JP2022182875A - Moistening water composition for offset-printing, and concentrated moistening water composition - Google Patents

Abstract

To provide a moistening water composition for offset-printing excellent in developavility in initial printing, and favorable in reduction of contamination of a water supply roller when using for a long time, stable water width aptitude small in emulsification change, and surface-adjusting properties when re-operating a printing machine after stoppage.SOLUTION: The moistening water composition for offset-printing is a moistening water composition used for offset-printing which contains a phosphorus-containing compound, and 3,6-dimethyl-4-octine-3,6-diol.SELECTED DRAWING: None

Description

The present invention relates to dampening water compositions for offset printing and dampening water concentrate compositions.

Offset printing is a printing method using a planar printing plate without unevenness, and is mainly used for printing applications such as magazines, books, newspapers and commercial advertisements. Offset printing plates consist of oleophilic image areas that accept ink during the printing process and hydrophilic non-image areas that accept dampening water. A conventional offset printing plate is made by mask-exposing a plate having a lipophilic photosensitive resin layer on a hydrophilic support through a lith film, and then dissolving and removing the non-image area with a developer. (PS version) was common.
In recent years, computers electronically process, store, and output images as digital information. Therefore, the image forming process according to the digital image information forms an image directly on the offset printing original plate by scanning exposure using actinic radiation with high directivity such as laser light, without going through the lith film. A plate is made by dissolving and removing the image area with a developer. A technique for making a printing plate from digital image information without using a lith film is called computer-to-plate (CTP).

In offset printing, the prepared printing plate is set in the printing press, dampening water is applied to the surface of the printing plate using a water supply roller, and the non-image area of the printing plate is covered with the dampening water. It is printed by putting it on the part and then transferring the ink to the paper. Offset printing uses the property that water and oil do not mix. Good print quality can only be obtained if the ink loaded is stable. In order to stabilize the ink for a long time from the start of printing and to obtain high-quality printing, various chemical substances are added to the dampening water, and we diligently study to maximize its performance. It has been.

Patent Document 1 discloses a compound consisting of a propylene oxide group and an ethylene oxide group, sodium alkylbenzenesulfonate or sodium dialkylsulfosuccinate, and 2,5,8,11-tetramethyl-6-dodecine-5,8-diol or 2, A dampening solution concentrate composition for offset printing comprising 5,8,11-tetramethyl-6-decyne-5,8-diol, and containing these substances in combination to reduce waste from printing It does not cause troubles such as roller peeling and poor transfer during long-run printing, and maintains wettability in non-image areas during high-speed printing. It is

In these printing plates using conventional PS plates and CTP plates, during plate making, a step of dissolving and removing the non-image area after exposure (development processing), and after washing the developed printing plate with water, a surface active agent is added. It requires a post-treatment process of treating with a rinsing solution and then treating with a desensitizing solution containing gum arabic or a starch derivative, and the environmental burden caused by the waste liquid in each treatment has been a problem.

Therefore, in order to reduce the amount of materials used and waste from the perspective of reducing the environmental impact, non-processing type (on-machine development type) offset printing plates that do not use these additional processes have been developed. It's been done. In offset printing using such a non-process offset printing plate, the plate after image formation is set in the printing press as it is, and the same process as printing is started, and the plate is made non-toxic by permeating and swelling dampening water. A process called "on-machine development" is performed in which the image area is peeled off using the tackiness of the ink and washed off with dampening water to remove it, and then printing is performed. In the process of on-press development, when dampening water, which is usually used for conventional PS plates and CTP plates, is used, the non-image areas are not sufficiently peeled off, and stains occur in the non-image areas of the resulting printed matter, resulting in printing problems. Problems peculiar to on-press development sometimes occurred, such as an increase in initial wasted paper.

Patent Document 2 discloses a fountain solution composition for offset printing containing a polymer having at least one structure selected from the group consisting of a polyallylamine structure, a polyallylamine salt structure, a polydiallylamine structure, and a polydiallylamine salt structure. and is excellent in suppressing dampening water contamination and ink receptivity, and can also be used for on-press development.

