JPH10181234A - Lithographic printing dampening water composition and condensed dampening water for lithographic printing using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic polymer, which has both film-forming properties and surface-active effect and is useful as a condensed lithographic printing dampening water and a condensed dampening water, which includes the above- mentioned polymer and does not include an IPA, conforms to the regulations of the Fire Services Act and the laborers Safety and Health Act. SOLUTION: A lithographic printing dampening water composition is a polymerized compound obtained from one or more kinds of monomers represented by a formula, in which R represents H2 C=CH- or CH2 =C(CH3 )- and (x), (y) and (z) respectively represent an integer from 0 or 1 through 20 under the condition that x+y+z is an integer at least larger than 1. Further, as a condensed lithographic printing dampening water, a polymerized compound, which is obtained from one or more kinds of the nomoners represented by the formula and a water-soluble monomer, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fountain solution composition for lithographic printing useful for offset printing of a lithographic printing plate, and a concentrated fountain solution containing the composition.

[0002]

2. Description of the Related Art The offset printing method using a lithographic printing plate is a printing method which skillfully utilizes the property that water and oil are not essentially mixed. The printing plate surface has a portion that receives water and repels ink. And a portion that repels water and receives ink. The former is a non-image area, and the latter is an image area. In this method, it is important to supply the ink and the fountain solution to the plate surface in an appropriate balance. If the fountain solution is applied too much, the emulsification of the ink becomes severe, and poor transfer occurs. On the other hand, if the amount of the dampening solution is too small, the ink adheres to the non-image area, causing stains.

To maintain the balance between the ink and the fountain solution, isopropyl alcohol (hereinafter abbreviated as IPA) has been added to the fountain solution, and various hydrophilic substances such as gum arabic, carboxymethyl cellulose (C
MC), citric acid, various surfactants, etc., solubilities of acids such as phosphoric acid as a surface smoothing agent to remove plate surface oxides, ammonium bichromate, nitrate and other additives as plate corrosion inhibitors. An organic solvent or the like to be adjusted is added. Here, the effects of adding IPA include the effect of lowering the surface tension of the dampening solution to improve the wetting of the hydrophilic non-image area, and the effect of increasing the viscosity of the dampening solution to increase the dampening solution on the plate surface. The effect of smoothing the supply of water.

[0004] However, IPA falls under the category of dangerous alcohols of the fourth class, and it is necessary to pay close attention to fire when used. In addition, since it is a second-class organic solvent in the Organic Solvent Prevention Regulations (Organic Regulations), it is usually added to fountain solution at a concentration of about 5 to 20% by weight. There was a problem.

Therefore, in recent years, a fountain solution or a fountain solution composition has been proposed in which IPA is not used at all, or even if it is used, the concentration of the fountain solution is 5% by weight or less. For example, IPA
JP-A-57-1792 and 57-199,69 are compounds obtained by adding another organic solvent as an alternative compound of the above.
No. 3, No. 63-4,994, JP-A-2-48,996
No. 2-269,094, No. 2-292,092
No. 2-310,092, 3-63,187,
3-63,188, 3-90,389, 3-
Nos. 90,390, 3-155,991, 4-1
No. 091, 4-201, 495, 5-92, 67
No. 7, No. 5-201, 167, No. 6-64, 362
Nos. 6-183,171 and 6-206,391
No. 8-132,753, Tokuhei 4-46,760
JP, JP-A-7-41,748, JP-A-7-85,94
No. 7 and No. 7-96, 344. These IPA substitute compounds are high-boiling organic compounds. It has been found that the boiling point organic solvent is concentrated and remains as a residue, and has a problem that the image area of the lithographic printing plate is affected. Further, it is necessary to mix and use a large amount of water in order to satisfy the Fire Service Law (organic solvent less than 40%, flash point 40 ° C. or more, burning point 60 ° C. or more). There was a problem that it was easily unstable.

Attention is also paid to the surface tension lowering ability of IPA, and various surfactants are added thereto, for example, as described in JP-A-63-25093 and JP-A-63-134293.
JP-A-2-48,996 and JP-A-2-196,696.
No. 2-209,294, No. 2-255,386
No. 2-269,094, No. 3-63,187,
3-63,188, 3-90,389, 4-
Nos. 351,593, 5-92,677 and 5-11
No. 2,085, No. 5-116,476, No. 5-13
No. 9,068, No. 5-201, 167, No. 5-22
No. 1,179, No. 5-221, No. 180, No. 5-28
6,279, 6-32,082, 6-64,3
Nos. 62, 6-183, 171 and 6-206, 39
No. 1, 6-219, 076, 7-195, 859
No., JP-B-7-41,748 and JP-B-7-96,
No. 344, and the like. However, in order to keep the fountain solution containing various surfactants described therein at an appropriate surface tension necessary for printing, the surfactant concentration in the fountain solution is considerably increased. It is necessary to keep it high, and as a disadvantage, it is easy to foam when the fountain solution is concentrated at the time of use. In particular, in the case of a polyoxyethylene compound having a high molecular weight (polymerization degree of 15 or more), an image by a plate tray is used. Fatal defects tended to occur, such as damage to parts. In actual lithographic printing, the ink and water violently move under the ink roll, printing plate, and dampening water supply roll rotating at high speed, so that water adheres to the ink film,
There are problems such as the diffusion of ink on the surface of water, but the surfactants proposed above were not sufficient to completely eliminate these problems.

