JPH1120331A - Concentrated dampening solution for lithographic printing - Google Patents

Abstract

(57) [Summary] The object of the present invention is to provide excellent liquid stability that does not contain isopropyl alcohol and conforms to the regulations of the Fire Service Law and the Industrial Safety and Health Law. It is an object of the present invention to provide a concentrated dampening solution capable of obtaining a dampening solution having excellent dampening solution characteristics that a high-quality printed matter free from defects can be easily obtained. SOLUTION: The concentrated fountain solution for lithographic printing contains a sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof as a fountain solution material for lithographic printing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a concentrated fountain solution for lithographic printing useful for offset printing of a lithographic printing plate.

[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.

In order 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 (for example, gum arabic and carboxymethyl cellulose) have been used. Adjust the solubility of various additives, such as various surfactants, acid such as phosphoric acid and citric acid as surface conditioning agent to remove plate surface oxides, and ammonium bichromate and nitrate as plate corrosion inhibitor Organic solvents and the like are 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 maintain 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 tend 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.

On the other hand, the anomeric position of the oligosaccharide (1 position,
As a compound in which an aromatic is introduced into aglycone as a protecting group for a hydroxyl group at a reducing end), JP-A-1-3111094
And Japanese Patent Application Laid-Open No. Sho 62-289595, and Japanese Patent Application Laid-Open No. Hei 2-28995 in which nitrophenyl was introduced as an optically measurable chromophore for measuring α-amylase in serum.
No. 11,595, and JP-A-63-183595 in which naphthalene, anthracene and the like are introduced, all of which use maltooligosaccharides composed of glucose as a sugar.

As for the alkyl derivative or alkylene derivative of an oligosaccharide, a derivative of a glucose polymer having sugar chains randomly bonded is known as a surfactant application, but its chemical structure is quite clear. (JP-A-58-194901; U.S. Pat. No. 3,839,318).

In the case of a sugar chain having a clear structure, a compound in which glucose has a 1 → 4 bond has been used. For example, the Journal of the American Oil Chemistry Society (Journal of the Ameri)
(can Oil Chemist's Society)
47 pages, 162; JP-A-1-68312.

[0010] Regarding the sulfated ester of sugar,
Sulfate esters of monosaccharides and polysaccharides have been known for a long time, and there are many references. For example, Advances in Carbohydrate Chemistry
in Carbohydrate Chemistr
y) Volumes 20, 183, 25, 407 and JP-A-1-103,601, 1-151,521, 1-254,701, 2-108,624, and 2
-145,601, 3-43,401 and WO
No. 89/03684 describes sulfated sugars, but none of them has a glycoside structure.

A sulfated oligosaccharide derivative in which a sugar hydroxyl group of an oligosaccharide derivative is sulfated is disclosed in JP-A-3-32.
No. 4,532, No. 5-78,382, No. 5-21
Nos. 3,982 and 5-279,381 are known, but no compounds have been known in which some of the hydrogen atoms of the hydroxyl groups are further aromatic-acylated.

US Pat. No. 4,840,815 discloses an esterified alkyl derivative comprising an oligosaccharide, which is an aliphatic esterified product. Further, in Japanese Patent Application Laid-Open No. 4-264102, compounds in which the sugar hydroxyl group of galactomannan is aliphatic, araliphatic or aromatic alkylated or esterified can be seen, but unlike the present invention, in the case of the sulfated compound, Absent.

Sulfate esters of oligosaccharide derivatives are disclosed in US Pat. No. 4,806,275 and JP-A-8-272,
No. 031 is known, but it was not used as a fountain solution material for lithographic printing. Japanese Unexamined Patent Publication (Kokai) No. 6-256373 discloses a compound in which a partial sugar hydroxyl group of an oligosaccharide derivative is sulfated and a part of the hydrogen atom of the hydroxyl group is aromatically acylated. As disclosed in JP-A-9-15,783.
In the issue, the effect of silver halide emulsion as a spreading agent,
It was not known at all as a good material for concentrated fountain solution for lithographic printing.

[0014]

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.

[0015]

SUMMARY OF THE INVENTION The object of the present invention is to provide a method wherein the hydrogen of the hydroxyl group at the 1-position of the terminal sugar of an oligosaccharide comprising the same or different monosaccharides as constituents is represented by the following general formula: A part of the hydrogen atoms of the sugar hydroxyl group except for the 1-position of the sugar moiety, which is substituted by (I), is aromatically acylated by a substituted or unsubstituted benzoyl group, and a part of the remaining unsubstituted hydroxyl group or This is achieved by a concentrated fountain solution for lithographic printing containing a sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof (hereinafter abbreviated as the compound of the present invention) as a fountain solution for lithographic printing. Was.

Formula (I) — (Q) _m — (O) _n —R (wherein R represents an alkyl group, alkylene group or alkynyl group having 1 to 30 carbon atoms which may be substituted,
m represents 0 or 1, n represents 0 or 1, Q represents an optionally substituted arylene group or a divalent heterocyclic group, and O represents an oxygen atom. n is 0 when m = 0
Represents 0 or 1 when m = 1. )