However, in recent years, from the aspect of printing cost, there is an increasing demand for offset printing to achieve high quality and high speed printing in a short time while maintaining high print quality.
In offset printing using dampening water, if the ink remains in the non-image areas where the dampening water permeates, the printing will be smeared, leading to a decrease in print quality. For this reason, the aptitude required for dampening water is the ability to produce clean prints in a short period of time after the start of printing (printability), and the ability to print clean prints in a short time after restarting the printing press. In the case of on-press development type printing plates, the ability to wash off the developed photosensitive film (on-press developability) is required.
At the same time, there is a demand for high-quality printing even when printing for long periods of time. If dirt derived from ink components accumulates on the surface of the water supply roller, it will lead to a decline in printing quality. Even if the amount of water emulsified in the ink changes (water width) during long-term printing, the ink can be stably emulsified in the dampening water, and the printing quality of the image area is not affected. It was required of dampening water not to give. However, until now there has been no dampening solution that satisfies all these demands for high quality and high speed.

JP 2009-126132 A Japanese Patent Application Laid-Open No. 2020-104338

Therefore, the present invention provides excellent printability in the early stage of printing, reduction of water supply roller contamination during long-term use, stable water width suitability with little change in emulsification, and alignment when restarting the printing press after stopping. An object of the present invention is to provide a dampening water composition for offset printing having good surface properties.
In addition, when the dampening solution of the present invention is used for on-press development type printing, the dampening solution composition for on-press development offset printing has excellent on-press developability that allows on-press development to be performed in a short time. The purpose is to provide goods.

The present inventors have achieved the above object by providing a fountain solution composition for offset printing characterized by containing a phosphorus-containing compound and 3,6-dimethyl-4-octyne-3,6-diol. can be achieved, and have completed the present invention.

That is, the present invention
(1) A fountain solution composition for offset printing, comprising a phosphorus-containing compound and 3,6-dimethyl-4-octyne-3,6-diol;
(2) The dampening water composition for offset printing according to (1), containing 0.001 to 1 part by mass of the 3,6-dimethyl-4-octyne-3,6-diol.
(3) The dampening water composition for offset printing according to (1) or (2), which further contains polyoxyethylene polypropylene glycol;
(4) The fountain solution composition for offset printing according to any one of (1) to (3), wherein the polyoxyethylene polypropylene glycol has a number average molecular weight of 1,000 to 11,000.
(5) The method according to any one of (1) to (4), wherein the offset printing plate is exposed and used for on-press development in which the offset printing plate is set on the printing press and printing is started without chemical treatment after exposure. The dampening solution composition for offset printing described in
(6) A concentrated dampening water composition for offset printing that becomes the composition of the dampening water composition for offset printing according to any one of (1) to (5) by diluting with water;
is.

According to the present invention, excellent printability at the beginning of printing, reduction of water supply roller contamination during long-term use, stable water width suitability with little change in emulsification, and when restarting the printing press after stopping It is possible to provide a dampening water composition for offset printing with good surface regularity.
Further, when the dampening solution of the present invention is used for on-press development type printing, the dampening solution composition for on-press development offset printing also has excellent on-press developability that enables on-press development to be performed in a short time. can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is merely one form for carrying out the present invention, and the present invention is not limited by the present embodiment, and various modifications and embodiments can be made without departing from the gist of the present invention. is possible.

In the present specification, "-" indicates that upper and lower limits are included unless otherwise specified. Further, the molecular weight is the number average molecular weight obtained by measuring the hydroxyl value unless otherwise specified.

The dampening water composition for offset printing according to the present invention is suitable both in the offset printing method for an offset printing plate in which development is performed using a developer and in the method for preparing an offset printing plate and the offset printing method in which on-press development is performed. can be used for Above all, the dampening water composition according to the present invention can be particularly suitably used as a dampening water composition for offset printing in which on-press development is performed.
The dampening water composition is often concentrated and commercialized on a commercial basis. use as an object.

The dampening water composition for offset printing of the present invention will be described in detail below.

The fountain solution composition of the present invention preferably contains a phosphorus-containing compound and 3,6-dimethyl-4-octyne-3,6-diol.

3,6-Dimethyl-4-octyne-3,6-diol, when used in combination with a phosphorus-containing compound, has excellent printability in the early stages of printing, reduces contamination of the water supply roller during long-term use, and improves emulsification. It has the effect of stabilizing water width aptitude with little change, and of improving surface smoothness when the printing press is restarted after being stopped. This can be obtained from Fuji Film Wako Pure Chemical Industries, Ltd. and the like.

