JP2012030548A - Water composition for lithographic printing and heat-set-off-rotary printing - Google Patents

Abstract

Provided is a fountain solution for lithographic printing, which suppresses blanket piling and is excellent in preventing contamination due to scratches in a non-image area.
An acyclic hydrocarbon compound having two OH groups and a total carbon number of 9, and at least one selected from an oxygen acid group and a carboxy group of phosphorus in a side chain, a sulfonic acid group, and A fountain solution for lithographic printing comprising a water-soluble copolymer having at least one selected from betaine structures; a heatset type off-wheel ink, and the fountain solution composition Heat set-off ring printing method used.
[Selection figure] None

Description

  The present invention relates to a fountain solution composition for lithographic printing, and more specifically to a fountain solution composition for lithographic printing that is preferably used in an offset printing method, particularly in a heat-set-off wheel printing method.

Lithographic printing is a printing method that uses the property that water and oil do not essentially mix, and the printing plate surface is a non-image area that accepts water and repels oil-based ink, and an image area that repels water and accepts oil-based ink. Consists of. By moistening the non-image area with the fountain solution, the difference in interfacial chemistry with the image area is increased, and the ink repellency of the non-image area and the ink receptivity of the image area are increased.
A lithographic printing machine is usually an offset printing system, and ink and fountain solution are supplied onto the plate, ink is deposited on the image area, and fountain solution is deposited on the non-image area. The image on the plate is printed by transferring to a blanket and then transferring from the blanket to paper.

As a conventional fountain solution, an aqueous solution to which colloidal substances such as dichromate, phosphate, gum arabic, and carboxymethylcellulose (CMC) are added is known. However, when only these compounds are contained, the non-image area of the plate is difficult to wet uniformly, and there is a problem that the printed matter is soiled, and considerable skill is required to adjust the supply amount of dampening water. .
In order to remedy this drawback, a Dahlglen system has been proposed in which an aqueous solution containing about 20 to 25% of isopropyl alcohol is used as a fountain solution. However, since isopropyl alcohol is easy to evaporate, a special device for keeping the concentration in the dampening water constant is required. In addition, isopropyl alcohol has an unpleasant odor and is not preferable in the working environment.

As dampening water not containing isopropyl alcohol, for example, dampening water containing a specific propylene glycol-based compound (see Patent Document 1) or dampening water containing a compound obtained by adding ethylene oxide and propylene oxide to ethylenediamine ( A fountain solution containing a compound obtained by adding ethylene oxide and propylene oxide to diethylenetriamine (see Patent Document 2) has been proposed.
When printing is continued for a long time, the ink component and paper component gradually accumulate on the non-image area on the blanket, and the deposit may hinder ink transfer to paper and cause ink imperfection. As a technique for improving this phenomenon (referred to as blanket piling), a fountain solution composition containing a specific diol compound has been proposed (see Patent Document 4). Further, it has been proposed that a printing chemical containing a water-soluble polymer having an adsorbable group and a sulfonic acid group that can be adsorbed on the surface of a lithographic printing plate support is useful for preventing contamination of a non-image area (Patent Document 5). reference).
Thus, while various devices have been proposed for the fountain solution composition, for example, the fountain solution composition proposed in Patent Document 4 is excellent in the effect of suppressing blanket piling. There may be a decrease in insensitivity due to scratches (scratching, abrasion, adhesion of foreign matter, etc.) or dirt on the printing plate surface during stoppage. According to the study by the present inventors, the plate surface protection action against scratches is not sufficient. I found out.

JP 2001-138655 A JP 2007-50665 A JP 2007-55182 A JP 2009-96177 A JP 2007-38483 A

  An object of the present invention is to provide a fountain solution for lithographic printing that suppresses blanket piling and is excellent in preventing contamination due to scratches in non-image areas.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have added a specific diol compound and a water-soluble polymer having at least two specific groups or structures in the side chain to the dampening water. Thus, it was found that not only the blanket piling is suppressed, but also excellent in preventing scratches.
Accordingly, the present invention provides an acyclic hydrocarbon compound having two OH groups and a total carbon number of 9, and at least one selected from a phosphorus oxyacid group, a sulfonic acid group, and a betaine structure in the side chain. A fountain solution for lithographic printing, comprising a water-soluble copolymer having:
In a preferred embodiment of the present invention, the acyclic hydrocarbon compound is 2-butyl-2-ethyl-1,3-propanediol and / or 2,4-diethyl-1,5-pentanediol. Shimizu composition. A preferable embodiment of the present invention further includes a fountain solution for lithographic printing containing a compound represented by the following general formula (I).
R ¹ —O— (CH ₂ CHR ² O) _m —H (I)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R ² represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 5).
The fountain solution for lithographic printing according to the present invention can be preferably used in a heat-set off-wheel printing system. Therefore, the present invention further includes a heat-set type off-wheel ink, and the fountain solution composition. Is directed to a heat-set-off-wheel printing method using the

  According to the fountain solution composition of the present invention, not only the occurrence of blanket piling is suppressed, but also the stain prevention due to scratches in the non-image area is excellent, and a good print quality can be stably obtained even after continuous printing for a long time. It is done. Furthermore, according to the fountain solution composition of the present invention, it is possible to easily adjust the supply amount of the fountain solution without using a volatile organic solvent such as isopropyl alcohol conventionally used in the fountain solution. It can be performed and is preferable in the working environment.

