JP4684825B2 - Dampening solution composition for lithographic printing - Google Patents

Description

  The present invention relates to a fountain solution composition for lithographic printing, and more specifically to a fountain solution composition useful for an offset printing method of a lithographic printing plate.

Lithographic printing is a printing method that skillfully uses the property that water and oil do not essentially mix, and the printing plate surface consists of an area that receives water and repels oil-based ink, and an area that repels water and receives oil-based ink. Thus, the former is a non-image area and the latter is an image area.
In the lithographic printing method, a non-image area is generally moistened with a fountain solution to increase the interfacial chemical difference between the image area and the non-image area. Ink receptivity is increased.
The fountain solution is usually supplied first in the form of a concentrated solution, and is diluted with tap water or well water when used. Calcium ions, etc. contained in the tap water or well water react with the components in the damp water to produce precipitates, which can adhere to the rolls of the printing press and cause adverse effects on printing. There is.

Furthermore, in recent years, recycled paper, which is increasing from the viewpoint of environmental conservation, and light weight with a coating layer on the surface containing a large amount of polyvalent metal salts such as calcium carbonate to increase the whiteness of recycled paper. Recycled coated paper is increasing, and when printing using these printing papers, the dampening water will drop calcium carbonate particles from the surface coat layer of the paper under long-term continuous use conditions. There is a problem of triggering. In addition, when printing is performed using printing ink containing a large amount of calcium carbonate pigment to improve the abrasion resistance of the printed matter or to reduce the cost, the dampening solution will be wet under long-term continuous use conditions. Water that dissolves the surface of extender pigment or calcium carbonate particles, calcium oxide particles, etc. that are added as extenders in the ink, and the ink structure comprising the varnish component of the ink and the dispersion state of these pigment components There is also the problem of destroying and inducing pigment particle shedding from the ink.
Precipitates caused by calcium ions in the fountain solution as described above, or particles such as calcium carbonate that has fallen off from peripheral materials (ink, paper, etc.) used in printing adhere to the ink roll of the printing press, As a result, the normal transferability of the ink is deteriorated, so-called roller strip phenomenon occurs, and there is a problem that printability is deteriorated, specifically, ink landing property is deteriorated.

Furthermore, in recent years, recycled paper, which is increasing from the viewpoint of environmental conservation, and light weight with a coating layer on the surface containing a large amount of polyvalent metal salts such as calcium carbonate to increase the whiteness of recycled paper. Recycled coated paper is increasing, and when printing using these printing papers, the dampening water will drop calcium carbonate particles from the surface coat layer of the paper under long-term continuous use conditions. There is a problem of triggering. In addition, when printing is performed using printing ink containing a large amount of calcium carbonate pigment to improve the abrasion resistance of the printed matter or to reduce the cost, the dampening solution will be wet under long-term continuous use conditions. Water that dissolves the surface of extender pigment or calcium carbonate particles, calcium oxide particles, etc. that are added as extenders in the ink, and the ink structure comprising the varnish component of the ink and the dispersion state of these pigment components There is also the problem of destroying and inducing pigment particle shedding from the ink.
Precipitates caused by calcium ions in the fountain solution as described above, or particles such as calcium carbonate that has fallen off from peripheral materials (ink, paper, etc.) used in printing adhere to the ink roll of the printing press, As a result, the normal transferability of the ink is deteriorated, so-called roller strip phenomenon occurs, and there is a problem that printability is deteriorated, specifically, ink landing property is deteriorated.

  In order to solve these problems, it has been proposed to add a compound capable of chelating with calcium as a calcium sequestering agent in the fountain solution (see, for example, Patent Documents 1 to 4). Patent Document 1 describes a specific biodegradable chelating agent. These compounds chelate against calcium dissolved in dampening water and form water-soluble salts, so that organic acids and carbonates contained in dampening water as pH buffering components are converted into calcium and water. It has the effect of preventing the formation and precipitation of sparingly soluble salts. On the other hand, these compounds have the effect of eluting calcium ions from the calcium carbonate contained in ink and paper and increasing the concentration of calcium ions in the fountain solution. As a result, the calcium concentration in water rises, and as a result, it is not possible to sufficiently suppress the precipitation of calcium salt of organic acid or carbonic acid on the ink roll.

Patent Document 2 proposes to include a specific organic phosphonic acid in the fountain solution. This compound hardly causes calcium ions to be eluted from ink or paper, but the chelate compound with calcium is not sufficiently stable. Therefore, once water-soluble calcium chelate is formed, salt exchange with organic acid or carbonic acid occurs over time, and precipitation of calcium salt of organic acid or carbonic acid carbonate that is poorly water-soluble is sufficiently suppressed. Can not.
Further, when these chelating agents are used in combination, there is a strong tendency to dissolve the grained surface of the aluminum support of the printing plate, and soiling may occur when long-run imprint printing is performed.
Patent Documents 3 and 4 propose diethylenetriaminepentaacetic acid or a salt thereof as a chelating agent. When this compound is included in the fountain solution composition, although there is a tendency that precipitation of calcium salt of organic acid or carbonic acid on the ink roll tends not to occur, it is not enough to completely suppress the roller strip. It was.