The content of 3,6-dimethyl-4-octyne-3,6-diol is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, relative to the dampening water composition. more preferred. If the amount exceeds 1% by mass, the dampening water is over-emulsified in the ink, and the printability at the initial stage of printing may deteriorate. Width aptitude and printability at the initial stage of printing may deteriorate, and dirt may accumulate on the water supply roller during long-term printing.

As the compound containing phosphorus, a phosphoric acid-based compound is preferable. Specific examples of phosphoric acid compounds include phosphoric acid, phosphonic acid, phosphinic acid, phytic acid, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid (tripolyphosphoric acid, tetraphosphoric acid, etc.), metaphosphoric acid, and ultraphosphoric acid. Among these, phosphoric acid and phytic acid are particularly preferred. These phosphoric acid compounds may be contained as phosphates, preferably at least one selected from among them, and two or more of them may be used in combination. Examples of the salts include alkali metal salts, alkaline earth metal salts or ammonium salts of the above organic acids and/or inorganic acids, and organic amine salts. Specific examples include ammonium nitrate, phosphate, citrate, and p-toluenesulfonate are preferred.

The content of the phosphorus-containing compound is preferably 0.25 to 90 mg/l, more preferably 15 to 80 mg/l, relative to the dampening water composition. If it exceeds 90 mg/l, there is a possibility that the image area may be affected, and there is a concern that the quality of the paper surface will be deteriorated. If it is less than 0.25 mg/l, the surface smoothness is lowered, and the water supply roller may be stained.

Preferably, the dampening water composition for offset printing of the present invention further contains polyoxyethylene polypropylene glycol.

The polyoxyethylene polypropylene glycol preferably has a molecular weight of 1,000 to 11,000. If the molecular weight is less than 1,000 or more than 11,000, water width aptitude may be deteriorated.
Here, the molecular weight is the number average molecular weight obtained by measuring the hydroxyl value of polyoxyethylene polypropylene glycol.

The content of the polyoxyethylene polypropylene glycol is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.1% by mass, relative to the dampening water composition. When used in combination with a phosphorus-containing compound within the range, it has the effect of improving developability and water width aptitude.

<Water>
The dampening solution composition for offset printing of the present invention uses water as a solvent.
Water is not particularly limited, and may be tap water, well water, distilled water, ion-exchanged water, pure water, or the like. Among them, it is preferable to use distilled water, ion-exchanged water, or pure water.
The content of water, which is the remainder other than the components described later, is preferably 10% by mass or more, and 20% by mass or more and 99.99% by mass or less, based on the total mass of the dampening water composition. more preferably 30% by mass or more and 99.9% by mass or less, and particularly preferably 40% by mass or more and 99% by mass or less.

<pH adjuster>
Further, the dampening water composition for offset printing of the present invention is preferably adjusted to a preferred pH value with a pH adjuster. It is preferable to use the pH value in the acidic range of 3-7, but it can also be used in the alkaline range of pH 7-11. A water-soluble organic acid, an inorganic acid, or a salt thereof can be used as the pH adjuster.
Preferred organic acids include acetic acid, citric acid, oxalic acid, malic acid, tartaric acid, succinic acid, lactic acid, ascorbic acid, gluconic acid, hydroxyacetic acid, malonic acid, phthalic acid, levulinic acid, sulfanilic acid, p-toluenesulfonic acid, Phytic acid, organic phosphonic acid, and the like. Examples of inorganic acids include nitric acid, sulfuric acid, and polyphosphoric acid. Phosphoric acid and phosphoric acid may be used. Alkaline earth metal salts, ammonium salts, or organic amine salts are also suitably used. You may use these as a mixture of 2 or more types. The content of these pH adjusters in dampening water is generally in the range of 0.001 to 0.3 mass %.

<Chelate compound>
The dampening water composition for offset printing of the present invention may contain a chelate compound. In particular, when the dampening water composition is diluted with tap water, well water, or the like and used as dampening water, the inclusion of the chelate compound allows printing of calcium ions, etc. contained in the diluted tap water or well water. It is possible to suppress the influence on the printed matter and suppress the smudge on the printed matter.
Chelate compounds include, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; , its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2-propanoltetraacetic acid, its Aminopolycarboxylic acids such as potassium salts, sodium salts thereof, 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salts thereof, sodium salts thereof; 2-phosphonobutanetricarboxylic acid-2,3,4 , its potassium salt, its sodium salt; 1-phosphonoethanetricarboxylic acid-1,2,2, its potassium salt, its sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt, its sodium salt organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri(methylenephosphonic acid), its potassium salt, its sodium salt, and the like.
Ammonium or organic amine salts are also effective in place of the sodium or potassium salts of the above chelating agents.