The present invention is described in detail below.
The acyclic hydrocarbon compound used in the present invention is a diol compound having two OH groups and a total carbon number of 9. Here, when the total number of carbon atoms is 9, the solubility is good and the intended effect of the present invention is achieved.
In the diol compound used in the present invention, a preferred range of the shortest carbon number between the two OH groups is 2-6, and a more preferred range is 3-5.
Specific examples (1) to (15) of the diol compound used in the present invention are shown below, but are not limited thereto.

Among the specific examples of the diol compounds used in the present invention, (7) 2-butyl-2-ethyl-1,3-propanediol and (10) 2,4-diethyl-1,5-pentanediol are: Excellent in reducing blanket piling.
In the fountain solution composition of the present invention, the diol compound may be used alone or in combination of two or more.
As an example of the fountain solution composition of the present invention, two or more diol compounds are contained, and 2-butyl-2-ethyl-1,3-propanediol is 1% by mass or more based on the total mass of the diol compounds. Fountain solution composition. In this example, 2-butyl-2-ethyl-1,3-propanediol preferably accounts for 3% by mass or more, more preferably 10% by mass or more of the total mass of the diol compound.
2,4-diethyl-1,5-pentanediol as a diol compound used in combination with 2-butyl-2-ethyl-1,3-propanediol in a fountain solution composition containing two or more diol compounds Is particularly mentioned.

  The addition amount of the diol compound in the fountain solution composition of the present invention is suitably 0.001 to 2.0% by mass in the fountain solution composition at the time of use. Is sufficiently obtained and no dissolution failure or water supply roller contamination occurs, preferably 0.05 to 1.0% by mass, more preferably 0.1 to 0.7% by mass, and still more preferably 0.00. 2 to 0.5% by mass.

  The fountain solution composition is usually first prepared as a concentrated solution, and it is preferable to dilute and use the concentrated solution at the time of use, and the dilution rate is particularly preferably about 30 to 100 times. If the concentration rate is too high, problems such as precipitation and liquid separation in the concentrated solution are likely to occur. Hereinafter, the fountain solution composition in use is simply referred to as “fountain solution”.

The fountain solution composition of the present invention further has a water-soluble copolymer having at least one selected from an oxygen acid group and a carboxy group of phosphorus and at least one selected from a sulfonic acid group and a betaine structure in the side chain. Includes coalescence.
The water-soluble copolymer includes at least a monomer unit having an oxygen acid group and / or carboxy group of phosphorus (hereinafter also referred to as “acidic monomer unit”), a monomer unit having a sulfonic acid group, and / or a copolymer unit. It may be a water-soluble copolymer having a monomer unit having a betaine structure (these two types of monomer units are hereinafter also referred to as “hydrophilic monomer units”). Hereinafter, the water-soluble copolymer is also referred to as a specific copolymer.

Specific examples of the oxygen acid group of phosphorus include a phosphonic acid group (—PO (OH) ₂ ) and a phosphoric acid group (—OPO (OH) ₂ ), and has a monomer unit having the above group as a copolymer unit. A water-soluble copolymer is preferred.
The oxygen acid group of the above phosphorus may form a salt, and the counter cation other than the proton (H ⁺ ) is not particularly limited, and may be an inorganic cation such as a metal cation or an organic cation such as a metal cation. It may be a tetraalkylammonium ion or the like, or may be a polymer type cation. The counter cation may be a monovalent counter cation or a divalent or higher counter cation.

（式（Ｕ−１）〜（Ｕ−３）中、Ｒ¹は、水素原子又はアルキル基を表し、Ａ¹は、単結合又は（ｎ＋１）価の有機基を表し、Ｘ¹及びＸ²はそれぞれ独立に、水素原子又はプロトン（Ｈ⁺）以外の対カチオンを表し、ｎは１以上の整数を表す。） The acidic monomer unit is preferably a monomer unit represented by the following formulas (U-1) to (U-3), and is a monomer unit represented by the following formula (U-1) or (U-2). It is more preferable that

(In the formulas (U-1) to (U-3), R ¹ represents a hydrogen atom or an alkyl group, A ¹ represents a single bond or an (n + 1) -valent organic group, and X ¹ and X ² represent Each independently represents a counter cation other than a hydrogen atom or a proton (H ⁺ ), and n represents an integer of 1 or more.)