JP 11-291659 A JP 2001-105764 A JP-A-7-186567 JP 2002-254852 A

  An object of the present invention is to solve the problems in the prior art, exhibit a good calcium sequestration effect without promoting calcium elution from ink and paper, and provide a calcium salt on the ink roll of a printing press. In addition to preventing the precipitation of inorganic pigment particles such as calcium carbonate, the occurrence of ink peeling (roller strip phenomenon) on the ink roll is suppressed, and lithographic printing showing good printability It is in providing the fountain solution composition. The object of the present invention is also to exhibit stable printability without causing problems such as dirt even when long run printing is performed, to obtain excellent printed matter, and to enable stable continuous printing for a long time. And providing a fountain solution for lithographic printing.

（式中、Ｍ₁〜Ｍ₅はそれぞれ独立して水素原子、Ｎａ、Ｋ、ＮＨ₄又はＮ(Ｒ)₄（Ｒは置換又は未置換のアルキル基を表す。）を表す。）
で示される化合物、
下記一般式(II)：
Ｍ₆ＮＯ₃ (II)
（式中、Ｍ₆は水素原子、Ｎａ、Ｋ、ＮＨ₄又はＮ(Ｒ)₄（Ｒは置換又は未置換のアルキル基を表す。）を表す。）
で示される化合物、及び
下記一般式（III)：

（式中、Ａ及びＢはそれぞれ独立に−ＣＨ₂ＣＨ₂Ｏ−又は−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−を表し、Ａ及びＢは互いに異なる基であって、ａ〜ｈは各々０以上の整数を表し、ａ〜ｈは−ＣＨ₂ＣＨ₂Ｏ−の合計モル数が２〜１０、及び−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−の合計モル数が４〜３０となる値を表す。）で示される化合物
を含有することを特徴とする、平版印刷用湿し水組成物である。 As a result of repeated research on a fountain solution for lithographic printing in order to achieve the above-mentioned problems, the present inventors have found that an excellent fountain solution composition can be obtained by using a combination of specific compounds. The headline and the present invention have been completed.
Accordingly, the present invention provides the following general formula (I):

(Wherein, M _{1 to} M ₅ each independently represents a hydrogen atom, Na, K, NH ₄ or N (R) ₄ (R represents a substituted or unsubstituted alkyl group).)
A compound represented by
The following general formula (II):
M ₆ NO ₃ (II)
(In the formula, M ₆ represents a hydrogen atom, Na, K, NH ₄ or N (R) ₄ (R represents a substituted or unsubstituted alkyl group).)
And a compound represented by the following general formula (III):

(In the formula, A and B each independently represent —CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, wherein A and B are groups different from each other, and a to h are each 0 or more. A to h represent values in which the total mole number of —CH ₂ CH ₂ O— is 2 to 10 and the total mole number of —CH ₂ CH (CH ₃ ) O— is 4 to 30. A fountain solution for lithographic printing, comprising a compound represented by the formula:

The present invention combines a chelating agent having a specific structure, nitric acid or nitrate, and a compound obtained by adding ethylene oxide and propylene oxide to ethylenediamine, so that precipitation of calcium salt and adhesion or deposition on an ink roll such as calcium carbonate can be achieved. A unique phenomenon that is suppressed occurs, the occurrence of roller peeling is suppressed, an previously unknown effect is obtained, and the emulsification stability of the ink is improved without causing excessive emulsification of the ink Is found.
As an embodiment of the present invention, a compound represented by the following general formula (IV) and / or 2-ethyl-1,3-hexanediol can be further contained.
R ¹ O — (— CH ₂ CH (R ² ) —O—) _m —H (IV)
(In the formula, R ¹ represents an alkyl group having 3 to 8 carbon atoms, R ² represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3).
As a preferred embodiment of the present invention, at least one selected from citric acid, tartaric acid, malic acid, malonic acid, succinic acid, glutaric acid, maleic acid, gluconic acid, lactic acid and salts thereof as a component having pH buffering property. There is a fountain solution for lithographic printing as described above which contains a seed compound.