The chelate compound may be contained singly or in combination of two or more.
The content of the chelate compound is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass, relative to the total mass of the dampening water composition.

<Organic solvent>
From the viewpoint of improving wettability, the dampening water composition for offset printing of the present invention may contain an organic solvent such as glycols and/or alcohols as a wetting agent.
Glycols include propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and pentapropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butylene glycol, hexylene glycol, ethylene glycol monotertiary butyl ether, Propylene glycol monobutyl ether and the like can be mentioned, among which propylene glycol, ethylene glycol monotertiary butyl ether and propylene glycol monobutyl ether are more preferred.
Alcohols include ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, isobutyl alcohol, t-amyl alcohol, benzyl alcohol, pentaerythritol, methoxyethanol, ethoxyethanol and butoxyethanol.

The dampening water composition for offset printing of the present invention may contain one type of organic solvent alone, or two or more types thereof. The content of the organic solvent is preferably 0.1% by mass to 6% by mass, more preferably 0.3% by mass to 2% by mass, relative to the total mass of the dampening water composition. If it exceeds 6% by mass, the ink may be over-emulsified, and if it is less than 0.1% by mass, the wettability to the printing plate surface may decrease.

The dampening water composition contains a diol-based acyclic hydrocarbon having two OH groups, the shortest number of carbon atoms between the two OH groups being 2 to 6, and the total number of carbon atoms being 9. It may contain a compound. Assuming that the shortest number of carbon atoms between OH groups is 2, specifically, 1,2-nonanediol, 2,3-nonanediol, 3,4-nonanediol, 2-methyloctane-2,3-diol , 2-methyl-3,4-octanediol, 2,2,5-trimethyl-3,4-hexanediol, 3,3-dimethyl-1,2-heptanediol, 2-ethylheptane-1,2-diol , 3-ethyl-5-methyl-1,2-hexanediol, 2,3-dimethylheptane-2,3-diol, 3-ethyl-4-methylhexane-3,4-diol, 4-methyl-4, 5-octanediol, 3-isopropyl-4-methyl-2,3-pentanediol and the like. Specific examples of those having 3 carbon atoms between OH groups are 2-butyl-2-ethyl-1,3-propanediol, 2,4-dimethylheptane-3,5-diol, 1,3 -nonanediol, 2,4-nonanediol, 4,6-nonanediol, 2,4-dimethylheptane-1,3-diol, 2,4-dimethyl-3,5-heptanediol, 2,2-dimethyl- 3,5-heptanediol, 2,6-dimethyl-3,5-heptanediol, 3,4-dimethyl-3,5-heptanediol, 2-methyloctane-3,5-diol, 2,6-dimethylheptane -3,5-diol, 2-[(1R)-1-methyl-3-methylbutyl]-1,3-propanediol, 2-sec-butyl-2-ethyl-1,3-propanediol, 2-butyl -2-ethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2-hexylpropane-1,3-diol, 2-methyl-2-(1-methylbutyl)- 1,3-propanediol, 2-methyl-2-pentyl-1,3-propanediol, 2-methyl-2,4-octanediol, 2-methyloctane-1,3-diol, 2,2-dipropyl- 1,3-propanediol, 2,4,5-trimethylhexane-2,4-diol, 2,2,4,4-tetramethylpentane-1,3-diol, 2,4-dimethylheptane-2,4 -diol, 3-propyl-1,3-hexanediol, and the like. Examples of those having 4 carbon atoms at the shortest between OH groups include 1,4-nonanediol, 2,5-nonanediol, 3-methyloctane-1,4-diol, 4,6-dimethyl- 2,5-heptanediol, 2-(1,2-dimethylpropyl)butane-1,4-diol, 2-isopentyl-1,4-butanediol, 2-ethyl-1,4-heptanediol, 2,2 ,3,3-tetramethyl-1,4-pentanediol, 2,4-dimethylheptane-1,4-diol, 4-methyloctane-1,4-diol, 6,6-dimethyl-2,5-heptane and diols. As the shortest carbon number between OH groups is 5, specifically, 1,5-nonanediol, 2,6-nonanediol, 2,4-diethyl-1,5-pentanediol, 4,6- dimethylheptane-1,5-diol, 2,6-dimethylheptane-1,5-diol, 2-isopropyl-1,5-hexanediol, 2-ethyl-1,5-heptanediol, 2,6-dimethyl- 2,6-heptanediol, 3,3,5-trimethylhexane-1,5-diol, 6,6-dimethyl-1,5-heptanediol, 7-methyl-1,5-octanediol and the like. Specific examples of those having 6 carbon atoms between OH groups are 1,6-nonanediol, 2-methyl-2,7-octanediol, and 2,2,4-trimethyl-1,6-hexane. diol, 2,4,4-trimethyl-1,6-hexanediol, and the like. Among them, 2-butyl-2-ethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol are preferred.
It is at least one selected from these, and may be used in combination of two or more, and may be used in combination with the organic solvent.