Further, it is essential to add a hydrophilic polymer compound having a film-forming property to the fountain solution for lithographic printing, and the addition of the hydrophilic polymer compound imparts hydrophilicity to the non-image area of the lithographic printing plate. It has the effect of increasing the viscosity of the dampening water and smoothing the supply of the dampening water to the plate surface together with the action of imparting. One of the effects of adding IPA to the dampening solution is a thickening effect of the dampening solution. When removing IPA from the dampening solution, it is necessary to take some measures for thickening. For this reason, various hydrophilic polymer compounds have been proposed.

Japanese Patent Application Laid-Open No. 54-114,302 discloses an example of using such a hydrophilic polymer compound as a natural compound.
Nos. 57-1792 and 61-189,997
JP-A-2-255,386, JP-A-2-258,39
Nos. 0, 3-73,394 and 4-363,297
Nos. 5-112,085 and 5-116,476
No. 5,147,371, No. 6-219,076 and No. 7-125,472, but the compounds using these natural compounds as raw materials do not always have constant physical properties. However, there are also problems such as difficulty in reproducibility, and problems such as not solving the problems pointed out earlier when used in combination with an organic solvent or a surfactant.

Further, as another proposal, a method of adding a hydrophilic polymer compound by a synthesis method is disclosed in, for example,
4-65,606 and JP-B-62-15,360, copolymers of acrylate and methacrylic acid, JP-A-54-138,703 and JP-B-61
-55,480, a polyacrylic acid compound, a copolymer of acrylic acid and vinyl acetate according to JP-A-61-273,996, and a dicarboxylic acid of an ethylene oxide-propylene oxide adduct according to JP-A-2-175,191. Compound, polyacrylamide compound according to JP-A-5-286,279, itaconic acid or maleic acid as a copolymerization component according to JP-A-8-112,980 having 1 to 10 mol% in the molecule and a saponification degree of 80 to 100 Mol%
Polyvinyl alcohol, JP-A-8-132,75
Having a mercapto group at one end as a substituent according to No. 2,
The degree of saponification is 50 to 100 mol%, and the number average degree of polymerization is 2
There are polyvinyl alcohols of 0 to 2000, but these compounds are not used alone as in the case of compounds using natural compounds as raw materials, and they need to be used in combination with an organic solvent or a surfactant. It did not sufficiently solve the aforementioned problems.

Japanese Patent Application Laid-Open No. 4-161,386 proposes adding a copolymer of an acrylate or methacrylate containing a fluoroaliphatic group and a polyoxyalkylene / acrylate or methacrylate to dampening water. However, when using this synthetic compound, it is necessary to simultaneously use a compound having film-forming properties as an essential component, and this synthetic compound alone cannot be used as a substitute for a hydrophilic polymer compound.

[0011]

Accordingly, the first aspect of the present invention is as follows.
The object of the present invention is to provide a concentrated fountain solution for lithographic printing which is free from the danger and toxicity of a conventional fountain solution containing IPA and has excellent liquid stability in conformity with the regulations of the Fire Service Law and the Industrial Safety and Health Law. It is in. A second object of the present invention is to make it possible to easily adjust the supply amount when performing a printing operation, not only to prevent dirt and blinding of the printing plate, but also to prevent damage to the image area of the printing plate, It is an object of the present invention to provide a concentrated fountain solution for lithographic printing having excellent fountain solution characteristics that can easily obtain high-quality printed matter. A third object of the present invention is to
A lithographic plate used as a concentrated fountain solution for lithographic printing, using a synthetic polymer that can be easily synthesized with good reproducibility and is effective not only as a hydrophilic polymer compound having a film-forming property but also at the same time as having a surfactant effect. It is to provide a fountain solution composition for printing.

[0012]

The object of the present invention is to provide at least a monomer 1 represented by the following general formula (I):
A polymer or copolymer obtained from at least one species (hereinafter abbreviated as polymer compound 1),

[0013]