The sugars constituting the oligosaccharide of the compound of the present invention include glucose, galactose, mannose, xylose, fucose, talose, idose, altrose,
Aldoses such as allose, growth, arabinose, threose, lyxose, ribose, erythrose,
Polysaccharides such as aldoheptose, (2-deoxypentoses, 6-deoxyhexoses, 2-deoxyhexoses, 2,6-dideoxyhexoses, 3,
6-dideoxyhexoses), uronic acids such as iduronic acid, galacturonic acid, glucuronic acid, guluronic acid, mannuronic acid, 3-O-methylgalactose, 4-O-methylglucuronic acid, 3-O-methyl Glucose, 2,3-di-O-methyl glucose,
Acofuriose, Acobenose, Digitalose, 6-deoxy-2,3-di-O-methylgalactose, 6-deoxy-3-O-methylaltrose, 6-deoxy-
2-O-methylgalactose, tebetoose, oleandrose, salmentose, digitinose, simarose, carcose, sugar methyl ethers such as lancabose, apiose, alkanose, cladinose, chromose B, cordyseose, streptose, nobiose, hamamelose, micarose, Branched sugars such as thioglucose and methylthioribose, amosamine, canosamine, galactosamineuronic acid, glucosamineuronic acid, glucosamine, glosamine, talosamine, desosamine, galactosamine, neosamine, neumosamine, fucosamine, mannosaminonuronate, mannosamine, N-acetylgalactamine N-acetylglucosamine, N-acetylmuramic acid, 3-amino-3-deoxyribose, micaminose, mycosamine, The summing, the same monosaccharide or different monosaccharide selected from the group consisting of an amino sugars having an amino group or substituted amino group, such as N- methyl-glucosamine is used.

The number of monosaccharides constituting the oligosaccharide portion of the compound of the present invention varies depending on the type of saccharide used. However, the number of monosaccharides is usually determined due to the aggregation precipitation effect of the emulsion and the solubility in water, which are observed in the case of sulfated polysaccharide. It is preferably 32 or less. Particularly preferably, the oligosaccharide moiety of the compound of the present invention has 3 to 20 monosaccharides.

Glycosidic bonds between the monosaccharides of the compound of the present invention are (1 → 2), (1 → 3), (1 → 4), (1 → 4).
5) or (1 → 6). Also, the binding mode may be either α or β.

Specific examples of the oligosaccharide moiety of the compound of the present invention include xylo-oligosaccharides, galacto-oligosaccharides, gluco-oligosaccharides, mannooligosaccharides, fructooligosaccharides,
Glycosaminooligosaccharides, homooligosaccharides such as uronic acid oligosaccharides, oligosaccharides composed of pentose and hexose, oligosaccharides composed of different hexoses, oligosaccharides containing deoxy sugar, oligosaccharides containing amino sugar and uronic acid, amino sugar Heterooligosaccharides such as oligosaccharides containing uronic acid and the like, and the chemical properties of these oligosaccharides are described in, for example, “Biochemical Data Book”, 5th edition, edited by The Biochemical Society of Japan, Tokyo Chemical Industry. Doujin,
1989, pp. 458-480, describe in detail the properties of these compounds. Further, the degree of polymerization n derived from homopolysaccharides or heteropolysaccharides described in the above-mentioned "Biochemical Data Book", pp. 480 to 498, is 30.
The compounds described above can also be used as the compound of the oligosaccharide moiety of the compound of the present invention without departing from the gist of the present invention. Furthermore, the oligosaccharides usable in the present invention include all oligosaccharides derived from combinations of various monosaccharides as described above. Among the above-mentioned oligosaccharides, particularly preferred are those in which the oligosaccharide partial structure is composed of repeating monosaccharides,
→ 3) Galactose is (1 → 4) β-linked at position 4 of the galactose moiety of the oligosaccharide or lactose consisting of β-linked, and galactose is (1 → 4) sequentially at position 4 of the terminal galactose.
Oligosaccharides having β-bonds can be mentioned.

The aglycone represented by the general formula (I) of the present invention is represented by m (0 or 1) and n (0) in the general formula (I).
Or 1) from the combination of the following general formulas (II) and (II)
I) and (IV).

Mn aglycone general formula General formula number 00 -R (II) 10 -QR (III) 11 -QOR (IV)

In the formulas (I), (II), (III) and (IV), R represents a linear, branched or cyclic alkyl group or alkylene group having 1 to 30 carbon atoms which may be substituted. Or an alkynyl group.

Examples of the substituent which may be substituted include lower alkyl groups such as methyl, ethyl, propyl and butyl, lower alkoxy groups such as methoxy and ethoxy, lower alkylene groups such as vinyl and allyl, carbomethoxy and carboethoxy. Lower alkoxyl carbonyl group such as, methyl ester, lower alkyl ester group such as ethyl ester, acetyl, lower alkyl carbonyl group such as propionyl, phenyl optionally substituted by lower alkyl group or alkoxyl group, aryl group such as naphthyl, Represents an aldehyde group, a cyano group, a hydroxyl group, a carbonyl group, etc.
A ring such as a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring may be formed.

Specific examples of R in the formulas (I), (II), (III) and (IV) include, for example, methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2,2-dimethyl -1-propyl, n-butyl,
n-pentyl, 2-methyl-1-butyl, 3-methyl-
1-butyl, n-hexyl, 2,3,5-trimethyl-
1-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 3-ethyl-1-pentyl, 3,3-dimethyl-1-butyl,
3,3-dimethyl-1-pentyl, n-heptyl, 2-
Methyl-1-pentyl, n-octyl, 2-ethyl-1
-Hexyl, 3,7-dimethyl-1-octyl, n-nonyl, 6-methyl-1-octyl, 4-ethyl-5-methyl-1-octyl, 4-isopropyl-5-propyl-1-octyl, n -Decyl, 2,7,8-trimethyl-1-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-
Hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl, n-eicosyl, n-docosyl, tetracosyl, hexacosyl, octacosyl, triacontyl, allyl, 2-propynyl, 2-butenyl, 2-pentenyl, 2-penten-4-ynyl, isopropylbenzyl, indanyl, cyclopropyl, Cyclopentyl,
Cyclohexyl, cyclohexenyl, cycloheptyl,
Neopentyl, neryl, 3-phenylpropyl, benzyl, isoprenyl, geranyl, neryl, linalyl, phytyl, hexamethyltetracosyl, 9,12-octadecadienyl, 9,12,15-octadecatrienyl,
Phytosteroyl, 9-octadecenyl, borranyl,
Bornenyl, Bornezenyl, Norvolanil, Mentanyl, Karanyl, Tujanil, Tuenyl, Tsuyadienyl,
Norcaranyl, carenyl, carradienyl, pinanyl, norpinanyl, pinenyl, pinadenyl, 5-gonanyl,
Examples include 5-estranyl, 5-androstanyl, 5-pregnanyl, 5-cholanyl, mandelonitriyl, isobutylnitryl, nodaketinyl, and the like, but the invention is not limited thereto.