In the above formula, R ¹ represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.
In the formula, the counter cation other than the proton (H ⁺ ) in X ¹ and X ² is not particularly limited, and even if it is an inorganic cation such as a metal cation (for example, an alkali metal ion such as lithium, potassium or sodium), an ammonium ion (For example, primary ammonium ions such as NH ₄ ⁺ and benzylammonium, secondary ammonium ions such as ethylbenzylammonium, tertiary ammonium ions such as triethylammonium, tetrabutylammonium ions, and fourth such as benzyltriethylammonium. Organic cation such as quaternary ammonium ion, pyridinium, imidazolium) or polymer type cation. The counter cation may be a monovalent counter cation or a divalent or higher counter cation.
The n represents an integer of 1 or more, preferably an integer of 1 to 5, preferably 1 or 2, and particularly preferably 1.

In the formula, the (n + 1) -valent organic group in A ¹ is preferably a group formed from at least one element selected from the group consisting of carbon, hydrogen, oxygen and nitrogen, and carbon, hydrogen and oxygen More preferably, it is a group formed from at least one element selected from the group consisting of a group obtained by removing (n + 1) hydrogen atoms from a hydrocarbon, or m from a hydrocarbon (where m is It is more preferably a group in which two or more groups selected from the group consisting of an ester bond and an ether bond are combined. When A ¹ is an (n + 1) valent organic group, the number of carbon atoms is generally in the range of 3-20.

（式（Ｕ−４）及び（Ｕ−５）中、Ｒ¹は、水素原子又はアルキル基を表し、Ａ²は、二価の有機基を表し、Ｘ¹及びＸ²はそれぞれ独立に、水素原子又はプロトン（Ｈ⁺）以外の対カチオンを表す。） The acidic monomer unit is more preferably a monomer unit represented by the following formula (U-4) or (U-5).

(In formulas (U-4) and (U-5), R ¹ represents a hydrogen atom or an alkyl group, A ² represents a divalent organic group, and X ¹ and X ² each independently represent hydrogen. (Represents a counter cation other than an atom or a proton (H ⁺ ).)

R ^1, X ¹ and X ² in Formula (U-4) and (U-5) has the same meaning as R ^1, X ¹ and X ² in the formula (U-1) ~ (U -3), preferred The range is the same.
The divalent organic group in A ² of the formula (U-5) is preferably a group formed from at least one element selected from the group consisting of carbon, hydrogen, and oxygen, an alkylene group, or More preferably a group in which two or more groups selected from the group consisting of an alkylene group, an ester bond and an ether bond are combined, and further an alkylene group or a group in which an alkylene group and an ether bond are combined. An alkylene group or a polyalkyleneoxy group is particularly preferable. In addition, the phosphorus atom side terminal of the polyalkyleneoxy group may be a carbon atom or an oxygen atom. Further, the alkylene group and the polyalkyleneoxy group may be linear or branched.
In the monomer unit represented by the formula (U-5), the terminal group of the monomer unit is a phosphonic acid group or a salt thereof depending on whether the terminal of A ² is a carbon atom or an oxygen atom. In some cases, it may be a phosphate group or a salt thereof.
Further, (U-5) carbon atoms of A ² in is preferably 2 to 60, more preferably from 2 to 20, more preferably 2 to 10.

Specific examples of the acidic monomer unit are preferably monomer units represented by the following (A-1) to (A-6). Moreover, the monomer unit which the phosphonic acid group of the monomer unit represented by the following (A-1)-(A-6), the phosphoric acid group, or the carboxy group forms the salt can also be illustrated preferably. In the present invention, the hydrocarbon chain of the compound or its partial structure may be described by a simplified structural formula in which symbols for carbon (C) and hydrogen (H) are omitted.

The specific copolymer used in the present invention may have only one kind of the above-mentioned acidic monomer unit or may have two or more kinds.
The content ratio of acidic monomer units in the specific copolymer that can be used in the present invention is preferably 2 to 80 mol%, and preferably 2 to 70 mol%, based on all monomer units of the specific copolymer. More preferably, it is more preferably 5 to 50 mol%, and particularly preferably 10 to 40 mol%.

The specific copolymer used in the present invention also has at least one hydrophilic monomer unit selected from a monomer unit having a sulfonic acid group and a monomer unit having a betaine structure.
Here, the sulfonic acid group includes a sulfonic acid group (—SO ₃ H) and a salt thereof (—SO ₃ M (where M represents a counter cation other than proton (H ⁺ ))).
The betaine structure is a structure having both a cation structure and an anion structure in one monomer unit, and the charge is neutralized in the same monomer unit. The cation structure in the betaine structure is not particularly limited, but is preferably a quaternary nitrogen cation. The anionic structure in the betaine structure is not particularly ^{_{limited, -COO -, -SO 3 -,}} -PO 3 2-, and / or, -PO ₃ H ^- is preferably, -COO ^-, and More preferably, it is —SO ₃ ^— .

（式（Ｕ−６）〜（Ｕ−８）中、Ｒ¹は、水素原子又はアルキル基を表し、Ｒ²及びＲ³はそれぞれ独立に、水素原子又は一価の炭化水素基を表し、Ａ³は、単結合又は（ｎ＋１）価の有機基を表し、Ａ⁴は、（ｎ＋１）価の有機基を表し、Ａ⁵はそれぞれ独立に、二価の有機基を表し、Ｘ¹はそれぞれ独立に、水素原子又はプロトン（Ｈ⁺）以外の対カチオンを表し、ｎは１以上の整数を表す。） Preferable examples of the hydrophilic monomer unit include monomer units represented by the following formulas (U-6) to (U-8), and among them, represented by the following formula (U-7) or (U-8). More preferred are monomer units.