## STR2 ## Formula (I) (Wherein R is H ₂ C ＝ CH— or H ₂ C ＝ C (CH ₃ )
Represents-. X, y and z each represent 0 or an integer of 1 to 20. However, x + y + z is an integer of at least 1 or more. And / or the general formula (I)
And at least one monomer selected from the group consisting of acrylamide, N-methylacrylamide, N-ethylacrylamide, N
-Propylacrylamide, N-isopropylacrylamide, N- (dimethylaminomethyl) acrylamide, N- (dimethylaminoethyl) acrylamide, N
-(Dimethylaminopropyl) acrylamide, N, N
-Dimethylacrylamide, N-methyl-N-ethylacrylamide, acrylic acid, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, 3- (acrylamidyl) butylsulfonic acid,
-(Acrylamidyl) butylsulfonic acid, 3- (acrylamidyl) propylsulfonic acid, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-
Isopropyl methacrylamide, N- (dimethylaminomethyl) methacrylamide, N- (dimethylaminoethyl) methacrylamide, N- (dimethylaminopropyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-ethylmeth Acrylamide, methacrylic acid, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, 3- (methacrylamidyl) butylsulfonic acid, 4- (methacrylamidyl) butylsulfonic acid, 3- (meth A copolymer obtained from at least one water-soluble monomer selected from acrylamidyl) propylsulfonic acid, aryl glycol and acroylmorpholine (hereinafter abbreviated as polymer compound 2). Do It could be achieved by a plate printing fountain solution compositions and concentrated dampening lithographic printing containing these dampening water composition of water.

The polymer compound 1 used in the present invention will be described. The polymer compound 1 is obtained by random polymerization of various monomers represented by the general formula (I), and there is no particular limitation on their composition ratio. However, if the polymerization reaction is carried out while fixing the monomer used and the composition ratio according to the purpose, it is possible to obtain a copolymer having similar properties with good reproducibility.

The monomer represented by the general formula (I) used in the present invention excludes the case where x = y = z = 0, that is, the case where the polymer compound 1 is polyacrylic acid or polymethacrylic acid. When the general formula (I) is y = z = 0, it represents a polyethylene glycol monoester of acrylic acid or methacrylic acid, and x is a monomer of 1 to 20. When the general formula (I) is x = z = 0, it represents a polypropylene glycol monoester of acrylic acid or methacrylic acid, and y is a monomer of 1 to 20. When the general formula (I) is x = y = 0, it represents a polytetramethylene glycol monoester of acrylic acid or methacrylic acid, and z is a monomer of 1 to 20. When the general formula (I) is x = 0, it represents a random polymer monoester of polypropylene glycol of acrylic acid or methacrylic acid and polytetramethylene glycol, y and z are each an integer from 1 to 20, and It is a monomer selected from a combination of an integer and an integer of z. When the general formula (I) is y = 0, it represents a random polymer monoester of polyethylene glycol and polytetramethylene glycol of acrylic acid or methacrylic acid, x and z are each an integer from 1 to 20, and It is a monomer selected from a combination of an integer and an integer of z. When the general formula (I) is z = 0, it represents a random polymer monoester of polyethylene glycol and polypropylene glycol of acrylic acid or methacrylic acid, wherein x and y are each an integer from 1 to 20, and It is a monomer selected from a combination of integers of y. In the general formula (I), when none of x, y and z is 0, it represents a random polymer monoester of polyethylene glycol, polypropylene glycol and tetramethylene glycol of acrylic acid or methacrylic acid, wherein x, y and z are respectively It is an integer of 1 to 20, and is a monomer selected from a combination of an integer of x, an integer of y, and an integer of z.

The polymer compound 1 obtained by the above method
Is used in the range of 230 to 100,000, preferably 500 to 20,000.

In order to obtain the polymer compound 2, in the presence of at least one monomer selected from the general formula (I) and at least one water-soluble monomer described in claim 3, the polymer compound 1 is obtained in exactly the same manner. It can be synthesized by the operation method. The weight average molecular weight of the polymer compound 2 is from 300 to 200,000, and preferably a compound having a weight of 1,000 to 50,000 is used. Further, with respect to the monomer composition ratio of the polymer compound 2, the weight ratio of the monomer represented by the general formula (I) is between 99.5% and 40.0%.

The present invention further relates to a concentrated fountain solution, wherein the concentrated fountain solution of the present invention contains the lithographic fountain solution of the present invention in an amount of 0.01 to 20% by weight, preferably 0.1 to 20% by weight. To 15% by weight of the concentrated fountain solution.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The monomers represented by the general formula (I) are commercially available for specific monomers (for example, “Nissan Blemmer Series (Monomer 2)” by NOF Corporation) and others. Necessary monomers can be easily obtained by contract production or the like.

In order to obtain a polymer compound 1 by selecting one or more of the above monomers, a usual radical polymerization reaction is used. That is, any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization may be used as the polymerization method, and the radical generation method may also include thermal polymerization, thermal initiation polymerization, photopolymerization, photosensitized polymerization, and radiation polymerization. Either method may be used. However, usually, a thermal polymerization reaction using an initiator and a chain transfer agent by a solution polymerization method is preferably selected from the viewpoint of easy control of the polymerization reaction and uniformity and reproducibility of the obtained polymer.

As a specific polymerization method, a reactor equipped with a stirrer and a cooling condenser is used, and under an inert gas atmosphere such as helium gas, nitrogen gas, argon gas, etc., it is suitable for a fountain solution described later as a reaction solvent. In addition to the organic solvents used, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, 2-
Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,
Using N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like, add necessary amounts of monomers, a polymerization initiator, a chain transfer agent, and the like; The mixture is heated and stirred until the polymerization reaction is completed. Usually, the reaction time is 1 to 24 hours at 10 to 120 ° C. Thereafter, the solvent used is removed to obtain the desired polymer compound 1. If necessary, it can be purified using a technique such as reprecipitation. Also,
After the reaction, the polymer can be used as a raw material for the concentrated fountain solution together with the solvent without purifying the polymer.