In the present invention, general formulas (I) and (III)
And Q in the formulas (IV) represents an optionally substituted arylene group or a divalent heterocyclic group, and the optionally substituted substituent may be a saturated or unsaturated linear or branched alkyl group. Groups, alkoxycarbonyl groups such as methoxy and ethoxy, alkoxylcarbonyl groups such as carbomethoxy and carboethoxy, alkyl ester groups such as methyl ester and ethyl ester, alkylcarbonyl groups such as acetyl and propionyl, and alkyl and alkoxyl groups. Represents an aryl group such as phenyl and naphthyl, an aldehyde group, a cyano group, a hydroxyl group, a carbonyl group and the like, and may be substituted with a plurality of substituents. A three-membered ring between further substituted substituents,
A ring such as a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, and an eight-membered ring may be formed, or a polycyclic compound in which these rings are condensed may be formed.

Specific examples of the aglycone represented by the general formulas (III) and (IV) in the present invention include, for example, tocopheryl, o, m, p-tolyl, o, m, p-
Ethylphenyl, o, m, p-propylphenyl, o,
m, p-butylphenyl, o, m, p-pentylphenyl, o, m, p-pentylphenyl, o, m, p-hexylphenyl, o, m, p-heptylphenyl, o,
m, p-octylphenyl, o, m, pt-octylphenyl, o, m, p-nonylphenyl, o, m, p-
Decylphenyl, o, m, p-dodecylphenyl, o,
m, p-tetradecylphenyl, o, m, p-hexadecylphenyl, o, m, p-octadecylphenyl,
o, m, p-methoxyphenyl, o, m, p-ethoxyphenyl, o, m, p-propoxyphenyl, o, m,
p-butoxyphenyl, o, m, p-pentyloxyphenyl, o, m, p-hexyloxyphenyl, o,
m, p-heptyloxyphenyl, o, m, p-octyloxyphenyl, o, m, p-nonyloxyphenyl, o, m, p-decyloxyphenyl, o, m, p-
Dodecyloxyphenyl, o, m, p-tetradecyloxyphenyl, o, m, p-hexadecyloxyphenyl, o, m, p-octadecyloxyphenyl, phenyl, flavonyl, isoflavonyl, flavonoyl, flavanonyl, hydroxyphenyl, o , M, p-Methoxycarbonylphenyl, vanillinyl, eugenyl, coniferyl, methoxyconiferyl, salicyl, 3,5-dimethoxyphenyl, p-acetophenyl, 2-methoxycarbonyl-5-methoxyphenyl, rapontigeniyl, esculetinyl, skin methynyl, daphnetyl , Furacekitinyl, chrysofanil, methynyl 2-cinnamate, naphthyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, benzofuranyl, indolizinyl, chromanyl, quinolinyl Isokiniriniru, quinoxalinyl, and the like can be mentioned, aglycone of the present invention is not limited to these specific examples.

The benzoyl group in which part of the hydrogen atoms of the sugar hydroxyl group except for the 1-position of the oligosaccharide moiety of the compound of the present invention is aromatically acylated may be either an unsubstituted benzoyl group or a substituted benzoyl group. Examples of the substituent of the substituted benzoyl group include methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2,2-dimethyl-1-propyl, n-butyl, n-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, n-hexyl, 2,
3,5-trimethyl-1-hexyl, 2-methyl-1-
Pentyl, 3-methyl-1-pentyl, 4-methyl-1
-Pentyl, 3-ethyl-1-pentyl, 3,3-dimethyl-1-butyl, 3,3-dimethyl-1-pentyl,
n-heptyl, 2-methyl-1-pentyl, n-octyl, 2-ethyl-1-hexyl, 3,7-dimethyl-1
-Octyl, n-nonyl, 6-methyl-1-octyl,
4-ethyl-5-methyl-1-octyl linear or branched alkyl group having 1 to 10 carbon atoms, lower alkoxy group such as methoxy and ethoxy, carbon number such as vinyl, allyl, butenyl, hexenyl, octenyl and decenyl 1
To 10 alkylene groups, carbomethoxy, lower alkoxylcarbonyl groups such as carboethoxy, methyl ester, lower alkyl ester groups such as ethyl ester,
Acetyl, lower alkylcarbonyl groups such as propionyl, phenyl optionally substituted by lower alkyl groups and alkoxyl groups, aryl groups such as naphthyl, aldehyde groups, cyano groups, hydroxyl groups, carbonyl groups, and the like. A ring such as a 3-, 4-, 5-, 6-, 7-, or 8-membered ring may be formed between the substituted substituents. Preferred examples of the substituent include an alkyl group and an alkylene group having 1 to 10 carbon atoms. Further, the number of substituents of the substituted benzoyl group may be not only one but also a plurality of substituents.

Specific examples of the substituted benzoyl group of the compound of the present invention include, for example, 4-methylbenzoyl, 4-ethylbenzoyl, 4-propylbenzoyl, 4-butylbenzoyl, 4-hexylbenzoyl, 4-octylbenzoyl, Decylbenzoyl, 4-octadecylbenzoyl, 4-methoxybenzoyl, 4-ethoxybenzoyl, 4-vinylbenzoyl, 4-allylbenzoyl,
-Carbomethoxybenzoyl, 3-carboethoxybenzoyl, 3-acetylbenzoyl, 3-cyanobenzoyl, 2,4-dimethylbenzoyl, 3,5-dimethylbenzoyl and the like.