(In the formulas (U-6) to (U-8), R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group, ³ represents a single bond or an (n + 1) -valent organic group, A ⁴ represents an (n + 1) -valent organic group, A ⁵ independently represents a divalent organic group, and X ¹ represents each independently Represents a counter cation other than a hydrogen atom or a proton (H ⁺ ), and n represents an integer of 1 or more.)

R ^1, X ¹ and n in Formula (U-6) ~ (U -8) have the same meanings as R ^1, X ¹ and n in the formula (U-1) and (U-2), preferable range It is the same.
The (n + 1) -valent organic group in A ³ of the formula (U-6) is preferably a group formed from at least one element selected from the group consisting of carbon, hydrogen, oxygen and nitrogen. A group obtained by removing (n + 1) hydrogen atoms from a hydrocarbon, or a group obtained by removing m hydrogen atoms from a hydrocarbon (where m represents an integer of 1 or more), an ester bond, an amide bond, and an ether A group obtained by combining two or more groups selected from the group consisting of a bond is more preferable.
The (n + 1) -valent organic group in A ⁴ of the formulas (U-7) and (U-8) is a group formed from at least one element selected from the group consisting of carbon, hydrogen, oxygen, and nitrogen And more preferably a group formed from at least one element selected from the group consisting of carbon, hydrogen and oxygen, a group obtained by removing (n + 1) hydrogen atoms from a hydrocarbon, or And a group obtained by combining two or more groups selected from the group consisting of an ester bond and a group obtained by removing m hydrogen atoms (however, m represents an integer of 1 or more) from a hydrocarbon. .
The divalent organic group in A ⁵ in the formulas (U-7) and (U-8) is a group formed from at least one element selected from the group consisting of carbon, hydrogen, and oxygen. Preferably, it is an alkylene group. The alkylene group may be linear or branched.

R ² and R ³ in the formulas (U-7) and (U-8) each independently represent a hydrogen atom or a monovalent hydrocarbon group, preferably a monovalent hydrocarbon group, The alkyl group is more preferably an alkyl group having 1 to 8 and even more preferably a methyl group.

（式（Ｕ−９）〜（Ｕ−１２）中、Ｒ¹は、水素原子又はアルキル基を表し、Ｒ²及びＲ³はそれぞれ独立に、水素原子又は一価の炭化水素基を表し、Ａ⁶、Ａ⁷及びＡ⁸はそれぞれ独立に、二価の有機基を表し、Ｘ¹はそれぞれ独立に、水素原子又はプロトン（Ｈ⁺）以外の対カチオンを表す。） Moreover, as a more preferable example of the said hydrophilic monomer unit, the monomer unit represented by following formula (U-9)-(U-12) is mentioned.

(In the formulas (U-9) to (U-12), R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group, ⁶ , A ⁷ and A ⁸ each independently represent a divalent organic group, and X ¹ each independently represents a hydrogen atom or a counter cation other than a proton (H ⁺ ).

R ¹ and X ¹ in Formula (U-9) ~ (U -12) has the same meaning as R ¹ and X ¹ in Formula (U-1) and (U-2), and preferred ranges are also the same.
R ² and R ³ in the formula (U-9) ~ (U -12) , the formula (U-7) and (U-8) have the same meanings as R ² and R ³ in the preferred range is also the same .

A ⁶ in the formulas (U-9) and (U-10) represents a divalent organic group, preferably a linear or branched alkylene group, and is a linear or branched alkylene group having 2 to 20 carbon atoms. More preferably, it is more preferably a linear or branched alkylene group having 2 to 10 carbon atoms.
A ⁷ in the formulas (U-11) and (U-12) represents a divalent organic group, preferably a linear or branched alkylene group, and is a linear or branched alkylene group having 2 to 20 carbon atoms. More preferably, it is more preferably a linear or branched alkylene group having 2 to 10 carbon atoms.
A ⁸ in the formulas (U-11) and (U-12) represents a divalent organic group, preferably a linear or branched alkylene group, and is a linear or branched alkylene group having 1 to 10 carbon atoms. More preferably, it is more preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

Specific examples of the hydrophilic monomer unit include monomer units represented by the following (H-1) to (H-8). Moreover, the monomer unit which the sulfonic acid group of the monomer unit represented by the following (H-1)-(H-4) forms the salt can also be illustrated preferably.

The specific copolymer used in the present invention may have only one kind of the above-mentioned hydrophilic monomer unit, or may have two or more kinds.
The content ratio of the hydrophilic monomer unit in the specific copolymer used in the present invention is generally in the range of 20 to 98 mol%, and in the range of 30 to 98 mol%, based on all monomer units of the specific copolymer. It is preferably 40 to 90 mol%, more preferably 50 to 90 mol%.