Examples of the polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, Various peroxides such as t-butyl hyponitrite, persulfate, azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanecarbonitrile, hydrogen peroxide-iron (II) salt, Redox catalysts such as persulfate-sodium bisulfite, cumene hydroperoxide-iron (II) salt, and benzoyl peroxide-dimethylaniline can be used.

Examples of the chain transfer agent include 2-mercaptoethylamine, laurylmercaptan, thioglycerin, mercaptoethanol, (2-mercaptoethyl) phosphoric acid diethyl ester, (2-mercaptoethylamino) phosphoric acid diethyl ester, pentaerythritol tetra ( Thiol derivatives such as mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate), bis (2-naphthalene) disulfide, bis (3-anilino) disulfide, 4,4′-dithiodibenzoic acid, thiophenylphenyl Disulfides such as sulfones, halides, metal ions, 2-bromomethylacrylic acid methyl ester, α-
Addition / decomposition type chain transfer agents such as benzyloxystyrene can also be used.

The polymer compound 1 obtained by the above method
Is used in the range of 230 to 100,000, preferably 500 to 20,000.

The polymer compound 2 used in the present invention is obtained by copolymerizing one or more of the water-soluble monomers described in claim 3 during the polymerization reaction of the polymer compound 1 described above. It is a polymer, and can change the cloud point and water solubility of the polymer compound 1 or can change the viscosity and surface tension of the polymer compound 1 when added to a fountain solution.

In order to obtain the polymer compound 2, the same method as that for obtaining the polymer compound 1 in the presence of at least one kind of monomer selected from the general formula (I) and at least one kind of the water-soluble monomer described in claim 3 is used. It can be synthesized by the operation method. The weight average molecular weight of the polymer compound 2 is from 300 to 200,000, and preferably a compound having a weight of 1,000 to 50,000 is used. Further, with respect to the monomer composition ratio of the polymer compound 2, the weight ratio of the monomer represented by the general formula (I) is between 99.5% and 40.0%. When the proportion of the monomer represented by the general formula (I) is 40.0% or less,
The properties of the hydrophilic high molecular compound having a surface active effect according to the present invention become dilute, and when it is 99.5% or more, it is difficult to sufficiently obtain the modifying effect by the water-soluble monomer.

Next, the concentrated dampening solution according to the present invention will be described. The concentrated dampening solution for lithographic printing of the present invention contains the fountain solution composition for lithographic printing of the present invention in an amount of 0.01 to 20% by weight, preferably 0.1 to 15% by weight. Water, and a film-forming hydrophilic polymer, pH
Buffers, wetting agents, organic solvents, defoamers, preservatives, rust inhibitors,
It may contain a coloring agent, a chelating agent and the like.
When the content of the fountain solution for lithographic printing is less than 0.01% by weight, the surface tension is not sufficiently reduced, and the ink spreads to the surface of the fountain solution, causing floating stains on printed matter. And soiling comes out. On the other hand, if the content exceeds 20% by weight, the drainage is improved in terms of increasing the viscosity of the dampening solution, but it is disadvantageous in terms of cost, and further increase of the content is not desirable. . As the fountain solution composition for lithographic printing used in the concentrated fountain solution for lithographic printing of the present invention, a compound selected from polymer compound 1 and / or polymer compound 2 is used. They can be used together.

The action of fountain solution in lithographic printing is to increase the surface chemical difference between the image area and the non-image area by wetting the non-image area of the printing plate surface, and to improve the ink repellency of the non-image area. It has the effect of increasing the ink receptivity of the image area, and a film-forming hydrophilic polymer, pH buffer, wetting agent, organic solvent,
It is composed of an antifoaming agent, a preservative, a rust inhibitor, a coloring agent, a chelating agent and the like. The polymer compound 1 and the polymer compound 2 according to the present invention are compounds having both properties as a film-forming hydrophilic polymer and properties as a wetting agent, and have been used for a concentrated fountain solution containing the polymer compound according to the present invention. It is not always necessary to include a known film-forming hydrophilic polymer or wetting agent, but it is possible to add and use a known film-forming hydrophilic polymer or wetting agent as a minute adjustment.

The fountain solution for lithographic printing of the present invention is diluted 10 to 100 times with water such as tap water or well water, and used on a printing machine as a fountain solution for lithographic printing. At this time, the concentrated fountain solution for lithographic printing which has been diluted exhibits good performance as a fountain solution for lithographic printing.