<Water-soluble polymer compound>
The dampening solution composition for offset printing of the present invention may contain a water-soluble polymer compound. Specific examples of water-soluble polymer compounds include gum arabic, starch derivatives (e.g., dextrin, enzymatically decomposed dextrin, hydroxypropylated enzymatically decomposed dextrin, carboxymethylated starch, phosphate starch, octenyl succinated starch, etc.), alginate, Natural products of cellulose derivatives (e.g., carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, their glyoxal denatured products, etc.) and their modified products, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, polyacrylamide and copolymers thereof, polyacrylic acid and its copolymers, vinyl methyl ether/maleic anhydride copolymers, vinyl acetate/maleic anhydride copolymers and the like.
At least one selected from these is preferable, and two or more may be used in combination.
The content of the water-soluble polymer compound is preferably 0.00005% by mass to 0.5% by mass, more preferably 0.0005% by mass to 0.05% by mass, relative to the total mass of the dampening water composition. It is more preferable to have If the amount exceeds 0.5% by mass, the ink may be over-emulsified, and if the amount is less than 0.0005% by mass, the paper surface may be stained.

<Group consisting of saccharides and glycerin>
The fountain solution composition of the present invention may contain the group consisting of sugars and glycerin. Sugars can be selected from monosaccharides, disaccharides, oligosaccharides, and the like, including sugar alcohols obtained by hydrogenation. Specific examples 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-arlo-heptulose, β-D-altro-3-heptulose, saccharose, lactose, D - maltose, isomaltose, inurobiose, hyalbiouron, maltotriose, D,L-arabit, ribbit, xylit, D,L-sorbit, D,L-mannitol, D,L-idit, D,L-talit, dulcit , allodulcit, maltitol, and reduced starch syrup.
At least one selected from these is preferable, and two or more may be used in combination.

The content of the group consisting of sugars and glycerin is 0 to 5% by mass, more preferably 0 to 4% by mass, and preferably 0.01 to 3% by mass, relative to the dampening water composition. More preferred.

The fountain solution composition of the present invention may contain polyethylene oxide and propylene oxide adducts of ethylenediamine. As polyethylene oxide and propylene oxide addition compounds of ethylenediamine, the polypropylene glycol portion (hydrophobic group) has a molecular weight of 1,500 to 5,000, the ethylene oxide addition weight % in the total molecule is 10 to 40%, and the molecular weight is 2,000. Among them, those having a molecular weight of 2,000 to 4,000 in the polypropylene glycol portion and 10 to 20% by weight of ethylene oxide added to the total molecules are more preferable.
The content of these addition compounds is 0 to 5% by mass, more preferably 0.0001 to 3% by mass, more preferably 0.001 to 2% by mass, relative to the dampening water composition. preferable.