The fountain solution composition for lithographic printing of the present invention does not promote the elution of calcium from ink or paper, and exhibits a good calcium sequestration effect, and precipitates calcium salts and the like on the ink roll of a printing press. As well as preventing adhesion and accumulation of inorganic pigment particles such as calcium carbonate, it is possible to sufficiently suppress the occurrence of ink peeling (roller strip phenomenon) on the ink roll. According to the fountain solution composition for lithographic printing of the present invention, even when a large number of copies are printed without changing the printing plate over a long period of time, scumming occurs in the non-image area or the dot highlight A high-quality printed matter can be stably obtained without causing image omission such as part skipping, and printing efficiency and productivity can be improved.
The fountain solution composition for lithographic printing of the present invention has excellent wettability to the printing plate surface, and does not excessively emulsify the ink, and prints the ink on the ink roll even under long-time continuous printing conditions. It can be stably maintained in a suitable state. According to the fountain solution composition for lithographic printing of the present invention, during printing, continuous printing can be performed stably for a long period of time without causing problems such as stains on the printing plate, blinding, water loss, and poor ink deposition. The printability is good.
The fountain solution composition for lithographic printing according to the present invention can also replace isopropyl alcohol in the fountain solution composition in various continuous water supply type printing presses without requiring expert skill in the printing operation. it can.

Hereinafter, the present invention will be described in detail.
The fountain solution is generally concentrated and commercialized when used on a commercial basis, and when used, such a concentrate is appropriately diluted and used as a fountain solution. In the present specification, the concentrated product is referred to as a fountain solution composition.
Unless otherwise indicated, the contents and addition amounts of various components referred to below in this specification are based on the total mass of dampening water at the time of use.

（式中、Ｍ₁〜Ｍ₅はそれぞれ独立して水素原子、Ｎａ、Ｋ、ＮＨ₄又はＮ(Ｒ)₄（Ｒは置換又は未置換のアルキル基を表す。）を表す。）
式中、Ｍ₁、Ｍ₂、Ｍ₃、Ｍ₄又はＭ₅がＮ(Ｒ)₄（Ｒは置換又は未置換のアルキル基を表す。）を表すとき、該アルキル基は一般に炭素原子数１〜８のアルキル基であり、置換基としては水酸基、炭素原子数６以下のアルコキシ基、ハロゲン原子、アミノ基などが挙げられる。
上記一般式（Ｉ）で示される化合物は市場で一般に入手することができ、本発明において市販品を使用することができる。一般式（Ｉ）の化合物の市販品の例として、キレスト社製の商品名キレストＰＡ、及びキレストＰなどがある。
一般式（Ｉ）で示される化合物の湿し水における含有量は、一般に０．０００５〜０．２質量％の範囲である。この化合物の含有量がこの範囲にあると、インキロール上へのカルシウム塩などの析出や炭酸カルシウムなどの無機顔料粒子の付着、堆積を防止でき、インキロール上のインキ剥げに関して充分な抑制効果が得られる点で好ましい。
一般式（Ｉ）で示される化合物の量は、より好ましくは０．００１〜０．１質量％であり、特に好ましくは０．００２〜０．０５質量％である。 [Compound represented by the general formula (I)]
The fountain solution composition for lithographic printing according to the present invention contains a compound represented by the following general formula (I).

(Wherein, M _{1 to} M ₅ each independently represents a hydrogen atom, Na, K, NH ₄ or N (R) ₄ (R represents a substituted or unsubstituted alkyl group).)
In the formula, when M ₁ , M ₂ , M ₃ , M ₄ or M ₅ represents N (R) ₄ (R represents a substituted or unsubstituted alkyl group), the alkyl group generally has 1 carbon atom. -8 alkyl groups, and examples of the substituent include a hydroxyl group, an alkoxy group having 6 or less carbon atoms, a halogen atom, and an amino group.
The compound represented by the general formula (I) can be generally obtained on the market, and a commercially available product can be used in the present invention. As an example of a commercial item of the compound of general formula (I), there are a trade name Cylest PA and Cylest P manufactured by Cylest.
The content of the compound represented by the general formula (I) in the fountain solution is generally in the range of 0.0005 to 0.2% by mass. When the content of this compound is within this range, it is possible to prevent precipitation of calcium salts and the like and adhesion and deposition of inorganic pigment particles such as calcium carbonate on the ink roll, and there is a sufficient suppression effect on ink peeling on the ink roll. It is preferable at the point obtained.
The amount of the compound represented by the general formula (I) is more preferably 0.001 to 0.1% by mass, and particularly preferably 0.002 to 0.05% by mass.

