, causes hardly any ink-stain (ink feedback) on the dampening roller, and further causes no damage to image areas, resulting in no plate damage. Therefore according to the combination use of diol compounds and cationic compounds, favorable printed matter can be obtained, and it is apparent that excellent printing performance is exhibited thereby. 
     In Examples 1 to 11, a concentrated solution having 50-200 fold higher concentration over the working solution was prepared, and the working solution was prepared by diluting the concentrated solution with tap water and used to confirm the same effect as described above could be observed. 
     Examples 12-21 
     Exactly the same experiment as described in Example 7 was conducted except that ethylene glycol mono-t-butyl ether and propylene glycol were replaced with the compounds shown in Table 2 below. In Example 21, isopropyl alcohol was used and the amount thereof to be added was increased to 15 fold higher (i.e. to 7.5%) than those of the compounds used in other examples (0.5%). In Example 21, even when water volume was increased, stains were still prone to occur by ink attachment to the non-image areas on the printed matter, unless the additive amount of isopropyl alcohol was increased. The results are shown in Table 2. 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                   
                   
                   
                 Ink-stain 
                   
               
               
                   
                   
                   
                   
                 on 
               
               
                   
                   
                   
                 Blanket 
                 dampening 
                 Plate 
               
               
                 Example 
                 Compound 1 
                 Compound 2 
                 piling 
                 roller 
                 damage 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 7 
                 Ethylene 
                 Propylene 
                 48 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-t- 
               
               
                   
                 butyl ether 
               
               
                 12 
                 Ethylene 
                 Propylene 
                 54 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-n- 
               
               
                   
                 butyl ether 
               
               
                 13 
                 Propylene 
                 Propylene 
                 52 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-n- 
               
               
                   
                 butyl ether 
               
               
                 14 
                 Ethylene 
                 Propylene 
                 60 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono 
               
               
                   
                 isopropyl 
               
               
                   
                 ether 
               
               
                 15 
                 Ethylene 
                 Propylene 
                 68 
                 Δ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-n- 
               
               
                   
                 hexyl ether 
               
               
                 16 
                 3-methoxy- 
                 Propylene 
                 70 
                 Δ 
                 ◯ 
               
               
                   
                 3-methyl-1- 
                 glycol 
               
               
                   
                 butanol 
               
               
                 17 
                 Propylene 
                 Dipropylene 
                 55 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-n- 
               
               
                   
                 butyl ether 
               
               
                 18 
                 Propylene 
                 Tripropylene 
                 57 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-n- 
               
               
                   
                 butyl ether 
               
               
                 19 
                 Propylene 
                 Diethylene 
                 70 
                 Δ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-n- 
               
               
                   
                 butyl ether 
               
               
                 20 
                 Propylene 
                 No additive 
                 72 
                 Δ 
                 ◯ 
               
               
                   
                 glycol 
               
               
                   
                 mono-n- 
               
               
                   
                 butyl ether 
               
               
                 21 
                 Isopropyl 
                 No additive 
                 65 
                 Δ 
                 ◯ 
               
               
                   
                 alcohol 
               
               
                   
                 (7.5 g/100 g) 
               
               
                   
               
            
           
         
       
     
     As seen from Table 2, the intended effect according to the present invention is more highly exhibited in Examples 7, 12 to 14, 17 and 18 wherein the compound of formula (III) and the compound of formula (IV) were used in combination. 
     A concentrated solution having a concentration 50-fold higher than the working solution was prepared, and it was found out that use of the compounds of formula (III) and formula (IV) was preferable in terms of solubility stability. 
     Experimental Example 1 
     The same printing experiment as described in Example 7 was conducted except that the amounts of diol compound (10) to be added were altered. As a result, it was revealed that the additive amount thereof is preferably not less than 0.05%, more preferably not less than 0.1%, and particularly preferably not less than 0.2%. On the other hand, an additive amount exceeding 1% was prone to slightly aggravate ink-stain (ink feedback) on the dampening roller. 
     Further, in Example 7, the amounts of diol compound (10) to be added were decreased to 99%, 97%, 90% and 50% respectively, and each decrement of 1%, 3%, 10% and 50% represented diol compound (7). As the result, the same effect was observed as Example 7. 
     Examples 22-24 
     Exactly the same experiment as described in Example 5 was conducted except that ethylene glycol mono-t-butyl ether and propylene glycol were replaced with the compounds shown in Table 3 below. The results are shown in Table 3. 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                   
                   