The specific copolymer used in the present invention may have other monomer units in addition to the above acidic monomer units and hydrophilic monomer units.
Other monomer units are not particularly limited, and may be monomer units derived from known monomers. As another monomer unit, the monomer unit which has a hydroxyl group and / or a polyalkyleneoxy group can illustrate preferably.
The content ratio of the other monomer units in the specific copolymer used in the present invention is preferably 40 mol% or less, more preferably 30 mol%, based on the total monomer units of the specific copolymer. More preferably, it is 20 mol% or less.

The specific copolymer used in the present invention is also a vinyl copolymer.
The vinyl copolymer is, for example, a monomer having an ethylenically unsaturated bond such as acrylates, methacrylates, styrenes, aromatic vinyl compounds, aliphatic vinyl compounds, allyl compounds, acrylic acid, methacrylic acid, and the like. It is a copolymer obtained by copolymerizing two or more monomers.
The specific copolymer may be any copolymer such as a random copolymer, a block copolymer, or a graft copolymer, but is preferably a random copolymer.
The acidic monomer unit, the hydrophilic monomer unit, and other monomer units are monomer units obtained from monomers having an ethylenically unsaturated bond.

The fountain solution composition of the present invention may contain one specific copolymer alone or two or more.
The content of the specific copolymer in the fountain solution composition of the present invention is suitably 0.005 to 10% by mass in the fountain solution from the viewpoint that the anti-stain effect of the non-image area is sufficiently exhibited. It is preferable that it is 0.01-5 mass%, and it is still more preferable that it is 0.01-3 mass%.
The weight average molecular weight of the specific copolymer is preferably 5,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, 500,000 or less. It is more preferable that
The number average molecular weight of the specific copolymer is preferably 1,000 or more, more preferably 2,000 or more, preferably 500,000 or less, and 300,000 or less. It is more preferable.
The polydispersity (weight average molecular weight / number average molecular weight) of the specific copolymer is preferably 1.1-10.

In the fountain solution composition of the present invention, in addition to the acyclic hydrocarbon compound and the water-soluble copolymer, at least a compound of the following general formula (I) is used as a solubilizing agent when preparing a concentrate. One type is preferably used, and these compounds synergistically enhance the effects of the present invention.
Compounds of general formula (I) R ¹ —O— (CH ₂ CHR ² O) _m —H (I)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R ² represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 5).
Specifically in the compound of general formula (I), in the formula, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, specifically a hydrogen atom, a methyl group, There are an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. From the viewpoint of increasing the solubility of the diol compound and suppressing blanket piling, a hydrogen atom, an n-butyl group or A t-butyl group is particularly preferred. M represents an integer of 1 to 5, an integer of 1 to 3 is preferable, and 1 is particularly preferable.

Specific examples of the compound represented by the general formula (I) include, when R ¹ is an alkyl group, ethylene glycol mono t-butyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol Monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tetrapropylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monopropyl ether, Propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether Ter, tripropylene glycol monoisopropyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoisobutyl ether, propylene glycol Examples include monotertiary butyl ether, dipropylene glycol monotertiary butyl ether, and tripropylene glycol monotertiary butyl ether. Of these, n-butyl or t-butyl ether of propylene glycol or ethylene glycol can be preferably used.

Specific examples of R ^{1 in the} general formula (I) are hydrogen atoms include propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and pentapropylene glycol. Among these, in order to increase the solubility of the diol compound, propylene glycol, dipropylene glycol and tripropylene glycol are preferable, and propylene glycol is most preferable.

The compound represented by the general formula (I) is preferably used in combination of a plurality of the above compounds. In particular, when a compound in which R ¹ is an alkyl group and a compound in which R ¹ is a hydrogen atom are used in combination, blanket piling and roller strip are prevented. it can.
The addition amount of the compound represented by the general formula (I) is suitably 0.05 to 5.0% by mass in the fountain solution from the viewpoint of suppressing blanket piling and suppressing problems such as roller strips, and more preferably It is the range of 0.1-3.0 mass%.

  The fountain solution composition of the present invention also has, as a wetting solvent, 3-methoxy-3-methylbutanol, 3-methoxybutanol, ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol, hexylene glycol, glycerin, diglycerin. Polyglycerin, trimethylolpropane and the like can be used. These solvents may be used in the range of 0.1 to 3% by mass, preferably 0.3 to 2% by mass of dampening water.

The fountain solution composition of the present invention can further contain a water-soluble polymer compound. Examples of the water-soluble polymer compound used in the fountain solution composition of the present invention include gum arabic, starch derivatives (for example, dextrin, enzymatically degraded dextrin, hydroxypropylated enzymatically degraded dextrin, carboxymethylated starch, phosphate starch, Octenyl succinated starch), alginate, fibrin derivatives (for example, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose) and other natural products, polyethylene glycol and copolymers thereof, Polyvinyl alcohol and its derivatives, polyvinyl pyrrolidone, polyacrylamide and its copolymers, polyacrylic acid and its copolymers, vinyl methyl ether / maleic anhydride Acid copolymer, vinyl acetate / maleic anhydride copolymer include a composite of polystyrene sulfonic acid and copolymers thereof. Among the water-soluble polymer compounds, carboxymethylcellulose, polyvinylpyrrolidone, hydroxypropylcellulose, and hydroxypropylmethylcellulose can be particularly preferably used.
The molecular weight of these water-soluble polymer compounds is preferably 300 to 500,000, more preferably 300 to 100,000, and particularly preferably 500 to 30,000.
The content of the water-soluble polymer compound is suitably 0.0001 to 0.1% by mass of dampening water, and more preferably 0.0005 to 0.05% by mass.