[Compound represented by the general formula (II)]
The fountain solution composition for lithographic printing of the present invention contains a compound represented by the following general formula (II).
M ₆ NO ₃ (II)
(In the formula, M ₆ represents a hydrogen atom, Na, K, NH ₄ or N (R) ₄ (R represents a substituted or unsubstituted alkyl group).)
In the formula, when M ₆ is N (R) ₄ (R represents a substituted or unsubstituted alkyl group), the alkyl group is generally an alkyl group having 1 to 8 carbon atoms. Examples include a hydroxyl group, an alkoxy group having 6 or less carbon atoms, a halogen atom, and an amino group.
A commercial product can also be used for the compound of the general formula (II).
The content of the compound represented by the general formula (II) in the fountain solution is generally in the range of 0.001 to 0.5 mass%. When the content of this compound is within this range, it is possible to prevent precipitation of calcium salts and the like and adhesion and deposition of inorganic pigment particles such as calcium carbonate on the ink roll, and there is a sufficient suppression effect on ink peeling on the ink roll. It is preferable at the point obtained.
The content of the compound represented by the general formula (II) is more preferably 0.005 to 0.3% by mass, and particularly preferably 0.01 to 0.2% by mass.

（式中、Ａ及びＢはそれぞれ独立に−ＣＨ₂ＣＨ₂Ｏ−又は−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−を表し、Ａ及びＢは互いに異なる基であって、ａ〜ｈは各々０以上の整数を表し、ａ〜ｈは−ＣＨ₂ＣＨ₂Ｏ−の合計モル数が２〜１０、及び−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−の合計モル数が４〜３０となる値を表す。）
上記一般式（III）で示される化合物において、エチレンオキサイドとプロピレンオキサイドの結合構造の例として、先にエチレンオキサイドを付加し、その後プロピレンオキサイドを付加したブロック構造、先にプロピレンオキサイドを付加し、その後エチレンオキサイドを付加したブロック構造、同時にエチレンオキサイドとプロピレンオキサイドを付加したランダム構造があるが、いずれの構造のものもほぼ同様の効果が得られる。 [Compound represented by formula (III)]
The fountain solution composition for lithographic printing of the present invention further contains a compound represented by the following general formula (III).

(In the formula, A and B each independently represent —CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, wherein A and B are groups different from each other, and a to h are each 0 or more. A to h represent values in which the total mole number of —CH ₂ CH ₂ O— is 2 to 10 and the total mole number of —CH ₂ CH (CH ₃ ) O— is 4 to 30. )
In the compound represented by the above general formula (III), as an example of the bond structure of ethylene oxide and propylene oxide, a block structure in which ethylene oxide is added first and then propylene oxide is added, and propylene oxide is added first, and then There are block structures to which ethylene oxide is added, and random structures to which ethylene oxide and propylene oxide are added at the same time, but the same effect can be obtained with any structure.

In the compound represented by the general formula (III), the total number of added moles of ethylene oxide (—CH ₂ CH ₂ O—) per molecule is 2 to 10, preferably 4 to 9, and 1 molecule. The total number of added moles of propylene oxide (—CH ₂ CH (CH ₃ ) O—) is 4 to 30, preferably 12 to 28.
As for the compound shown by general formula (III) used by this invention, the range of 300-2500 is suitable for a weight average molecular weight, Preferably it is 500-2400, More preferably, it is 1000-2300.
The compound represented by the general formula (III) can be produced by adding ethylene oxide and propylene oxide to ethylenediamine according to a conventional method. For example, ethylenediamine and / or propylene oxide is reacted with ethylenediamine in the presence of a catalyst. Let
The molecular weight of the compound and the ratio of ethylene oxide to propylene oxide can be determined by, for example, measurement of hydroxyl value and amine value, NMR measurement, and the like.
The addition amount of the compound represented by the general formula (III) in the fountain solution is suitably 0.001 to 1% by mass from the viewpoint of improving the wettability of the fountain solution and the emulsification stability of the ink. , Preferably it is 0.005-0.5 mass%, More preferably, it is 0.02-0.3 mass%.

[Wettability improver]
The fountain solution composition of the present invention can further contain a solvent or a surfactant that improves the wettability of the fountain solution.
Among these, a compound represented by the following general formula (IV) and 2-ethyl-1,3-hexanediol are particularly mentioned.
Compound represented by formula (IV):
_{^{R 1 O - (- CH 2}} CH (R 2) -O-) m-H (IV)
(In the formula, R ¹ represents an alkyl group having 3 to 8 carbon atoms, R ² represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3).
In the compound of the general formula (IV), R ¹ represents a linear or branched alkyl group having 3 to 8 carbon atoms, and R ¹ is specifically n-propyl group, isopropyl group, n-butyl group, Examples include isobutyl group, t-butyl group, n-pentyl group, isopentyl group, t-pentyl group, n-hexyl group, n-octyl group, and 2-ethylhexyl group. m represents an integer of 1 to 3.