                 Ink-stain 
                   
               
               
                   
                   
                   
                   
                 on 
               
               
                   
                   
                   
                 Blanket 
                 dampening 
                 Plate 
               
               
                 Example 
                 Compound 1 
                 Compound 2 
                 piling 
                 roller 
                 damage 
               
               
                   
               
             
            
               
                 5 
                 Ethylene 
                 Propylene 
                 50 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-t- 
               
               
                   
                 butyl ether 
               
               
                 22 
                 Propylene 
                 Propylene 
                 54 
                 ◯ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
                 mono-t- 
               
               
                   
                 butyl ether 
               
               
                 23 
                 3-methoxy- 
                 Propylene 
                 65 
                 Δ 
                 ◯ 
               
               
                   
                 3-methyl-1- 
                 glycol 
               
               
                   
                 butanol 
               
               
                 24 
                 Propylene 
                 Propylene 
                 60 
                 Δ 
                 ◯ 
               
               
                   
                 glycol 
                 glycol 
               
               
                   
               
            
           
         
       
     
     Examples 25-29 
     In the following formulation of fountain solution composition, the compound represented by the formula (VI) or (VII) was varied as shown in Table 4, and then various fountain solution compositions were prepared. 
     Formulation of the Fountain Solution Composition (Working Solution) of Use 
       
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Ingredients 
                 Additive amount 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Compound of the formula (VI) or (VII) 
                 0.06 
                 g 
               
               
                   
                 Polyvinylpyrrolidone K-15 
                 0.01 
                 g 
               
               
                   
                 Carboxymethylcellulose 
                 0.05 
                 g 
               
               
                   
                 Diol compound (7) 
                 0.40 
                 g 
               
               
                   
                 Tributylbenzyl ammonium chloride 
                 0.02 
                 g 
               
               
                   
                 D-sorbitol 
                 0.40 
                 g 
               
               
                   
                 Ammonium nitrate 
                 0.02 
                 g 
               
               
                   
                 Gluconic acid 
                 0.02 
                 g 
               
               
                   
                 2,2-dibromo-2-nitroethanol 
                 0.002 
                 g 
               
               
                   
                 2-methyl-5-chloro-4-isothiazolin-3-one 
                 0.002 
                 g 
               
               
                   
                 Water 
                 up to 100 
                 g in total 
               
               
                   
                   
               
            
           
         
       
     
     Using these fountain solution compositions, the same experiment was conducted as described in Example 1. The results are shown in Table 4. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                   
                   
                   
                 Ink-stain on 
                   
               
               
                   
                 Compound of the formula 
                 Blanket 
                 dampening 
                 Plate 
               
               
                 Example 
                 (VI) or (VII) 
                 piling 
                 roller 
                 damage 
               
               
                   
               
             
            
               
                 25 
                 Compound of formula (VI) 
                 55 
                 ◯ 
                 ◯ 
               
               
                   
                 (a = c = e = g = 1, b = d = f = h = 3, 
               
               
                   
                 molecular weight: 977) 
               
               
                 26 
                 Compound of formula (VI) 
                 68 
                 Δ 
                 ◯ 
               
               
                   
                 (a = c = e = g = 1, b = d = f = h = 1, 
               
               
                   
                 molecular weight: 513) 
               
               
                 27 
                 Compound of formula (VI) 
                 57 
                 ◯ 
                 ◯ 
               
               
                   
                 (a = c = e = g = 2, b = d = f = h = 4, 
               
               
                   
                 molecular weight: 1386) 
               
               
                 28 
                 Compound of formula (VI) 
                 70 
                 Δ 
                 ◯ 
               
               
                   
                 (a = c = e = g = 5, b = d = f = h = 15, 
               
               
                   
                 molecular weight: 4470) 
               
               
                 29 
                 Compound of formula (VII) 
                 57 
                 ◯ 
                 ◯ 
               
               
                   
                 (a = c = e = g = 1, b = d = f = h = 3, 
               
               
                   
                 molecular weight: 1195) 
               
               
                   
               
            
           
         
       
     
     Additionally, in Example 25, when propylene glycol mono-n-butyl ether and propylene glycol were added in amount of 0.3 g, respectively, an excellent effect was ascertained. 
     Examples 30-35 
     The same printing experiment as described in Example 16 was conducted except that a pyrrolidone derivative or acetylene derivative shown in Table 5 was added at a concentration of 0.01%. The obtained results are shown in Table 5. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                   
                   