Preferred specific examples of the film-forming hydrophilic high molecular compound used in the concentrated fountain solution for lithographic printing of the present invention include gum arabic, starch and derivatives thereof (for example, dextrin, enzyme-decomposed dextrin, Hydroxypropylated enzymatically decomposed dextrin, carboxymethylated starch, phosphate starch, octenyl succinate esterified starch), alginate, fibrin derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, methylcellulose,
Natural products such as hydroxypropylcellulose, hydroxypropylmethylcellulose, glyoxal-modified products thereof and the like, and polyvinylpyrrolidone, polyvinylalcohol and its derivatives polyacrylamide and its copolymer, polyacrylic acid and its copolymer And synthetic products such as vinyl methyl ether and maleic anhydride copolymer, and vinyl acetate and maleic anhydride copolymer. The use of these high molecular compounds is not always necessary, but when used, the concentration is preferably 5% by weight or less in concentrated fountain solution for lithographic printing. Two or more of these specific examples may be selected and used in combination.

The pH buffer used in the concentrated dampening solution for lithographic printing of the present invention may be a compound containing a water-soluble organic acid, inorganic acid or a salt thereof. It is effective in adjusting or pH buffering, moderate etching of the lithographic printing plate support or anticorrosion. Preferred organic acids include, for example, citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, gluconic acid, hydroxyacetic acid, oxalic acid, malonic acid, levulinic acid, phytic acid,
Organic phosphonic acids and the like can be mentioned. Examples of the inorganic acid include phosphoric acid, nitric acid, and sulfuric acid. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts of these organic acids and / or inorganic acids are also preferably used, and these organic acids, inorganic acids and / or salts thereof may be used alone or in combination. More than one kind may be used in combination. The concentration of these compounds in the concentrated fountain solution for lithographic printing of the present invention is preferably in the range of 0.01 to 15% by weight. The pH of the lithographic printing dampening solution diluted with water is preferably in the acidic range of 3 to 7, but contains alkali metal salts, phosphoric acid, alkali metal hydroxides, alkali metal carbonates, and silicates. It can be used in the alkaline range of pH 7 to 11.

The wetting agent used in the concentrated fountain solution for lithographic printing of the present invention includes various surfactants. Specific examples of the anionic surfactant include, for example, fatty acid salts,
Abietic acid salts, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, linear alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates, polyoxyethylenealkylsulfophenyl Ether salts, N-methyl-N-oleyltaurine sodium salts, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfone complex salts, sulfated castor oil, sulfated tallow oil, sulfates of fatty acid alkyl esters, polyoxyethylene Alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styrylphenyl ether Tersulfate salts, alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphate salts, partially saponified styrene and maleic anhydride copolymers, naphthalene sulfonate formalin condensates And the like.

Specific examples of the nonionic surfactant include:
Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, partially esterified glycerin fatty acids, partially esterified sorbitan fatty acids, pentaerythritol Fatty acid partial esterified products, propylene glycol monofatty acid esters, sucrose fatty acid partial esterified products, polyoxyethylene sorbitan fatty acid partial esterified products, polyoxyethylene sorbitol fatty acid partial esterified products, polyethylene glycol fatty acid esters, polyglycerin fatty acid Partially esterified products, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partially esterified products, fatty acids Examples include ethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, and polyoxyethylene-polyoxypropylene block polymers. . Other fluorine-based surfactants and silicon-based surfactants can also be used.

Specific examples of the cationic surfactant include:
Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylenepolyamine derivatives.

These surfactants may be used alone or in combination of two or more. It is not always necessary to use these surfactants in the concentrated fountain solution for lithographic printing of the present invention. However, when used, the concentration is preferably 2.0% by weight or less in the concentrated fountain solution for lithographic printing. is there.

As the organic solvent used in the concentrated fountain solution for lithographic printing of the present invention, monovalent, divalent and trivalent alcohols are used. Specific examples of the organic solvent include ethyl alcohol, n-propyl alcohol, butyl alcohol, isobutyl alcohol, n-amyl alcohol, benzyl alcohol, 3-butoxy-2-propanol,
3-methyl-3-butoxybutanol, neopentyl alcohol, 2-ethyl-1,3-hexanediol, hexyl cellosolve, hexyl carbitol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol , Hexylene glycol, tetraethylene glycol, 1,5-pentanediol, glycerin, diglycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, ethylene glycol monoethyl ether, diethyl Glycol monoethyl ether, triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol Propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether,
Dipropylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t
-Butyl ether, triethylene glycol mono-t-
Butyl ether, dipropylene glycol mono-t-butyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, glycerin, diglycerin, trigserin, trimethylolethane, trimethylolpropane, 3-methylpentane-1, 3,
Examples thereof include 5-triol, pentaerythritol, sorbitol and mannitol. The organic solvent may be used alone or in combination. The content in the concentrated fountain solution for lithographic printing of the present invention is 35% by weight or less, and preferably 25% by weight or less.

As the antifoaming agent used in the concentrated fountain solution for lithographic printing of the present invention, a silicon antifoaming agent and / or a fluorine-based antifoaming agent are preferably used. Among them, any of an emulsified dispersion type and a solubilized type can be used. A desirable addition amount is 1% by weight or less based on the whole concentrated fountain solution.