Specific examples of the compound of the general formula (II) include ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, ethylene glycol Monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, ethylene glycol monotertiary butyl ether, diethylene glycol monotertiary butyl ether and tripropylene Recall monotertiary butyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monopropyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether, propylene glycol monobutyl ether , Dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoisobutyl ether, propylene glycol monotertiary butyl ether, dipropylene glycol monotertiary rib Examples include tilether and tripropylene glycol monotertiary butyl ether. These compounds can be used alone or in combination of two or more.
Of these, n-butyl ether, isobutyl ether or t-butyl ether of propylene glycol, and t-butyl ether of ethylene glycol can be preferably used.
The content of at least one selected from the compound represented by formula (IV) and 2-ethyl-1,3-hexanediol in the fountain solution is suitably 0.05 to 5% by mass, preferably 0. It is 2-3 mass%, Most preferably, it is 0.4-2 mass%.

[Organic acid having pH buffering properties and salts thereof]
The fountain solution composition for lithographic printing of the present invention may contain at least one selected from organic acids having pH buffering properties and salts thereof.
In order for the compound represented by the general formula (I) to effectively capture calcium and suppress the generation of roller strips, it is desirable to maintain the pH of the fountain solution within a predetermined range. Specifically, in order to effectively exhibit the calcium scavenging function of the compound of the general formula (I), the pH of the fountain solution is maintained from the acidic region to the neutral region, and the carboxylic acid group of the compound of the general formula (I) It is preferable that a part of is dissociated. A suitable pH value for this purpose is in the range of 3-8, more preferably pH 4-7, particularly preferably in the range of pH 4.5-6.5.

In the present invention, the combination of the compound of the general formula (I) and the compound of the general formula (II) can maintain the pH value of the fountain solution composition within a preferable range, but further to maintain the pH value stably. The organic acid compound having pH buffering property is added to the fountain solution composition of the present invention.
Specific examples of organic acids having pH buffering properties include citric acid, malic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, maleic acid, gluconic acid, lactic acid, acetic acid, glycolic acid, succinic acid, ascorbic acid, levulinic acid Etc. Examples of the salts include alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts. Among these, citric acid, tartaric acid, malic acid, malonic acid, succinic acid, glutaric acid, maleic acid, gluconic acid, lactic acid, and their salts, even when multiple copies are printed, the background stains and halftone dot highlights jump out. This is preferable without causing printing trouble such as. Further, malic acid, succinic acid, glutaric acid and salts thereof are particularly preferable. These organic acids and salts thereof may be used as a mixture of two or more.
The above-mentioned organic acid can be adjusted to pH by adding an alkaline agent such as NaOH, KOH, ammonia, organic amines, or by using in combination with alkali metal salt, alkaline earth metal salt or ammonium salt of organic acid, organic amine salt, etc. Used by adjusting the value to the desired range.
The addition amount of these organic acids and / or salts thereof in the fountain solution is generally appropriately 0.002 to 0.2% by mass, preferably 0.005 to 0.1% from the viewpoint of suppressing the roller strip. It is mass%, Most preferably, it is 0.01-0.06 mass%.

  In the fountain solution composition for lithographic printing of the present invention, as other auxiliary agents, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, Triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, propylene Glycol, dipropylene Recall, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, polypropylene glycol having a molecular weight of 200 to 1000 and their monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether and monobutyl ether, ethylene glycol, diethylene glycol, triethylene glycol , Polyethylene glycol, butylene glycol, hexylene glycol, ethyl alcohol, n-propyl alcohol, benzyl alcohol, ethylene glycol monophenyl ether, 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, 1-butoxy-2 -Propanol, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol Le, methoxyethanol, and the like may be added butoxyethanol.

  A small amount of a surfactant may be added to the fountain solution composition of the present invention. For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid salts, linear alkylbenzenesulfonic acid salts, branched alkylbenzenesulfonic acid salts, alkylnaphthalene. Sulfonates, alkylphenoxy polyoxyethylenepropyl sulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, Hydrogenated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride Acid ester salts, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene Examples thereof include partially saponified products of maleic anhydride copolymers, partially saponified products of olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates. Among these, dialkyl sulfosuccinates, alkyl sulfates and alkyl naphthalene sulfonates are particularly preferably used.

  Nonionic surfactants include polyoxyalkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial esters, sorbitan fatty acid moieties. Esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid partial esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyglycerin fatty acid partial esters, poly Oxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxy Alkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, such as trialkylamine oxides. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used.

Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, and the like. Examples of amphoteric surfactants include alkyl imidazolines. In addition, examples of the fluorine-based anionic surfactant include fluorine-based surfactants, such as perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, and fluorine-based nonionic surfactants. Examples of the perfluoroalkylethylene oxide adduct, perfluoroalkylpropylene oxide adduct, and fluorine-based cationic surfactant include perfluoroalkyltrimethylammonium salts.
The content of these surfactants is 10% by mass or less, preferably 0.01 to 3.0% by mass in dampening water in view of foaming.