<Surfactant>
The dampening solution compositions of the present invention may contain small amounts of surfactants. Surfactants such as anionic surfactants include fatty acid salts, abietates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, straight-chain alkylbenzenesulfonates, and branched-chain alkylbenzenesulfonates. , alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyltaurate sodium salts, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfones acid salts, hydrogenated castor oil, sulfated beef tallow, fatty acid alkyl ester sulfate salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride sulfate ester salts, polyoxyethylene alkylphenyl ether sulfate ester salts, poly Oxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, partially saponified styrene-maleic anhydride copolymers, olefin-anhydride Partially saponified products of maleic acid copolymers, naphthalenesulfonate formalin condensates, and the like, among which dialkylsulfosuccinates, alkylsulfuric acid ester salts and alkylnaphthalenesulfonates are preferably used.
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters. , pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid partial esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyglycerin fatty acid partial esters, polyoxy Ethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N,N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, etc. Among them, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers, acetylene glycols, acetylene alcohols, and their ethylene oxide and/or propylene oxide adducts are preferably used.
Cationic surfactants include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives and the like.
Examples of amphoteric surfactants include alkyl imidazolines.
Furthermore, a fluorosurfactant is mentioned. Fluorinated anionic surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, and perfluoroalkyl phosphate esters. Fluorinated nonionic surfactants include perfluoroalkyl ethylene oxide adducts and perfluoroalkyl surfactants. Propylene oxide adducts and fluorine-based cationic surfactants include perfluoroalkyltrimethylammonium salts and the like.
Considering foaming problems and emulsification with ink, the content of these surfactants is preferably 5% by mass or less, more preferably 0 to 2% by mass, based on the dampening water composition.

<Preservative>
From the viewpoint of storage stability, the dampening solution composition for offset printing of the present invention preferably contains a preservative.
Specific examples of preservatives include benzoic acid and its derivatives, phenol or its derivatives, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benztriazole derivatives, amidine or guanidine derivatives, quaternary ammonium. salts, pyridine, quinoline or guanidine derivatives, diazine or triazole derivatives, oxazole or oxazine derivatives, halogenonitropropane compounds, bromonitropropanol of the bromonitroalcohol series, 1,1-dibromo-1-nitro-2-ethanol, 3-bromo-3-nitropentane-2,4-diol and the like.

The dampening water composition for offset printing of the present invention may contain one preservative alone or two or more.
The content of the preservative varies depending on the type of bacteria, fungi, and yeast, but is preferably 0.0001% by mass to 1% by mass of the total mass of the dampening water composition.

<Other additives>
The dampening water composition for offset printing of the present invention may contain additives other than those mentioned above.
Other additives are not particularly limited, and known additives can be used, and examples thereof include coloring agents, antirust agents, antifoaming agents, fragrances, masking agents, and the like.
Food dyes and the like can be preferably used as the coloring agent. For example, as a yellow pigment, CI No. 19140, 15985, and CI No. 15985 as a red dye. 16185, 45430, 16255, 45380, 45100, and CI No. as purple dyes. 42640, and CI No. 42640 as a blue dye. 42090, 73015, and CI No. 42090 and 73015 as green dyes. 42095 and the like.
Rust inhibitors include, for example, benzotriazole, 5-methylbenzotriazole, thiosalicylic acid, benzimidazole and derivatives thereof.
The antifoaming agent is preferably a silicone antifoaming agent. Both emulsifying and dispersing type and solubilizing type can be used as the silicone antifoaming agent. Also, a non-silicone antifoaming agent can be used in combination or alone.

The dampening solution composition for offset printing of the present invention further contains corrosion inhibitors such as magnesium nitrate, zinc nitrate, calcium nitrate, sodium nitrate, potassium nitrate, lithium nitrate and ammonium nitrate, and hardening agents such as chromium compounds and aluminum compounds. , cyclic ethers: organic solvents such as 4-butyrolactone, water-soluble surface-active organometallic compounds, and the like.

The content of these other additives is preferably 0.0001% by mass to 1% by mass based on the total mass of the dampening water composition.

<Print version>
The fountain solution composition of the present invention can be used for various offset printing plates.
For example, offset printing obtained by imagewise exposing and developing a photosensitive offset printing plate having an aluminum plate as a support and a photosensitive layer thereon (a printing plate that has been given photosensitivity in advance and is called a PS plate). Suitable for printing plates.
It can also be suitably used for CTP offset printing plates (CTP plates) that are directly exposed to visible or infrared lasers. Specific examples include photopolymer type digital plates (eg, Kodak LLC: Exthermo TP-W) and thermal positive type digital plates (eg, Fuji Film Global Graphic Systems Co.: XP series). .
The present invention can also be suitably used for non-process offset printing plates. Process-less offset printing plates are directly exposed to visible or infrared laser light on a printing press, washed off non-image areas other than the exposed areas with a dampening water composition, and then printed by a common offset printing method. Therefore, processing-less offset printing plates do not require the post-processing steps such as development processing, washing with water, and rinsing liquid processing used in conventional PS plates and CTP plates, so that these wastes are not discharged. Process-less offset printing plates include, for example, BLUE EARTH (manufactured by Konica Minolta Business Solutions Co., Ltd.), SUPERIA ZD series (manufactured by Fujifilm Global Graphic Systems Co., Ltd.), Azura series (manufactured by Agfa-Gewalt Japan Co., Ltd.). ), SONORA series (manufactured by Kodak LLC), and the like.