It is preferable that the fountain solution composition of the present invention is further adjusted to a preferred value by a pH adjuster. The pH value is preferably used in the acidic region in the range of 3 to 7, but can also be used in the alkaline region of pH 7 to 11. As said pH adjuster, water-soluble organic acid, inorganic acid, or those salts can be used.
Preferred organic acids include acetic acid, citric acid, succinic acid, malic acid, tartaric acid, lactic acid, ascorbic acid, gluconic acid, hydroxyacetic acid, malonic acid, levulinic acid, sulfanilic acid, p-toluenesulfonic acid, phytic acid, and organic phosphonic acid Examples of inorganic acids include phosphoric acid, nitric acid, sulfuric acid, and polyphosphoric acid, and alkali metal salts, alkaline earth metal salts or ammonium salts, and organic amine salts are also preferably used. These may be used as a mixture of two or more. The addition amount of these pH adjusters to the fountain solution is preferably in the range of 0.001 to 0.3% by mass.

The fountain solution composition of the present invention may further contain a pyrrolidone derivative or acetylene glycol / acetylene alcohol as an aid for improving wettability. Examples of the pyrrolidone derivatives include ethyl pyrrolidone, butyl pyrrolidone, pentapyrrolidone, hexapyrrolidone, octyl pyrrolidone, and lauryl pyrrolidone.
As acetylene glycol / acetylene alcohols, 3,5-dimethyl-1-hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetra Methyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2-butyne-1,4-diol, 3-methyl-1-butyn-3-ol, And ethylene oxide and / or propylene oxide adducts thereof. Of the above compounds, in particular octylpyrrolidone, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and 2,4 , 7,9-Tetramethyl-5-decyne-4,7-diol, preferably a compound having 4 to 10 ethylene oxides added thereto. These compounds are suitably used at 0.0001 to 1.0% by mass of dampening water, more preferably 0.001 to 0.1% by mass.

In the fountain solution composition of the present invention, 2-ethyl-1,3 is also used to adjust the dynamic surface tension, solubilize, or suppress the mixing rate (emulsification rate) of the printing ink within an appropriate range. -Hexanediol, ethylene oxide and / or propylene oxide adduct of 2-ethyl-1,3-hexanediol, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of glycerin, propylene oxide adduct of sorbitol, tetrahydrofluor Furyl alcohol or the like may be added, and 2-ethyl-1,3-hexanediol is particularly preferable, and tetrahydrofurfuryl alcohol is preferable as a solubilizer.
These compounds are suitably used at 0.01 to 7% by mass of dampening water, more preferably 0.05 to 5% by mass.

As other components of the fountain solution composition of the present invention, for example, a compound obtained by adding ethylene oxide and propylene oxide to ethylenediamine or diethylenetriamine can be further contained. Even when the remaining water droplets are left to evaporate and remain concentrated, the image area is not damaged.
In these, the addition mole number ratio of ethylene oxide and propylene oxide is suitably in the range of 5:95 to 50:50, more preferably in the range of 20:80 to 35:65. Each copolymer chain may have a block structure or a random structure. The addition compound used in the present invention has a weight average molecular weight of preferably 500 to 5,000, more preferably 800 to 1,500, and most suitable is one having a weight average molecular weight of about 1000, and the molecular weight, ethylene oxide and propylene oxide. The ratio can be determined by, for example, measurement of hydroxyl value and amine value, NMR measurement, and the like.
By including 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass of the above compound in the fountain solution composition, good printability is exhibited even if isopropyl alcohol is substituted. To do.

In the fountain solution composition of the present invention, a surfactant can be further used as an aid for improving wettability. Among the surfactants, for example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, alkyl benzene sulfonic acid salts, alkyl naphthalene sulfonic acid salts, Alkylphenoxy polyoxyethylenepropyl sulfonates, polyoxyethylene alkylsulfenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated castor oil, Sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxy Tylene alkylphenyl ether sulfate ester salt, polyoxyethylene styryl phenyl ether sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkylphenyl ether phosphate ester salt, styrene-maleic anhydride copolymer And partial saponification products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensates, and the like.
Among these, dialkyl sulfosuccinates, alkyl sulfates and alkyl naphthalene sulfonates are particularly preferably used.

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl 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 esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid die Noruamido acids, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides.
In addition, fluorine-based surfactants and silicon-based surfactants can also be used.
Among these, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used.
In the case of using a surfactant, considering the foaming point, the content thereof is 1.0% by mass or less, preferably 0.001 to 0.5% by mass of dampening water.