In the case of the compound of the present invention, 5% to 80%, preferably 10%, of the hydroxyl groups that can participate in aromatic acylation.
% To 80%, more preferably 10% to 60% of the hydroxyl hydrogen atoms are preferably aromatic acylated. Further, not only a single aromatic acylated compound but also a mixture of several aromatic acylated compounds having different acylation rates can be used. In that case, the weighted average of the aromatic acylation rates of the components constituting the mixture can be used as the provisional aromatic acylation rate of the mixture. The preferred aromatic acylation in the case of a mixture has an aromatic acylation rate of 10% or more and 60% or less as in the case of the mixture alone. Separately, the position of the aromatic acylated sugar hydroxyl group is not an important factor, but an important factor is the proportion of the hydroxyl group hydrogen atoms that are aromatic acylated.

After the aromatic acylation, the remaining unreacted hydroxyl groups are subjected to sulfate esterification to obtain the desired compound of the present invention. Therefore, the sulfate esterification is involved in the hydroxyl group other than the anomeric hydroxyl group in the range of 20% to 95%, preferably in the range of 20% to 90%, more preferably in the range of 40% to 90%. Will do. Also, regarding the sulfate esterification rate, not only the sulfation rate of a single compound but also a mixture of compounds having different sulfation rates is applied.In this case, the weighted average of the compounds having different sulfation rates is calculated as a temporary value of the mixture. It can be used as a sulfation rate. In the case of a mixture, the degree of sulfation is 20% or more and 95% or less, preferably 20% or more and 90% or less of hydroxyl groups other than anomeric hydroxyl groups, more preferably 40% or less, as in the case of using a single compound.
Not less than 90%.

The compound of the present invention is a sulfate ester or a salt thereof in which the hydroxyl group other than the 1-position of the oligosaccharide moiety is sulfated by 20% or more, and Li, Na, K Alkaline metals such as Be, Mg, Ca, etc.,
Group III metals such as B and Al, Ti, V, Cr, M
Examples thereof include metal cations such as transition metals such as n, Fe, Co, Ni, Cu, and Zn. Primary, secondary, tertiary and quaternary cations which form counter cations of organic cations in addition to these metal cations
Examples thereof include quaternary ammonium salts, and any cation can be used. Preferable cations include lithium cation, sodium cation, potassium cation, and quaternary ammonium cation.

Next, a general method for producing the sulfated benzoyl group-substituted oligosaccharide derivative of the present invention will be described.

Various methods can be considered for the production method.
As a method for synthesizing a derivative of an oligosaccharide which is an intermediate for obtaining the compound of the present invention, an ordinary method for converting a saccharide into a glycoside can be used as it is. That is, a method of reacting sugar peracetate with alcohols under acidic conditions,
Sugar peracetate in Koenig Knorr
igs-Knorr) method, then reacting with alcohols using silver salt or mercury salt, reacting glycosyl bromide with alcohols in the presence of tetraethylammonium bromide, sugar imidale Any method such as a method of reacting with alcohols can be used.

Of these, the method of reacting an alcohol under acidic conditions is the simplest, and will be described in detail below. That is, (first step) acetylation of raw material sugar, (second step) glycosylation (glycation) with aglycone raw material, (third step) deacetylation, (fourth step) aromatic acylation (benzoyl) ) And (fifth step) a reaction comprising five steps of sulfate esterification.

Next, each step will be described in more detail.

In the first step, a method of using acetic anhydride and sodium acetate to acetylate all of the sugar hydroxyl groups to form peracetate is advantageous for the next glycosylation reaction because more β-form is produced. Of course, acetylation by other methods may be used.

The glycosylation of the alcohol which is the aglycone raw material in the second step may be carried out by any of various methods, and any method may be used.
For example, zinc chloride, boron trifluoride ether, tin tetrachloride,
A method using titanium tetrachloride, iron chloride, triflate, trimethylsilyl triflate, or the like is preferable. Protonic acid,
For example, the reaction can of course be performed using an acid catalyst such as sulfuric acid or paratoluenesulfonic acid. Glycosides can be produced by reacting the peracetate produced in the first step in the presence or absence of a solvent in the presence of these acid catalysts. At this time, the amount of the acid catalyst used varies from the so-called catalytic amount to several mole times the amount of peracetate depending on the reaction conditions. Usually, when the reaction is carried out in a solvent, it is desirable to use a solvent in which the raw materials dissolve and are not affected by the catalyst. For example, benzene, toluene, xylene and the like can be used for aromatic hydrocarbons, and methylene chloride and dichloroethylene can be used for halogens. In addition, ether solvents such as nitrobenzene, dimethoxyethylene, and anisole can be used. Which of these solvents is selected also depends on the reaction conditions at that time, and it is not possible to unconditionally decide what is good. However, in general, it is preferable to use an aromatic hydrocarbon or a halogen-based solvent in the presence of a Lewis acid catalyst. The reaction conditions are not particularly limited, but the desired compound can be obtained at a preferable reaction temperature of -70 ° C to 150 ° C and a reaction time of about 0.5 to 10 hours. For example, when using a protonic acid or a Lewis acid, the temperature is relatively high (from room temperature to about 100 ° C.), and when using trimethylsilyl triflate, the temperature is relatively low (below 0 ° C.).

In the third step, the peracetyl glycoside is deacetylated by a conventional method, that is, by the action of ammonia gas, amines, alkoxides, metal hydroxides, etc. in a protic solvent, thereby easily converting the oligosaccharide. Derivatives can be obtained.