<Offset printing method>
In order to use the PS plate, CTP plate and non-process offset printing plate described above, the offset printing plate is prepared and used to form a printed matter through a printing process according to a general offset printing method.

As the base material used for the printed matter of the present invention, any paper can be used as long as it can be used for ordinary offset printing. Paper and the like are preferably used.

<On-machine development>
The dampening solution for offset printing according to the present invention is suitably used in both the offset printing method for an offset printing plate in which development is performed using a developer, and the offset printing plate preparation method and offset printing method in which on-press development is performed. can do.

<On-machine development process>
In a process called on-press development, the image-recording layer in the non-image area is formed by supplying the printing ink and the dampening water composition for offset printing of the present invention on the printing press to the image-exposed offset printing plate precursor. is removed to produce an offset printing plate.
That is, after image exposure, the offset printing plate precursor is mounted on the printing press as it is without any development treatment, or after mounting the offset printing plate precursor on the printing press, image exposure is performed on the printing press, and the printing ink and the book are printed. When printing is performed by supplying the water-diluted dampening solution composition for offset printing of the present invention, in the initial stage of printing, in the non-image area, the components of the supplied printing ink and dampening solution cause non-uniformity. The image recording layer in the image area swells, dissolves or disperses and is removed, and the hydrophilic surface is exposed in the removed area. On the other hand, in the image area, the image-recording layer forms a printing ink-receiving area having an oleophilic surface.
In this way, the offset printing plate precursor is developed on-press on a printing press, and after the image-recording layer in the non-image area is removed, it is used as it is for printing a large number of sheets. As the printing ink, printing ink for normal offset printing is preferably used.

The dampening solution for offset printing according to the present invention can effectively swell the non-image area of the on-press developing printing plate in the on-press development step, and wash away the peeled off image-recording layer of the non-image area. Therefore, it can be preferably used.

<Dampening water concentrated composition>
When used on a commercial basis, dampening water is often concentrated and commercialized, and when used, the concentrated dampening water composition for offset printing is appropriately diluted with water and used as the dampening water composition.
The concentrated dampening water composition for offset printing of the present invention is diluted with water 1.1 to 1,000 times to obtain the composition of the dampening water composition for offset printing of the present invention. If the dilution with water is less than 1.1-fold, the ingredients do not exhibit sufficient effects, and if the dilution is greater than 1,000-fold, over-emulsification may occur during printing, possibly impairing printability.

The water used for diluting the concentrated dampening water composition of the present invention is not particularly limited, and may be tap water, well water, distilled water, ion-exchanged water, pure water, or the like. Among them, it is preferable to use distilled water, ion-exchanged water, or pure water.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In the examples, "part" means "mass part" and "%" means "mass%".

Materials used in Examples and Comparative Examples are listed in Table 1.

[Preparation of concentrated dampening water composition and dampening water composition]
Concentrated dampening water compositions for offset printing were prepared according to the formulations in Tables 2 and 3, respectively. The resulting concentrated dampening water composition for offset printing was diluted 50 times with tap water to prepare dampening water compositions for Examples 1 to 11 and Comparative Examples 1 to 6, respectively.

The dampening water compositions for offset printing of Examples 1 to 11 and Comparative Examples 1 to 6 were subjected to an on-press development printing test using an on-press development type printing plate under the following conditions. was evaluated, and the results are shown in Table 4.
Printing machine: Kikuzen size single-sided four-color machine manufactured by Komori Corporation Printing speed: 12,000 sph
Printing version: SONORA CX2 manufactured by Kodak LLC
Printing ink: VP NS New Cervo Y type manufactured by Tokyo Ink Co., Ltd. Paper: OK Coat L manufactured by Nippon Paper Industries Co., Ltd.

[On-machine developability]
During the above-mentioned on-press development printing test, the printing plate was placed on the printing press, dampening water and ink supply were started, and after printing about 20,000 sheets from the start of printing, no image was formed on the ink roller and dampening roller. It was evaluated by visual observation whether or not a residue such as a part remained.
The evaluation was made according to the following three grades: ⊚: no residue, ∘: almost no residue, and x: dirt remained.