The fountain solution composition of the present invention may contain saccharides. Sugars used include sugar alcohols obtained by hydrogenation.
Specific examples of preferred saccharides include D-erythrose, D-throse, D-arabinose, D-ribose, D-xylose, D-erythro-pentulose, D-allulose, D-galactose, D-glucose, D-mannose, D-talose, β-D-fructose, α-L-sorbose, 6-deoxy-D-glucose, D-glycero-D-galactose, α-D-allo-heptulose, β-D-altro-3-heptulose, Saccharose, lactose, D-maltose, isomaltose, inulobiose, hyalbiouron, maltotriose, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-idit, D, L-Talit, Zulsit, Allozulsit, Maltitol, etc. And the like.
These saccharides may be used alone or in combination of two or more.
The saccharide content is suitably 0.01 to 1% by mass, preferably 0.1 to 0.8% by mass, of dampening water.

In the fountain solution composition of the present invention, calcium ions or the like contained in tap water or well water for diluting the concentrated liquid at the time of use may adversely affect printing and cause the printed matter to become dirty. In such a case, the above disadvantages can be eliminated by adding a chelating agent. Preferred chelating agents include potassium salts of the following acids and sodium salts thereof. Examples of the acid include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1-hydroxyethane-1,1-diphosphonic acid, and aminotri (methylenephosphonic acid). Organic phosphonic acids or phosphonoalkanetricarboxylic acids. An organic amine salt is also effective in place of the sodium salt or potassium salt of the chelating agent.
These chelating agents are selected so that they are stably present in the dampening water during use and do not impair the printability.
As content of the chelate compound in dampening water at the time of use, 0.001-0.5 mass% is suitable, Preferably it is 0.002-0.25 mass%.

  The fountain solution composition of the present invention may contain an ester that has been conventionally used as a fragrance as an odor masking agent. Among them, preferred are n-pentyl acetate, isopentyl acetate, n-butyl butyrate, n-pentyl butyrate and isopentyl butyrate, and n-butyl butyrate, n-pentyl butyrate and isopentyl butyrate are particularly preferable.

  Examples of the preservative used in the fountain solution composition of the present invention include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benztriazole derivatives, derivatives of amidine or guanidine, four Quaternary ammonium salts, pyridine, quinoline or guanidine derivatives, diazine or triazole derivatives, oxazole or oxazine derivatives, bromonitroalcohol-based bromonitropropanol, 2,2-dibromo-2-nitroethanol, 3-bromo-3- Examples thereof include nitropentane-2,4-diol. A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeast, etc., and is preferably in the range of 0.001 to 1.0% by mass of dampening water, and various molds, bacteria, It is preferable to use two or more preservatives that are effective against yeast.

In the fountain solution composition of the present invention, a food coloring or the like can be preferably used as a colorant. For example, CI No. 19140, 15985 as a yellow coloring matter, CI No. 16185, 45430, 16255, 45380, 45100, a purple coloring matter as a red coloring matter CI No. 42640, CI No. 42090 and 73015 as blue dyes, CI No. 42095 as green dyes, and the like.
Examples of the rust inhibitor usable in the present invention include benzotriazole, 5-methylbenzotriazole, thiosalicylic acid, benzimidazole and derivatives thereof.
As the antifoaming agent that can be used in the present invention, a silicon antifoaming agent is preferable, and any of emulsifying dispersion type and solubilizing type can be used.

The balance is water as a component of the fountain solution composition of the present invention.
The fountain solution composition is generally concentrated and commercialized when it is usually commercialized. Therefore, a concentrated solution can be obtained as an aqueous solution in which various components described above are dissolved using water, preferably demineralized water, that is, pure water.
When such a concentrated solution is used, it is diluted about 10 to 200 times, particularly about 30 to 100 times with tap water, well water or the like during normal use, and used as a dampening water during use.

The fountain solution composition of the present invention can be used for various lithographic printing plates. In particular, a photosensitive lithographic printing plate having an aluminum plate as a support and a photosensitive layer thereon is subjected to image exposure and development. Thus, it can be suitably used for the lithographic printing plate obtained.
A preferable example of such PS plate is a photosensitive layer comprising a mixture of a diazo resin (a salt of a condensate of p-diazodiphenylamine and paraformaldehyde) and a shellac as described in British Patent 1,350,521. On the aluminum plate, polymers having diazo resin and hydroxyethyl methacrylate unit or hydroxyethyl acrylate unit as main repeating units as described in British Patent Nos. 1,460,978 and 1,505,739 And a photosensitive polymer system containing a dimethylmaleimide group described in JP-A-2-236552 and JP-A-4-274429 was provided on an aluminum plate. A negative PS plate such as the one disclosed in JP-A-50-125806 It includes positive PS plate provided on an aluminum plate and a photosensitive layer comprising a mixture of O- quinonediazide photosensitive material and a novolac-type phenolic resins as described in.
It can also be used for a positive PS plate that has been burned.