The fourth step is an esterification reaction between the derivative produced in the third step and an aromatic carboxylic acid. This method is carried out by a dehydration esterification reaction using an aromatic carboxylic acid and dicyclocarbodiimide. It can be produced by an esterification reaction using N, N'-carbonylimidazole or the like, and further can be produced by reacting an acid chloride of an aromatic carboxylic acid with a derivative.

In the fifth step of sulfation, sulfation can be carried out by a method usually used in the case of sulfate esterification of a sugar hydroxyl group. That is, sulfur trioxide amine complex, sulfur trioxide pyridine complex, sulfur trioxide dimethylformamide complex,
Further, the objective compound of the present invention can be produced by reacting the benzoyl group-substituted oligosaccharide derivative obtained in the fourth step in a solvent with a sulfating agent such as piperidinesulfonic acid in a solvent. The sulfating agent used here varies depending on the desired degree of sulfation, but it is 0.3 to 3.0 equivalents, preferably 1.2 equivalents, based on the remaining hydroxyl groups of the benzoyl group-substituted oligosaccharide derivative.
Sulfation proceeds reliably by using up to 2.0 equivalents.
As the solvent used at this time, it is preferable to use a polar aprotic solvent such as dimethylformamide, pyridine and dimethylsulfoxide. The reaction temperature is from room temperature to 100 ° C,
Preferably, it can be produced by a stirring reaction in an inert gas at room temperature to 90 ° C. for 1 to 24 hours.

When the reaction after purification is carried out with a sodium salt, the reaction mixture is cooled to room temperature or under ice-cooling, and the resulting precipitate is separated from the solvent and dissolved in water. 0.0, preferably 7.5 to 10.0
An aqueous solution of caustic soda, sodium carbonate or the like is dripped to the extent. The aqueous solution after the dropping is desalted by a micro-acyler (a desalter manufactured by Asahi Kasei Kogyo Co., Ltd.), or desalted by gel filtration chromatography, reverse osmosis, ultrafiltration, etc.
The desired product can be obtained by concentrating the aqueous solution after desalting. Alternatively, a precipitate formed after cooling and precipitating the reaction product into an aqueous solution and then adjusting the hydrogen ion concentration to about 6.5 to 12.0, preferably 7.0 to 10.0 with an aqueous barium hydroxide solution. Is separated by centrifugation or filtration,
The aqueous solution is passed through a sodium-type cation exchange resin column to obtain a target sodium salt. The liquid passed through the column can be concentrated to obtain the desired product.

Further, the desired cation species is added to the aqueous solution of the separated and purified sulfated benzoyl group-substituted oligosaccharide derivative until the hydrogen ion concentration becomes 6.5 to 7.5, followed by concentration. A salt of the substituted oligosaccharide derivative can be easily obtained.

Of course, there are other methods for producing this compound group than the methods described here, but this method is a method which can be easily produced as compared with other methods. For details of specific synthesis methods and synthesis examples, see JP-A-3-324,5.
No. 32, No. 5-78,382, No. 5-213,982
And the synthesis examples and methods described in JP-A-5-279,381.

Next, specific examples of the sulfated benzoyl group-substituted oligosaccharide derivatives or salts thereof preferably used in the present invention will be described, but the present invention is not limited to these specific examples.

In the following examples, the counter cation of the sulfate ester is omitted, and only the sulfation is described. The aromatic acylation is indicated by the degree of substitution of the hydroxyl group with hydrogen (the number of acylations).

1 sulphated n-dodecyl di-O-benzoyl laminaripentaoside 2 sulphated n-dodecyl tri-O-benzoyllaminaripentaoside 3 sulphated n-dodecyl tetra-O-benzoyllaminaripentaoside Side 4 Sulfated n-dodecyl penta-O-benzoyllaminaripentaoside 5 Sulfated n-dodecyl hexa-O-benzoyllaminaripentaoside 6 Sulfated n-dodecyl hepta-O-benzoyllaminaripentaoside 7 Sulfated n-dodecyl octa-O-benzoyllaminaripentaoside 8 Sulfated n-dodecyl nona-O-benzoyllaminaripentaoside 9 Sulfated n-dodecyldeca-O-benzoyllaminaripentaoside 10 Sulfated n-dodecyl undeca-O-benzoyl laminalipentaoside 11 sulfated n Dodecyl dodeca-O-benzoyl laminaripentaoside 12 sulfated n-dodecyl di-Op-methylbenzoyllaminaripentaoside 13 sulfated n-dodecyl tri-Op-methylbenzoyllaminaripentaoside 14 Sulfated n-dodecyl tetra-Op-methylbenzoyl laminalipentaoside 15 Sulfated n-dodecyl penta-Op-methylbenzoyllaminaripentaoside 16 Sulfated n-dodecyl hexa-Op-methyl Benzoyl laminaripentaoside 17 sulfated n-dodecyl hepta-Op-methylbenzoyllaminaripentaoside 18 sulfated n-dodecyl octa-Op-methylbenzoyllaminaripentaoside 19 sulfated n-dodecyl Nona-Op-methylbenzoyl laminalipentaoside 20 sulfuric acid N-dodecyl deca-Op-methylbenzoyl laminalipentaoside