The preservatives used in the concentrated fountain solution for lithographic printing of the present invention include phenol or a derivative thereof, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzotriazole derivative, amidine Or a derivative of guadinine,
Examples include quaternary ammonium salts, pyridine or quinoline derivatives, diazine or triazole derivatives, oxazole or oxazine derivatives. Preferred addition amount is an amount that exerts a stable effect on bacteria, mold, yeast, etc., and varies depending on the kind of bacteria, mold, yeast, etc., but it is based on the concentrated fountain solution for lithographic printing of the present invention. It is preferably in the range of 4% by weight or less, and it is preferable to use two or more preservatives effective against various bacteria, molds and yeasts.

As the rust preventive used in the concentrated fountain solution for lithographic printing of the present invention, benzotriazole, 5-methylbenzotriazole, 5-methoxybenzotriazole,
4-chlorobenzotriazole, 4-bromobenzotriazole, 4-bromo-6-methylbenzotriazole, 4-bromo-6-trifluoromethylbenzotriazole, and the like. Compounds in which the 1H position of these compounds is substituted with an alkali metal salt (K, Na, Li) or NH ₄ , benzimidazole and its derivatives, mercapto compounds and / or thioether compounds and alkali metal salts of these compounds, alkaline earth Long-running salts, ammonium salts, organic amine salts and the like. The content of these compounds in the concentrated fountain solution for lithographic printing is preferably used in the range of 5% by weight or less. These rust inhibitors can be used alone or in combination of two or more.

As the colorant used in the concentrated fountain solution for lithographic printing of the present invention, a water-soluble food colorant or the like can be preferably used. For example, as a yellow pigment, CINo. 19
140, 15985 and CINo. 16
185, 45430, 16255, 45380, 451
00, and CI No. 42640, and as a blue pigment, CINo. 42090, 73015, CINo. 42095 and the like.

The chelating agents used in the fountain solution for lithographic printing of the present invention include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1-hydroxyethane-1 , 1
-Diphosphonic acid, aminotri (methylenephosphonic acid) and the like, and their sodium salts, potassium salts, and organic amine salts. These chelating agents are selected from those which are stably present in the concentrated fountain solution and do not inhibit printability. The amount of addition is 10% by weight or less in concentrated fountain solution for lithographic printing.

[0042]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention.

Example 1 Polymeric compound 1 according to the present invention was synthesized by the following synthesis method. Compound 1
And 400 ml of ethylene glycol mono-t- was added to a 1 liter reaction flask equipped with a stirrer, a reflux condenser, and an inlet and outlet for nitrogen gas.
Butyl ether, Blemmer-AE-350 (manufactured by NOF Corporation; polyethylene glycol monoacrylate;
(X = 6 to 8, y = z = 0 in the general formula (I)) 12
0.0 g, Blemmer AP-550 (manufactured by NOF Corporation; polypropylene glycol monoacrylate; y = 9 to 10, x = z = 0 in the general formula (I)).
0 g, azobisisobutyronitrile 3.0 g, and lauryl mercaptan 7.5 g are added, and the mixture is replaced with nitrogen gas for 1 hour while stirring. Thereafter, the temperature was raised to 90 ° C.
Keep reacting for hours. Further, after adding 3.0 g of azobisisobutyronitrile, the reaction was continued for 5 hours, and then the solvent was removed under reduced pressure to obtain 315.5 g of a solid substance (Compound 1). The weight average molecular weight of Compound 1 was 8350.

Example 2 Compound 2 was prepared as an example of polymerized compound 1 of the present invention by using the same apparatus and operation as in Example 1.
I got That is, Bremmer-AE-350 is used as a monomer.
(Manufactured by NOF Corporation; polyethylene glycol monoacrylate; x = 6 to 8, y = z in the general formula (I))
= 0) 270.0 g and 30.0 g of Blenmer PET series (manufactured by NOF Corporation; polyethylene glycol polytetramethylene glycol monomethacrylate; x = 10, y = 0, z = 2 in the general formula (I)). Further, 3.0 g of azobisisobutyronitrile and 9.0 g of lauryl mercaptan were added, and reacted at 90 ° C. for 8 hours. At 3 hours on the way, 3.0 g of azobisisobutyronitrile was added. The obtained solid substance (compound 2) weighed 314.7 g and had a weight average molecular weight of 697.
It was 0.

Example 3 By using the same apparatus and operation as in Example 1, Compound 3 was used as an example of the polymerized compound 2 of the present invention.
I got That is, as a monomer, Blemmer-AE-350
(Manufactured by NOF Corporation; polyethylene glycol monoacrylate; x = 6 to 8, y = z in the general formula (I))
= 0) 30.0 g, Bremma-AP-550 (manufactured by NOF Corporation; polypropylene glycol monoacrylate; y = 9 to 10, x = z = 0 in the general formula (I))
180.0 g and 90.0 g of dimethylaminoethyl acrylate were added, and 3.0 g of azobisisobutyronitrile and 7.5 g of lauryl mercaptan were further added and reacted at 90 ° C. for 8 hours. At 3 hours on the way, 3.0 g of azobisisobutyronitrile was added. The obtained solid substance (Compound 3) had a weight average molecular weight of 8,370 with a weight of 313.0 g.