In the composition forming the photosensitive layer, an alkali-soluble resin other than the alkali-soluble novolak resin can be blended as necessary.
For example, styrene-acrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer, alkali-soluble polyurethane resin, alkali-soluble vinyl resin described in JP-B-52-28401, alkali-soluble polybutyral resin, and the like. it can.
Further, a PS plate having a photosensitive layer of a photopolymerizable photopolymer composition as described in US Pat. Nos. 4,072,528 and 4,072,527 on an aluminum plate, British Patent Nos. 1,235,281 and A PS plate having a photosensitive layer made of a mixture of an azide and a water-soluble polymer on an aluminum plate as described in each specification of No. 1,495,861 is also preferable.
Furthermore, it can be suitably used for a CTP plate that is directly exposed with a visible or infrared laser. Specific examples include a photopolymer type digital plate (for example, LP-NX manufactured by Fuji Film Co., Ltd.), a thermal positive type digital plate (for example, LH-PI manufactured by Fuji Film Co., Ltd.), printing performed with dampening water and ink. Examples include an on-press developing plate (for example, ET-S manufactured by Fuji Film Co., Ltd.) and a thermal negative type digital plate (for example, LH-NI manufactured by Fuji Film Co., Ltd.).

Next, the present invention will be described more specifically with reference to examples.
% Indicates mass% unless otherwise specified.
[Examples 1 to 25 and Comparative Examples 1 to 11]
Various fountain solution compositions were prepared in exactly the same manner except that the diol compound and the water-soluble polymer compound were changed as shown in the following Table 1 using the same mass in the following formulation.
In the formula, the unit is gram, and the amount added when water is finally added to adjust to 100 gram, which is the same as mass%. The various fountain solution compositions thus obtained are subjected to a printing test without dilution, that is, these fountain solution compositions correspond to the fountain solution at the time of use.

Prescription component of fountain solution composition (use liquid) when used Addition amount propylene glycol mono-n-butyl ether 0.5 g
Propylene glycol 0.5g
0.3 g of diol compounds in Table 1
0.01 g of water-soluble polymer compounds in Table 1
Ammonium nitrate 0.05g
Citric acid 0.02g
2,2-Dibromo-2-nitroethanol 0.002 g
2-Methyl-5-chloro-4-isothiazolin-3-one 0.002 g
Benzotriazole 0.001g
Add water to make 100g

The structure of the water-soluble copolymer used as the water-soluble polymer compound is shown below together with the mol% of the monomer unit.

Printing test Using each fountain solution composition, by means of Lithron 26 printing machine manufactured by Komori Corporation, Toyo Ink Co., Ltd. ink: Super Leo Echo SOY Black L, Oji Paper Co., Ltd. fine coated paper: The following evaluation was performed after printing 20000 sheets with OK Top Coat +, Fuji Film Co., Ltd. plate: PN-V. Before printing, the non-image area on the plate was scratched by rubbing nylon sponge with a load of 7 g / cm ² .
(1) Blanket Piling Evaluation After printing is completed, the blanket is removed, and the height of the deposit on the non-image area is measured with a stylus type surface roughness meter (surf coder). The relative value was evaluated. A smaller value indicates a lower height of the pile.
(2) Scratch stain on non-image area After printing, the scratch-like stain on the printed material was visually observed and ranked as follows.
A: Scratches on the plate are hardly visible on the printed matter.
B: Scratches on the plate are slightly visible on the printed matter.
C: Scratches on the plate are clearly seen on the printed matter.

なお、比較例で用いた水溶性高分子の分子量は次のとおりである。
カルボキシメチルセルロース（０．３万）、リン酸デンプン（０．５万）、ポリスチレンスルホン酸（３．０万）

In addition, the molecular weight of the water-soluble polymer used in the comparative example is as follows.
Carboxymethylcellulose (30,000), starch phosphate (50,000), polystyrene sulfonic acid (30,000)

  From the results shown in Table 1, by using a fountain solution containing a specific diol compound and a specific water-soluble copolymer according to the present invention, while maintaining the blanket piling suppression effect by the diol compound well, the plate surface It can be seen that it is possible to satisfactorily protect the scratches of the prints, suppress the occurrence of scratches on the printed matter, and provide a high-quality printed matter stably.

Claims (4)

  An acyclic hydrocarbon compound having two OH groups and a total carbon number of 9, and at least one selected from an oxygen acid group and a carboxy group of phosphorus in the side chain, a sulfonic acid group and a betaine structure A fountain solution for lithographic printing, comprising a water-soluble copolymer having at least one selected from the group consisting of:   The lithographic printing according to claim 1, wherein the acyclic hydrocarbon compound contains at least one selected from 2-butyl-2-ethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol. Fountain solution composition. The fountain solution composition for lithographic printing according to claim 1 or 2, further comprising a compound represented by the following general formula (I).
R ¹ —O— (CH ₂ CHR ² O) _m —H (I)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R ² represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 5).   A heat-set-off-ring printing method using the heat-set type off-wheel ink and the fountain solution composition according to any one of claims 1 to 3.