21 Sulfated n-dodecyl undeca
Op-methylbenzoyl laminalipentaoside 22 sulfated n-dodecyl dodeca-Op-methylbenzoyllaminaripentaoside 23 sulfated n-dodecyl di-Op-pentylbenzoyllaminaripentaoside 24 Sulfated n-dodecyl tri-Op-pentylbenzoyl laminalipentaoside 25 Sulfated n-dodecyl tetra-Op-pentylbenzoyllaminaripentaoside 26 Sulfated n-dodecyl penta-Op-pentyl Benzoyl laminalipentaoside 27 Sulfated n-dodecyl hexa-Op-pentylbenzoyl laminalipentaoside 28 Sulfated n-dodecyl hepta-Op-P-pentylbenzoyllaminaripentaoside 29 Sulfated n-dodecyl Octa-Op-pentylbenzoyl laminalipentaoside 0 Sulfated n-dodecyl nona-Op-pentylbenzoyllaminaripentaoside 31 Sulfated n-dodecyldeca-Op-pentylbenzoyllaminaripentaoside 32 Sulfated n-dodecylundeca-Op- Pentylbenzoyl laminalipentaoside 33 Sulfated n-dodecyl dodeca-Op-pentylbenzoyllaminaripentaoside 34 Sulfated n-dodecyl di-Op-octylbenzoyllaminaripentaoside 35 Sulfated n- Dodecyl tri-Op-octylbenzoyl laminalipentaoside 36 Sulfated n-dodecyl tetra-Op-octylbenzoyllaminaripentaoside 37 Sulfated n-dodecylpenta-Op-octylbenzoyllaminaripentane Osid 38 sulfated n-dodecyl hexa-Op-octy Rubenzoyl laminalipentaoside 39 Sulfated n-dodecyl hepta-Op-octylbenzoyl laminalipentaoside 40 Sulfated n-dodecyl octa-Op-octylbenzoyl laminalipentaoside

41 Sulfated n-dodecyl nona-O-
p-octylbenzoyllaminaripentaoside 42 sulfated n-dodecyldeca-Op-octylbenzoyllaminaripentaoside 43 sulfated n-dodecylundeca-Op-octylbenzoyllaminaripentaoside 44 sulfated n-dodecyl dodeca-Op-octylbenzoyl laminalipentaoside 45 sulfated pn-octylphenyl di-O-benzoyllaminaripentaoside 46 sulfated pn-octylphenyl tri-O-
Benzoyl laminaripentaoside 47 Sulfated pn-octylphenyl tetra-O
-Benzoyl laminaripentaoside 48 sulfated pn-octylphenyl penta-O
-Benzoyl laminaripentaoside 49 sulfated pn-octylphenyl hexa-O
-Benzoyl laminaripentaoside 50 sulfated pn-octylphenyl hepta-O
-Benzoyl laminaripentaoside 51 sulfated pn-octylphenyl octa-O
-Benzoyllaminaripentaoside 52 sulfated pn-octylphenyl nona-O-
Benzoyl laminaripentaoside 53 sulfated pn-octylphenyl deca-O-
Benzoyl laminaripentaoside 54 sulfated pn-octylphenyl undeca-
O-benzoyl laminalipentaoside 55 sulfated pn-octylphenyl dodeca-O
-Benzoyl laminaripentaoside 56 sulfated pn-octylphenyl di-Op
-Methylbenzoyl laminalipentaoside 57 sulfated pn-octylphenyl tri-O-
p-Methylbenzoyl laminaripentaoside 58 sulfated pn-octylphenyl tetra-O
-P-methylbenzoyl laminaripentaoside 59 sulfated pn-octylphenyl penta-O
-P-methylbenzoyldodecyl laminalipentaoside 60 sulfated pn-octylphenyl hexa-O
-P-methylbenzoyldodecyl laminalipentaoside

61 Sulfated pn-octylphenyl hepta-Op-methylbenzoyldodecyl laminaripentaoside 62 Sulfated pn-octylphenyl octa-O
-P-methylbenzoyldodecyl laminalipentaoside 63 sulfated pn-octylphenyl nona-O-
p-Methylbenzoyldodecyl laminalipentaoside 64 sulfated pn-octylphenyl deca-O-
p-Methylbenzoyldodecyl laminalipentaoside 65 sulfated pn-octylphenyl undeca-
Op-methylbenzoyl laminalipentaoside 66 sulfated pn-octylphenyl dodeca-O
-P-methylbenzoyllaminaripentaoside 67 sulfated pn-octylphenyl di-Op
-Pentylbenzoyl laminalipentaoside 68 sulfated pn-octylphenyl tri-O-
p-pentylbenzoyldodecyl laminalipentaoside 69 sulfated pn-octylphenyl tetra-O
-P-pentylbenzoyldodecyl laminalipentaoside 70 sulfated pn-octylphenyl penta-O
-P-pentylbenzoyldodecyl laminalipentaoside 71 sulfated pn-octylphenyl hexa-O
-P-pentylbenzoyldodecyl laminalipentaoside 72 sulfated pn-octylphenyl hepta-O
-P-pentylbenzoyldodecyl laminalipentaoside 73 sulfated pn-octylphenyl octa-O
-P-pentylbenzoyldodecyl laminalipentaoside 74 sulfated pn-octylphenyl nona-O-
p-pentylbenzoyldodecyl laminalipentaoside 75 sulfated pn-octylphenyl deca-O-
p-pentylbenzoyldodecyl laminalipentaoside 76 sulfated pn-octylphenyl undeca
Op-pentylbenzoyl laminalipentaoside 77 sulfated pn-octylphenyl dodeca-O
-P-pentylbenzoyllaminaripentaoside 78 sulfated pn-octylphenyl di-Op
-Octylbenzoyllaminaripentaoside 79 sulfated pn-octylphenyl tri-O-
p-octylbenzoyllaminaripentaoside 80 sulfated pn-octylphenyl tetra-O
-P-octylbenzoyl laminalipentaoside