In order to evaluate the printability, surface smoothness, water width suitability, and water supply roller contamination prevention suitability of the dampening solution compositions for offset printing of Examples 1 to 11 and Comparative Examples 1 to 6, printing was performed under the following conditions. Tested and evaluated. Table 4 shows the evaluation results.
Printing machine: Kikuzen size single-sided four-color machine manufactured by Komori Corporation Printing speed: 12,000 sph
Printing plate: XP-F (CTP plate) AM175 line manufactured by Fujifilm Global Graphic Systems Co., Ltd. Printing ink: VP NS New Cervo Y type manufactured by Tokyo Ink Co., Ltd. Paper: OK Coat L manufactured by Nippon Paper Industries Co., Ltd.

[Printability]
During the printing test, the printed matter was visually observed every 10 sheets from the start of printing, and the number of sheets at which entanglement stains in the mesh portion of the printed matter were no longer observed was evaluated. The evaluation was made on the following four scales: ⊚: less than 20 sheets, ∘: 20 to less than 30 sheets, Δ: 30 to less than 50 sheets, ×: 50 or more sheets.

[Smoothness]
During the printing machine test, after printing 20,000 sheets, the printing machine was stopped for 60 minutes, and then restarted to print.
The evaluation was made on a two-point scale, ⊚: no smearing of printing was observed, and ×: smearing of printing was observed.

[Water width suitability]
Printing was started with the dampening water feeding amount dial value set to 15, and when 10,000 sheets were printed, the dampening water feeding amount dial value was increased to 30 and 20,000 sheets were printed. It was evaluated that by increasing the feeding amount of dampening water, no smearing or density unevenness on the printed matter due to excessive emulsification occurred.
The evaluation was made on a two-point scale: ⊚: No smearing on the paper surface even when the feeding amount was increased; ×: Staining and density unevenness on the paper surface by increasing the feeding amount.

[Water supply roller dirt prevention suitability]
10,000 sheets were printed by the above printing test. After printing 10,000 sheets, contamination on the water supply roller was visually confirmed and evaluated.
The evaluation was carried out on a four-point scale of ⊚: no staining, ∘: almost no staining, Δ: slightly staining, and ×: the entire roll was stained.

The present inventors have provided a dampening water composition for offset printing characterized by containing a phosphorus-containing compound , 3,6-dimethyl-4-octyne-3,6-diol , and polyoxyethylene polypropylene glycol. As a result, the inventors have found that the above object can be achieved, and have completed the present invention.

That is, the present invention
(1) A fountain solution composition for offset printing, comprising a phosphorus-containing compound , 3,6-dimethyl-4-octyne-3,6-diol , and polyoxyethylene polypropylene glycol ;
(2) The dampening water composition for offset printing according to (1), containing 0.001 to 1 part by mass of the 3,6-dimethyl-4-octyne-3,6-diol.
(3) The dampening water composition for offset printing according to any one of (1) to ( 2 ), wherein the polyoxyethylene polypropylene glycol has a number average molecular weight of 1,000 to 11,000.
(4) Any one of (1) to ( 3 ), which is used for on-press development in which the offset printing plate is exposed, and printing is started by setting the offset printing plate on the printing press without performing chemical treatment after exposure. The dampening solution composition for offset printing described in
(5) A concentrated dampening water composition for offset printing that becomes the composition of the dampening water composition for offset printing according to any one of (1) to ( 4 ) by diluting with water;
is.

Claims (6)

A fountain solution composition for offset printing, comprising a phosphorus-containing compound and 3,6-dimethyl-4-octyne-3,6-diol. 2. The dampening solution composition for offset printing according to claim 1, comprising 0.001 to 1 part by mass of 3,6-dimethyl-4-octyne-3,6-diol. 3. The dampening solution composition for offset printing according to claim 1, further comprising polyoxyethylene polypropylene glycol. The fountain solution composition for offset printing according to any one of claims 1 to 3, wherein the polyoxyethylene polypropylene glycol has a number average molecular weight of 1,000 to 11,000. The dampening agent for offset printing according to any one of claims 1 to 4, which is used for on-press development in which the offset printing plate is exposed, and printing is started by setting the offset printing plate on the printing press without performing chemical treatment after exposure. litter water composition. A concentrated dampening water composition for offset printing that, when diluted with water, becomes the composition of the dampening water composition for offset printing according to any one of claims 1 to 5.