The fountain solution composition of the present invention may further contain a water-soluble polymer compound, saccharide, glycerin, pH adjuster, chelate compound, preservative, colorant, rust inhibitor, antifoaming agent and the like. These additives will be described below.
Specific examples of water-soluble polymer compounds include gum arabic, starch derivatives (eg, dextrin, enzymatically degraded dextrin, hydroxypropylated enzymatically degraded dextrin, carboxymethylated starch, phosphate starch, octenyl succinated starch), alginate, cellulose Natural products such as derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, methylcellulose, glyoxal modified products thereof) and the like, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone , Polyacrylamide and its copolymer, polyacrylic acid and its copolymer, vinyl methyl ether / anhydrous Maleic acid copolymer, synthetic materials such as vinyl acetate / maleic anhydride copolymers. These polymer compounds can be used alone or as a mixture, and the addition amount thereof is appropriately in the range of 0.0001 to 5% by mass in dampening water, and preferably in the range of 0.003 to 1% by mass. .

Among the water-soluble polymer compounds, polyvinyl pyrrolidone can be particularly preferably used. The polyvinylpyrrolidone contained in the fountain solution composition means a homopolymer of vinylpyrrolidone. Polyvinylpyrrolidone having a molecular weight of 200 to 3,000,000 is appropriate, preferably having a molecular weight of 300 to 500,000, more preferably 300 to 100,000. Particularly preferred is 300 to 30,000.
These polyvinyl pyrrolidones can be used alone or in combination of two or more kinds having different molecular weights. Further, it can be combined with a low molecular weight polyvinyl pyrrolidone, for example, a vinyl pyrrolidone oligomer having a polymerization degree of 3 to 5.
As such polyvinyl pyrrolidone, a commercially available product can be used. For example, various grades such as K-15, K-30, K-60, K-90, and K-120 manufactured by ISP can be used.
The content of polyvinyl pyrrolidone in the fountain solution is suitably 0.001 to 0.3% by mass, preferably 0.005 to 0.2% by mass.

The fountain solution composition of the present invention preferably contains at least one selected from the group consisting of sugars and glycerin. The sugar to be used can be selected from monosaccharides, disaccharides, oligosaccharides, and the like, and includes sugar alcohols obtained by hydrogenation. Specific examples 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-alto-3-heptulose, saccharose, lactose, D Maltose, isomaltose, inulobiose, hyalbiouron, maltotriose, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-digit, D, L-talit, zulcit , Allozulcit, maltitol, reduced water candy, etc. It is. These saccharides may be used alone or in combination of two or more.
Glycerin may be used alone or in combination with sugars.
In the fountain solution, the content of at least one selected from the group consisting of sugars and glycerin is suitably 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass.

  In the fountain solution composition of the present invention, various acids such as inorganic acids, sulfonic acid acids, and phosphonic acid acids are used in combination in order to maintain the hydrophilicity of the printing plate non-image area due to the etching effect. May be. Examples include sulfanilic acid, p-toluenesulfonic acid, phytic acid, organic phosphonic acid, phosphoric acid, sulfuric acid, polyphosphoric acid and salts thereof (alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, etc.). Can be mentioned.

An additional chelate compound may be added to the fountain solution composition of the present invention. Examples of such chelating compounds include: ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotri Acetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2-propanoltetraacetic acid, its potassium salt, its sodium salt etc. Aminopolycarboxylic acids, 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt thereof, sodium salt thereof; 2-phosphonobutanetricarboxylic acid-2,3,4, potassium salt thereof, sodium salt thereof; 1-phosphonoethane Carboxylic acid-1,2,2, potassium salt, sodium salt thereof; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt thereof, sodium salt; aminotri (methylenephosphonic acid), potassium salt thereof, sodium Mention may be made of organic phosphonic acids such as salts or phosphonoalkanetricarboxylic acids.
Organic amine salts are also effective in place of the sodium or potassium salts of the above chelating agents.
These chelating agents are selected so that they are stably present in the dampening water and do not impair the printability. The amount to be added is 0.001 to 3% by mass, preferably 0.01 to 1% by mass in dampening water.

  The fountain solution composition of the present invention may contain a preservative. Specific examples of preservatives include benzoic acid and derivatives thereof, phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benztriazole derivatives, derivatives of amidine or guanidine, quaternary ammonium salts , Pyridine, quinoline or guanidine derivatives, diazine or triazole derivatives, oxazole or oxazine derivatives, halogenonitropropane compounds, bromonitroalcohol-based bromonitropropanol, 1,1-dibromo-1-nitro-2-ethanol, 3 -Bromo-3-nitropentane-2,4-diol and the like. A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the types of bacteria, molds, yeasts, but 0.0001-1.0 with respect to the fountain solution. The range of mass% is preferable, and it is preferable to use two or more preservatives that are effective against various molds, bacteria and yeasts.