Example 4 Compound 4 was prepared as an example of polymerized compound 2 of the present invention by using the same apparatus and operation as in Example 1.
I got That is, Blemmer AE-350 is used as a monomer.
(Manufactured by NOF Corporation; polyethylene glycol monoacrylate; x = 6 to 8, y = z in the general formula (I))
= 0) 30.0 g, Blemmer AP-550 (manufactured by NOF Corporation; polypropylene glycol monoacrylate; y = 9 to 10, x = z = 0 in the general formula (I))
180.0 g and 90.0 g of acrylamide were added,
Further, 3.0 g of azobisisobutyronitrile and 7.0 g of lauryl mercaptan were added and reacted at 90 ° C. for 8 hours. At 3 hours on the way, 3.0 g of azobisisobutyronitrile was added. The obtained solid substance (compound 4) had a weight average molecular weight of 9000 and 316.0 g.

Example 5 Compound 5 was prepared as an example of polymerized compound 2 of the present invention by using the same apparatus and operation as in Example 1.
I got That is, Blemmer AE-350 is used as a monomer.
(Manufactured by NOF Corporation; polyethylene glycol monoacrylate; x = 6 to 8, y = z in the general formula (I))
= 0) 30.0 g, Blemmer AP-550 (manufactured by NOF Corporation; polypropylene glycol monoacrylate; y = 9 to 10, x = z = 0 in the general formula (I))
180.0 g and 90.0 g of dimethylacrylamide
Azobisisobutyronitrile 3.0 g,
And lauryl mercaptan (6.5 g) at 90 ° C.
For 8 hours. At 3 hours on the way, 3.0 g of azobisisobutyronitrile was added. The obtained solid substance (compound 5) weighed 315.2 g and had a weight average molecular weight of 96.
00.

(Example 6) Concentrated fountain solutions 1 to 5 shown in Table 1 were prepared using the synthesized compounds 1 to 5.

[0049]

[Table 1]

However, the numbers in Table 1 represent g. Bestside 700 is a preservative manufactured by Dainippon Ink and Chemicals,
ETB indicates ethylene glycol mono-t-butyl ether, and HPC indicates hydroxypropyl cellulose manufactured by Shin-Etsu Chemical. Furthermore, in addition to this, 0.15 g of an antifoaming agent Megafax F-815 manufactured by Dainippon Ink and Chemicals, respectively.
Added

Next, each of the concentrated dampening solutions 1 to 5 according to the present invention was diluted 50-fold with water to prepare corresponding dampening solutions 1 to 5 for lithographic printing.

Separately, Comparative Examples 1 and 2 were prepared as comparative fountain solutions. Comparative Example 1 is a dampening solution containing isopropyl alcohol, which has been formulated for a long time, and contains 0.1 part of polyoxyethylene cetyl ether and 2 parts of citric acid.
Parts, 2 parts of phosphoric acid and 95.9 parts of water, using a concentrated fountain solution, 89.5 parts of water, 10 parts of isopropyl alcohol and 0.5 part of the above-mentioned concentrated fountain solution. It is. Comparative Example 2 was a formulation in which the action of isopropyl alcohol was replaced with an organic solvent, and water 570 was used.
Parts, hydroxypropylcellulose 19 parts, metaphosphoric acid 1 part, citric acid 5 parts, sodium nitrate 27 parts, Bestsite 700 8 parts, ethylene glycol mono-t-butyl ether 200 parts, polypropylene methyl ether 120
And 50 parts of butyl carbitol, diluted 50 times with water, and added 0.003 part of Megafac F-815 to obtain a fountain solution.

Table 2 shows fountain solution characteristics of the fountain solutions 1 to 5 and Comparative Examples 1 and 2 according to the present invention. The dynamic surface tension is a value at the maximum bubble pressure method at 25 ° C., and the plate test is performed by immersing a positive PS plate RP (manufactured by Polychrome Japan) in dampened water at room temperature for 24 hours. , A: No change at all, B: Slight change compared to the original,
C: change was observed but to the extent that there was no problem. D: partial plate printing occurred. E: overall evaluation of the plate printing in five stages. In the ink emulsification test, the dampening water holding power of the ink is measured by a dactet tester (manufactured by Kawamura Riken) using the ink "Gios G-Red N Type" (manufactured by Dainippon Ink and Chemicals) at setting conditions of 1500 rpm / 60 rpm and 40 ° C. Value.

[0054]

[Table 2]

From Table 2, it can be seen that the fountain solution of the present invention and the fountain solution to which 10% of isopropyl alcohol is added show the same value in terms of dynamic surface tension. In the ink emulsification test, all of the samples showed the same characteristics as the measurement ink in the ink emulsification test. From this, it can be seen that the fountain solution of the present invention is excellent in dynamic surface tension and plate printing, and has no problem in terms of the emulsifying properties of the ink as well as the fountain solution of the comparative example.