                   
                 Ink-stain on 
                   
               
               
                   
                 Pyrrolidone derivative/ 
                 Blanket 
                 dampening 
                 Plate 
               
               
                 Example 
                 acetylene derivative 
                 piling 
                 roller 
                 damage 
               
               
                   
               
             
            
               
                 16 
                 No additive 
                 70 
                 Δ 
                 ◯ 
               
               
                 30 
                 Butylpyrrolidone 
                 66 
                 Δ 
                 ◯ 
               
               
                 31 
                 Octylpyrrolidone 
                 50 
                 ◯ 
                 ◯ 
               
               
                 32 
                 3,5-Dimethyl-1-hexyne-3- 
                 68 
                 Δ 
                 ◯ 
               
               
                   
                 ol 
               
               
                 33 
                 3,6-Dimethyl-4-octyne-3,6- 
                 54 
                 ◯ 
                 ◯ 
               
               
                   
                 diol 
               
               
                 34 
                 2,4,7,9-Tetramethyl-5- 
                 60 
                 Δ 
                 ◯ 
               
               
                   
                 decyne-4,7-diol 
               
               
                 35 
                 Adduct compound of 4 
                 52 
                 ◯ 
                 ◯ 
               
               
                   
                 ethylene oxides to 2,4,7,9- 
               
               
                   
                 tetramethyl-5-decyne-4,7- 
               
               
                   
                 diol 
               
               
                   
               
            
           
         
       
     
     Examples 36 to 38 
     The same printing experiment as described in Example 24 was conducted except that a pyrrolidone derivative or acetylene derivative shown in Table 6 was added at a concentration of 0.01%. The obtained results are shown in Table 6. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
               
                   
                   
                   
                 Ink-stain on 
                   
               
               
                   
                 Pyrrolidone derivative/ 
                 Blanket 
                 dampening 
                 Plate 
               
               
                 Example 
                 acetylene derivative 
                 piling 
                 roller 
                 damage 
               
               
                   
               
             
            
               
                 24 
                 No additive 
                 60 
                 Δ 
                 ◯ 
               
               
                 36 
                 Butylpyrrolidone 
                 52 
                 ◯ 
                 ◯ 
               
               
                 37 
                 3,6-Dimethyl-4-octyne-3,6- 
                 55 
                 ◯ 
                 ◯ 
               
               
                   
                 diol 
               
               
                 38 
                 Adduct compound of 4 
                 53 
                 ◯ 
                 ◯ 
               
               
                   
                 ethylene oxides to 2,4,7,9- 
               
               
                   
                 tetramethyl-5-decyne-4,7- 
               
               
                   
                 diol 
               
               
                   
               
            
           
         
       
     
     Experiment Example 2 
     The same printing experiment as described in Examples 5 and 7 was performed respectively, except that the ink used for the experiment was changed as follows to confirm the effect of the fountain solution composition of the invention.
     TOYO INK MFG CO., LTD.
       Super LeoEcoo SOY: cyan, magenta, yellow   LeoEcoo SOY: black, cyan, magenta, yellow   LeoEcoo LTD pro: black, cyan, magenta, yellow   
       TOKYO PRINTING INK MFG. CO., LTD.
       WEB ACTUS SOY Major: black, cyan, magenta, yellow   
       DIC Corporation
       New ADVAN: black, cyan, magenta, yellow   
       THE INCTEC INC.
       SOYBI VISTA: black, cyan, magenta, yellow   
       

     The same effects as described in Examples 5 and 7 were observed for all inks for rotary offset of heat-set types listed above. The inks for which the fountain solution composition of the invention can be used are not limited to these, and the composition of the invention can be effectively used for fluorescent inks, mat inks, and a variety of neutral colour inks. 
     The fountain solution composition of the invention is also useful for rotary offset inks of non-heatset type used for printing of newspapers and inks for sheet-fed process other than rotary offset inks of heat-set types. In particular, rotary offset inks of heat-set types are preferable since the effect of the fountain solution composition of the invention can be prominently exercised in these inks. 
     Experiment Example 3 
     The same printing assay as described in Examples 5 and 7 was conducted after printing 50000 sheets, except that the printing machine was replaced with SYSTEM35S from KOMORI Corporation, and then the similar results were obtained as Examples 5 and 7.