81 Sulfated pn-octylphenyl penta-Op-octylbenzoyllaminaripentaoside 82 Sulfated pn-octylphenyl hexa-O
-P-octylbenzoyl laminalipentaoside 83 sulfated pn-octylphenyl hepta-O
-P-octylbenzoyl laminalipentaoside 84 sulfated pn-octylphenyl octa-O
-P-octylbenzoyl laminalipentaoside 85 sulfated pn-octylphenyl nona-O-
p-octylbenzoyl laminalipentaoside 86 sulfated pn-octylphenyl deca-O-
p-octylbenzoyl laminalipentaoside 87 sulfated pn-octylphenyl undeca-
Op-octylbenzoyl laminalipentaoside 88 Sulfated pn-octylphenyl dodeca-O
-P-octylbenzoyllaminaripentaoside 89 sulfated pn-hexylphenyl di-O-benzoyl-β-D-galactopyranosyl (1 → 4) -β
-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 90 sulfated pn-hexylphenyl tri-O-
Benzoyl-β-D-galactopyranosyl (1 → 4)-
β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 91 sulfated pn-hexylphenyl tetra-O
-Benzoyl-β-D-galactopyranosyl (1 → 4)
-Β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 92 sulfated pn-hexylphenyl penta-O
-Benzoyl-β-D-galactopyranosyl (1 → 4)
-Β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 93 sulfated pn-hexylphenyl hexa-O
-Benzoyl-β-D-galactopyranosyl (1 → 4)
-Β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 94 sulfated pn-hexylphenyl hepta-O
-Benzoyl-β-D-galactopyranosyl (1 → 4)
-Β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 95 sulfated pn-hexylphenyl octa-O
-Benzoyl-β-D-galactopyranosyl (1 → 4)
-Β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 96 sulfated n-octyl di-O-benzoyl-β
-D-galactopyranosyl (1 → 4) -β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 97 sulfated n-octyl tri-O-benzoyl-
β-D-galactopyranosyl (1 → 4) -β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 98 sulfated n-octyl tetra-O-benzoyl-β-D-galacto Pyranosyl (1 → 4) -β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 99 sulfated n-octyl penta-O-benzoyl-β-D-galactopyranosyl (1 → 4) -β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 100 sulfated n-octyl hexa-O-benzoyl-β-D-galactopyranosyl (1 → 4) -β -D-galactopyranosyl (1 → 4) -β-D-glucopyranoside

101 Sulfated n-octyl hepta-O
-Benzoyl-β-D-galactopyranosyl (1 → 4)
-Β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 102 sulfated n-octyl octa-O-benzoyl-β-D-galactopyranosyl (1 → 4) -β-D- Galactopyranosyl (1 → 4) -β-D-glucopyranoside 103 sulfated n-octyl di-Op-butylbenzoyl-β-D-galactopyranosyl (1 → 4) -β-
D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 104 sulfated n-octyl tri-Op-butylbenzoyl-β-D-galactopyranosyl (1 → 4) -β
-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 105 sulfated n-octyl tetra-Op-butylbenzoyl-β-D-galactopyranosyl (1 → 4)-
β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 106 sulfated n-octyl penta-Op-butylbenzoyl-β-D-galactopyranosyl (1 → 4)-
β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 107 sulfated n-octyl hexa-Op-butylbenzoyl-β-D-galactopyranosyl (1 → 4)-
β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 108 sulfated n-octyl hepta-Op-butylbenzoyl-β-D-galactopyranosyl (1 → 4)-
β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside 109 sulfated n-octyl octa-Op-butylbenzoyl-β-D-galactopyranosyl (1 → 4)-
β-D-galactopyranosyl (1 → 4) -β-D-glucopyranoside

In addition, many compounds can be exemplified by combinations of sugar chains, aglycones, and substituted benzoyl groups, but they will be understood even if omitted.

Further, there are two types of binding modes of the derivatives, α and β, and the exemplified compounds shown here indicate one of them.

[0055]

Next, the concentrated dampening solution according to the present invention will be described. The concentrated fountain solution for lithographic printing of the present invention contains the fountain solution for lithographic printing of the present invention in an amount of 0.01 to 20% by weight,
It is preferably a concentrated fountain solution characterized by containing 0.1 to 15% by weight, and further contains a film-forming hydrophilic polymer, a pH buffer, a wetting agent, an organic solvent, an antifoaming agent, a preservative,
It may contain a rust inhibitor, a coloring agent, a chelating agent and the like. When the content of the sulfated benzoyl group-substituted oligosaccharide derivative and / or a salt thereof, which is a fountain solution material for lithographic printing, is less than 0.01% by weight, the surface tension is not sufficiently reduced, and The phenomenon of ink diffusion to the water surface occurs, and floating stains and background stains appear on printed matter. 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. .

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 concentrated 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 amount of the polymer compound used is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, in the 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 fountain 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 its derivatives, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzotriazole derivatives, amidines 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.

The rust preventive used in the concentrated fountain solution for lithographic printing of the present invention includes 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 Metal salt, ammonium salt, organic amine salt and the like can be mentioned. 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 coloring agent used in the concentrated fountain solution for lithographic printing of the present invention, a water-soluble food coloring material 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 agent used in the fountain solution for lithographic printing of the present invention includes 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.

[0070]

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) Using the sulfated benzoyl group-substituted oligosaccharide derivative compounds 1 to 6 of the present invention shown in Table 1, concentrated fountain solutions 1 to 6 shown in Table 2 were prepared.