(Example 7) Printing tests were performed using dampening solutions 1 to 5 of the present invention and comparative example dampening solutions 1 and 2. The printing conditions are as follows. Printing machine: Roland R-700 (manufactured by Roland), printing speed: 10,000 sheets / 1 hour, printing paper: Jujo diamond coat 57.5 kg / A, dampening water mechanism: Rolandmatic, temperature and humidity: 23 to 24 ° C., 50-60% RH,
Ink: Geos G Beni-S (manufactured by Dainippon Ink and Chemicals),
PS version: RP (Polychrome Japan)

Each of the dampening solutions was subjected to a printing test of 10,000 parts, and the stains, water width, foaming and the degree of stain return of the printed matter were judged. Table 3 shows the results.

[0058]

[Table 3]

In Table 3, the stain on the printed matter was 10,0.
The degree of dirt in the non-image area after printing 00 copies is indicated by ○: no dirt,
x: Evaluation was made in terms of occurrence of stains and no printed matter. The water width is a water dial value when the amount of water supplied to the plate surface is reduced and the printed matter is stained. A smaller value indicates that the non-image area can be uniformly protected with a smaller amount of dampening water. The degree of foaming was evaluated by ◎: no foaming, ：: foaming was observed but no problem in printing, and x: foaming was severe and printing was difficult. Soil return was performed using isopropyl alcohol after printing the 5,000 copies of the printed material, stopping the printing machine for 10 minutes, and then restarting printing. The dampening solution was ○: standard, ◎: recovered at 2/3 or less of standard, Δ: standard of 1.
The recovery was at least three times, and x was evaluated based on the evaluation criteria for no recovery.

From the results shown in Table 3, it can be seen that the fountain solution according to the present invention does not contain isopropyl alcohol, but has the same or higher printability as the fountain solution containing isopropyl alcohol.

[0061]

The fountain solution composition of the present invention has both a film forming property and a surface active effect. Further, the concentrated fountain solution for lithographic printing containing the fountain solution composition for lithographic printing according to the present invention is a concentrated fountain solution which does not contain IPA and which is excellent in liquid stability and conforms to the regulations of the Fire Service Law and the Industrial Safety and Health Law. Water,
The fountain solution for lithographic printing prepared by diluting the concentrated fountain solution according to the present invention is a fountain solution having excellent fountain solution properties that a high-quality printed material free of stains on the printed material and no plate trace is easily obtained. It is water.

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Koji Oe 5-905 Higashima, Kitamoto-shi, Saitama 2-505 Kitamoto Kitamoto

Claims (6)

[Claims] 1. A fountain solution composition for lithographic printing, characterized in that it is a polymer or copolymer obtained from at least one monomer represented by the following general formula (I). ## STR1 ## Formula (I) (Wherein R is H ₂ C ＝ CH— or H ₂ C ＝ C (CH ₃ )
Represents-. X, y and z each represent 0 or an integer of 1 to 20. However, x + y + z is an integer of at least 1 or more. ) 2. The fountain solution composition for lithographic printing according to claim 1, wherein the polymer or copolymer has a weight average molecular weight of 230 to 100,000. 3. An acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-isopropylacrylamide, acrylamide, N-methylacrylamide, N-propylacrylamide, N-isopropylacrylamide, -(Dimethylaminomethyl) acrylamide, N- (dimethylaminoethyl) acrylamide, N- (dimethylaminopropyl) acrylamide,
N, N-dimethylacrylamide, N-methyl-N-ethylacrylamide, acrylic acid, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, 3- (acrylamidyl) butylsulfonic acid, 4- (acrylamidyl) ) Butylsulfonic acid, 3-
(Acrylamidyl) propylsulfonic acid, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, N- (dimethylaminomethyl) methacrylamide, N- (dimethyl Aminoethyl) methacrylamide, N- (dimethylaminopropyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-ethylmethacrylamide, methacrylic acid, dimethylaminomethyl methacrylate, dimethyl methacrylate Aminoethyl ester, 3- (methacrylamidyl) butylsulfonic acid, 4- (methacrylamidyl) butylsulfonic acid, 3- (methacrylamidyl) propylsulfonic acid, aryl group Call and acryloyl fountain solution composition which is a copolymer obtained from at least one or more water-soluble monomers selected from among morpholine. 4. The weight average molecular weight of the copolymer is 3
The fountain solution composition for lithographic printing according to claim 3, which is a copolymer having a size of from 00 to 200,000. 5. The above copolymer contains 99.5% by weight of a monomer represented by the general formula (I) as a monomer composition ratio.
The fountain solution composition for lithographic printing according to claim 3, wherein the fountain solution is a copolymer containing between 3 and 40.0% by weight. 6. The fountain solution composition for lithographic printing according to claim 1, 2, 3, 4 or 5.
Concentrated dampening solution for lithographic printing, characterized by containing from 01 to 20% by weight.