The fountain solution composition of the present invention may further contain a colorant, a rust inhibitor, an antifoaming agent, and the like. Food coloring agents and the like can be preferably used as the colorant. For example, CI No. 19140, 15985 as a yellow dye, CI No. 16185, 45430, 16255, 45380, 45100 as a red dye, CI No. 42640 as a purple dye, CI No. 42090, 73015 as a blue dye, CI No. 42095, and the like.
Examples of the rust inhibitor include benzotriazole and derivatives thereof, thiosalicylic acid, benzimidazole and derivatives thereof, and the like. Of these, benzotriazole and its derivatives can be preferably used. Specific examples of benzotriazole and derivatives thereof used in the present invention include benzotriazole (1,2,3-benzotriazole), methylbenzotriazole (4-methylbenzotriazole, 5-methylbenzotriazole, etc.), dimethylbenzotriazole (4,6-dimethylbenzotriazole, 5,7-dimethylbenzotriazole, etc.), carboxybenzotriazole, and 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole.
Of these, benzotriazole, methylbenzotriazole and dimethylbenzotriazole are preferably used.

  Commercially available products can be used for benzotriazole and its derivatives used in the present invention. The fountain solution composition of the present invention can be used singly or in combination of two or more selected from benzotriazole and its derivatives. By containing such a benzotriazole compound in the dampening water in the range of 0.00001 to 0.1% by mass, it is possible to exert an appropriate anticorrosion and rust prevention effect on the metal. More preferably, the benzotriazole compound is contained in the dampening water in an amount of 0.00005 to 0.01% by mass, particularly preferably 0.0002 to 0.005% by mass.

As the antifoaming agent, a silicon antifoaming agent is preferable, and any of an emulsified dispersion type and a solubilized type can be used.
The fountain solution composition of the present invention further comprises a hardening agent such as a chromium compound and an aluminum compound, a cyclic ether: an organic solvent such as 4-butyrolactone, and a water-soluble surface active described in JP-A-61-193893. It is also possible to add an organometallic compound or the like in the range of 0.0001 to 1% by mass in damp water.

  The balance is water as a component of the fountain solution composition of the present invention. Accordingly, a fountain solution composition that is a concentrated solution can be obtained as an aqueous solution in which the above-described various components are dissolved using water, preferably demineralized water, that is, pure water. Such a concentrated solution is diluted about 10 to 200 times with tap water, well water or the like during normal use to obtain a dampening water during use.

The fountain solution composition of the present invention can completely replace isopropyl alcohol without using it in combination with a volatile organic solvent. Therefore, the fountain solution composition of the present invention can be a fountain solution composition substantially free of volatile organic solvents. Here, “substantially free of volatile organic solvent” means that the amount of the volatile organic solvent is 10% or less in the fountain solution composition as a concentrate according to the measurement method of ASTM D 2369-95. means.
The measurement method of ASTM D 2369-95 is to determine the amount of volatile organic solvent by the following formula using a 3 ml sample in a hot air oven at 110 ° C. for 1 hour.
Formula: {(mass of sample−mass of heating residue−mass of moisture in sample) / (mass of sample)} × 100 = amount of volatile organic solvent (mass%)
Even if isopropyl alcohol up to about 15% by mass is used in dampening water during use, there is no problem in print quality.

  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 (previously photosensitive). The applied printing plate is called a PS plate) and can be suitably used for a lithographic printing plate obtained by image exposure and development. 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- Kinonjiado 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 Photo Film Co., Ltd.), a thermal positive type digital plate (for example, HP-S manufactured by Fuji Photo Film Co., Ltd.), and a thermal negative type digital plate (for example, Fuji Photo Film Co., Ltd. LH-NI).

Next, the present invention will be described more specifically with reference to examples. % Indicates mass% unless otherwise specified.
Various fountain solution compositions of Examples 1 to 5 and Comparative Examples 1 to 8 were prepared according to the composition of Table 1 below. In the table, the unit is gram, and water is finally added to make 1000 ml. These are all concentrated types and are diluted at the time of use.
In addition, Compound (I), Comparative Compound (I) -1, (I) -2 and (I) -3, Compound (II), Compound (III), and Comparative Compound (III) used in Examples and Comparative Examples The structures of -1 and (III) -2 are as follows.