[0072]

[Table 1]

[0073]

[Table 2]

Here, the numbers in Table 2 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 6 of the present invention was diluted 50-fold with water to prepare corresponding fountain solutions 1 to 6 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 3 shows the fountain solution characteristics of the fountain solutions 1 to 6 and Comparative Examples 1 and 2 according to the present invention. Dynamic surface tension is the value at the maximum bubble pressure method at 25 ° C. Plate Toretest shows the state of the plate when the positive type PS plate RP (manufactured by Polychrome Japan) is immersed in humidified water at room temperature for 24 hours.
"(A); no change at all, (B); slight change compared to the original, (C); noticeable change but no problem, (D); ;
It was evaluated on a five-point scale of “total edition tray”. In the ink emulsification test, the dampening water holding power of the ink was measured by a dactet tester (manufactured by Kawamura Riken) using the ink "Geos G-Red N Type" (manufactured by Dainippon Ink and Chemicals).
It is a value measured at 0 rpm / 60 rpm and 40 ° C.

[0078]

[Table 3]

From Table 3, it can be seen that the dynamic surface tension of the dampening solution of the present invention is almost the same as that of the dampening solution obtained by replacing isopropyl alcohol with an organic solvent. Water did not cause any plate tray at the same level as water alone, and in the ink emulsification test, all the samples showed the same characteristics with respect to the measured ink. This shows that the fountain solution according to the present invention is superior to the comparative example in the plate tray, and that the emulsifying properties of the ink are comparable to those of the comparative example and have no problem.

(Example 2) Printing tests were performed using dampening solutions 1 to 6 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)

A printing test of 10,000 copies was performed for each dampening solution, and the stains, water width, foaming and the degree of stain return of the printed matter were judged. Table 4 shows the results.

[0082]

[Table 4]

In Table 4, the stain on the printed matter was 10,0.
The degree of staining of the non-image area after printing 00 copies was evaluated as “(○): no staining, (x): occurrence of staining / impossible 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 recognized but no problem in printing, (x): foaming was severe and printing was difficult”. The return of stains was measured by printing the 5,000 copies of the printed matter, stopping the printing machine for 10 minutes, and restarting printing. The dampening solution (（): standard,
(◎): recovery is 2/3 or less of the standard, (△): 1.
3 times or more, (x): not recovered ".

From the results shown in Table 4, 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.

[0085]

EFFECT OF THE INVENTION The concentrated fountain solution for lithographic printing containing the fountain solution material for lithographic printing according to the present invention is a concentrated solution excellent in liquid stability which does not contain IPA and conforms to the regulations of the Fire Service Law and the Industrial Safety and Health Law. A fountain solution, which is a fountain solution for lithographic printing prepared by diluting the concentrated fountain solution according to the present invention, is an excellent fountain solution that can easily obtain a high-quality printed material without stains or plate marks on the printed material. It is a fountain solution with the characteristics of fountain solution.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Koji Oe 5-90 Higashima, Kitamoto City, Saitama Prefecture 2-505 Kitamoto Kitamoto (72) Inventor Yasuhiko Kojima 1-14-3-403 (72) Akamidai, Konosu City, Saitama Prefecture Inventor Tadao Tokaibayashi 6-36-13 Ojidai, Sakura City, Chiba Prefecture

Claims (9)

[Claims] 1. A fountain solution material for lithographic printing wherein the same or different monosaccharides are used as constituents, and the hydrogen of the hydroxyl group at the 1-position of the terminal sugar of the oligosaccharide formed by glycosidic bonding is
A part of the hydrogen atom of the sugar hydroxyl group except for the 1-position of the sugar moiety, which is substituted by the following general formula (I), is aromatically acylated by a substituted or unsubstituted benzoyl group, and the remaining unsubstituted hydroxyl group is further substituted. A concentrated fountain solution for lithographic printing, comprising a sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof, which is partially or entirely sulfated. Formula (I)-(Q) _m- (O) _n -R (wherein, R represents an alkyl group, an alkylene group or an alkynyl group having 1 to 30 carbon atoms which may be substituted;
m represents 0 or 1, n represents 0 or 1, Q represents an optionally substituted arylene group or a divalent heterocyclic group, and O represents an oxygen atom. n is 0 when m = 0
Represents 0 or 1 when m = 1. ) 2. The sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof is an oligosaccharide composed of repeating monosaccharides having the same oligosaccharide partial structure and comprising a (1 → 3) β bond of glucose. 2. The concentrated fountain solution for lithographic printing according to 1. 3. The sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof, wherein the oligosaccharide partial structure is such that galactose is (1 → 4) β-linked to the 4-position of the galactose moiety of lactose, and sequentially to the 4-position of the terminal galactose. , Galactose is (1 →
4) The concentrated fountain solution for lithographic printing according to claim 1, which is an oligosaccharide having a β bond. 4. The lithographic printing concentrate according to claim 1, wherein the sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof is an oligosaccharide having an oligosaccharide sugar chain consisting of 3 to 20 sugars. Fountain solution. 5. The sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof, wherein the oligosaccharide partial structure is 2 to 2
2. The concentrated fountain solution for lithographic printing according to claim 1, which is an oligosaccharide composed of repeating the same monosaccharide composed of zero saccharide. 6. The sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof, wherein the substituted benzoyl group has 1 to 1 carbon atoms.
The concentrated fountain solution for lithographic printing according to any one of claims 1 to 5, wherein the fountain solution is substituted with 0 alkyl groups or alkylene groups. 7. The sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof is substituted with an unsubstituted or substituted benzoyl group in which the hydrogen atom of the sugar hydroxyl group excluding the 1-position of the oligosaccharide sugar moiety is 10% to 60%. The concentrated moistening solution for lithographic printing according to any one of claims 1 to 6, wherein 40% or more and 90% or less of the sugar hydroxyl groups excluding the 1-position of the oligosaccharide sugar portion are substituted with a sulfate ester. water. 8. The concentrated wet for lithographic printing according to claim 1, which comprises at least one sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof in which m in formula (I) is 0. Water. 9. The concentrated fountain solution for lithographic printing according to claim 1, comprising 0.01 to 20% by weight of the sulfated benzoyl group-substituted oligosaccharide derivative or a salt thereof.