化合物(II)：一般式(II)においてＭ₆がアンモニウムイオンである。
化合物(III)：一般式(III)において−ＣＨ₂ＣＨ₂Ｏ−の合計付加モル数が８であり、及び−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−の合計付加モル数が２８である。
比較化合物(III)-１：一般式(III)において−ＣＨ₂ＣＨ₂Ｏ−の合計付加モル数が１であり、及び−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−の合計付加モル数が４である。
比較化合物(III)-２：一般式(III)において−ＣＨ₂ＣＨ₂Ｏ−の合計付加モル数が１４であり、及び−ＣＨ₂ＣＨ（ＣＨ₃）Ｏ−の合計付加モル数が３２である。

























Compound (I): In the formula (I), M _{1 to} M ₅ are hydrogen atoms.
Comparative compounds (I) -1 to (I) -3:

Compound (II): In the general formula (II), M ₆ is an ammonium ion.
Compound (III): In the general formula (III), the total number of added moles of —CH ₂ CH ₂ O— is 8 and the total number of added moles of —CH ₂ CH (CH ₃ ) O— is 28.
Comparative compound (III) -1: In the general formula (III), the total number of added moles of —CH ₂ CH ₂ O— is 1, and the total number of added moles of —CH ₂ CH (CH ₃ ) O— is 4. is there.
Comparative compound (III) -2: In the general formula (III), the total number of added moles of —CH ₂ CH ₂ O— is 14, and the total number of added moles of —CH ₂ CH (CH ₃ ) O— is 32. is there.

  Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 8 prepared as described above was diluted 40 times with pseudo-hard water having a hardness of 400 ppm, and the pH became around 4.8 to 5.3. Thus, it was adjusted with NaOH / dilute nitric acid to obtain a dampening solution that was actually used.

[Test method]
The printing machine uses Heidel MOV (Alcolor Water Supply), Fuji ink of Toyo Ink Mfg. Co., Ltd.'s name High Unity SOY, and Fuji Photo Film Co., Ltd. positive PS plate VS. Using a film of FQI chart made by photographic film, exposure with Ushio PS light, developing with Fuji Photo Film Developer DP-4, and gumming with Fuji Photo Film Gum Liquid FP-2 The following printing test was carried out using the light-weight coated paper of Chuetsu Pulp Co., Ltd. and the name Emine. The results are shown in Table 2 below.

(A) Continuous printing stability:
The amount of dampening water that does not cause stains and does not cause water loss (minimum water raising amount) was determined, and continuous printing was performed using the water scale. Judgment is made based on the number of printed sheets until the printed material becomes dirty or loses water and no good printed material is obtained.
20000 or more A
20000 to 5000 sheets B
Less than 5000 sheets C
(B) Emulsification:
The state of emulsification of the ink on the ink kneading roll when 10,000 sheets were printed was examined.
Good A
Slightly bad B
Bad C
(C) Roller strip resistance:
When 50,000 sheets were printed, the operation of the printing press was stopped, and the accumulation of calcium salt on the ink roll and the presence or absence of ink baldness were examined.
A Calcium salt is not deposited on the ink roll, and no ink baldness is generated. B Calcium salt is not deposited on the ink roll, but there is ink baldness. C There is much calcium salt deposited on the ink roll, and ink baldness is generated. is there

  From the above results, it is understood that the fountain solution according to the example of the present invention is excellent in all of the continuous printing stability, the emulsifying property, and the roller strip resistance. Furthermore, even when not containing a volatile organic solvent like the fountain solution composition of Examples 1-3, when containing a volatile organic solvent like the fountain solution composition of Examples 4 and 5, and Similarly good performance is obtained. The fountain solution compositions of the above examples also show good printability without using a highly volatile solvent component such as isopropyl alcohol, thus eliminating the problem of occupational safety, and organic The amount of solvent used can be reduced, which is very preferable from the viewpoint of the environment.

Claims (4)

Compound represented by the following general formula (I), a compound represented by the following formula (II), a compound represented by the following Symbol formula (III), and malic acid as a component having a pH buffering property, succinic acid, glutaric acid And a fountain solution for lithographic printing, comprising at least one compound selected from the group consisting of salts thereof.

(Wherein, M ₁ ~M ₅ each independently represent a hydrogen atom.)
M ₆ NO ₃ (II)
(In the formula, M ₆ represents a hydrogen atom, Na, K, NH ₄ or N (R) ₄ (R represents a substituted or unsubstituted alkyl group).)

(In the formula, A and B each independently represent —CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, wherein A and B are groups different from each other, and a to h are each 0 or more. A to h represent values in which the total mole number of —CH ₂ CH ₂ O— is 2 to 10 and the total mole number of —CH ₂ CH (CH ₃ ) O— is 4 to 30. ) The fountain solution composition for lithographic printing according to claim 1, wherein the component having pH buffering properties is malic acid and / or a salt thereof. The fountain solution composition for lithographic printing according to claim 1 or 2, further comprising a compound represented by the following general formula (IV) and / or 2-ethyl-1,3-hexanediol.
_{^{R 1 O - (- CH 2}} CH (R 2) -O-) m -H (IV)
(In the formula, R ¹ represents an alkyl group having 3 to 8 carbon atoms, R ² represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3). The fountain solution composition for lithographic printing according to claim 3, comprising 2-ethyl-1,3-hexanediol.