JPS6015476A - Printing ink composition and additive for ink - Google Patents

Abstract

PURPOSE:To provide an ink compsn. which does not stain non-image areas, gives a sufficient density to image areas, hardly cause emulsification and makes it possible to carry out litho printing using dampering water, containing an organopolysiloxane contg. two specified kinds of substituents. CONSTITUTION:An ink compsn. for litho printing contains an organopolysiloxane contg. at least one subsituent of formula I (wherein X is 0-4; a is 1-50; b is 0-50; R' is H, alkyl, acyl) and at least one substituent of formula II or III(wherein Y is 0-4; R'', R''' are each a 1-30C hydrocarbon group contg. no unsaturated bonds at its terminal; Z is 2-30). The ink compsn. can be obtd. by mixing or kneading a conventional vehicle for ink compsn., said organopolysiloxane, a pigment and optionally other additives with a solvent or diluent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lithographic printing ink composition using dampening water and an ink additive.

A lithographic printing plate consists of an oleophilic printed area that accepts oil-based ink and an oil-repellent non-printed area that does not accept ink.
Generally, the non-image area is composed of a hydrophilic area that receives water. Therefore, in normal lithographic printing, both ink and water are supplied to the printing plate, and the image area selectively receives colored ink and the non-image area receives water, and the ink on the image is applied to a substrate such as paper. This is done by being transcribed. Lithographic printing plates that use dampening water include presensitized plates (so-called PS plates) that use diazonium compounds, electrophotographic lithographic printing plates that use zinc oxide or organic photoconductors,
Lithographic printing plates based on silver salt photography using silver halide emulsions as photosensitive components are known, and there are many types of inks used for printing with such lithographic printing plates. Are known. However, conventional printing inks are
Even if good prints can be obtained using a particular printing plate or dampening solution, various defects may occur due to changes in the type of plate or printing conditions, and in some cases In some cases, it may not be possible to use it at all. The properties required for such printing ink are as follows:
It goes without saying that it is important that a sufficient amount of ink adheres to the printed area and that no ink adheres to the non-printed area, but it is also important that the This means that the characteristics must be obtained. Further, as described above, it is desirable that the printing method be unaffected even if the plate material, type of dampening solution, printing conditions, etc. change.

An object of the present invention is to provide a lithographic printing ink composition using dampening water that satisfies the above-mentioned requirements.

Another object of the present invention is to provide an ink additive for the above ink composition.

As a result of extensive research to achieve the above object, the present inventors have found that by using an ink composition containing the compounds described below, stains are less likely to occur in non-image areas.
It has been found that it is possible to perform lithographic printing using dampening water, which provides sufficient density to the image area, prevents emulsification, and is highly tolerant to changes in conditions. Such a compound is an organopolysiloxane containing at least one substituent each of substituent A and substituent B. Here, substituent A (formula % formula %) (in the formula, X is an integer of 0 to 4, a is an average number of 1 to 50,
b represents an average number of 0 to 50, R' represents a hydrogen atom, an alkyl group, or an acyl group), and the substituent B is represented by the formula % (in the formula, y represents an integer of D to 4, R' and R/// represents a saturated or unsaturated hydrocarbon having 1 to 60 carbon atoms that does not contain a terminal unsaturated bond, and 2 represents an integer of 2 to 60).

The use of organopolysiloxanes in ink compositions for dry lithographic printing is described, for example, in JP-A-N'F34B-410.
It is publicly known in Publication No. 7. However, many of the various organopolysiloxanes can be mixed with commercially available printing inks and printed on a lithographic printing plate that uses dampening water, such as a PS plate, if there is no background smudge. In some cases, not enough ink is applied to the printed area, or not enough ink is applied to the printed area even though there is background smearing, or when a sufficient amount of ink is applied to the printed area, the background smear is severe. It was not possible to obtain good prints due to emulsification.

The present inventors have repeatedly conducted improvement research in view of the above-mentioned problems with lithographic printing ink compositions that use dampening water, and have discovered that the functional groups contained in organopolysiloxane are groups that have relatively high compatibility with water, that is, hydrophilic. The present invention was achieved as a result of discovering that the presence of a sexual group plays an important role.

As described in the above-mentioned Japanese Patent Application Laid-Open No. 48-4107, organopolysiloxane acts as an agent for reducing adhesion energy to non-printing areas and is effective in preventing scumming of dry lithographic printing plates. However, in a lithographic printing plate using fountain solution containing an ink composition containing an organopolysiloxane having a hydrophilic group of the present invention, emulsification and scumming may occur.
[It was unexpected that it would be possible to achieve a sufficient print density in the printed area for DJ'ing.

Representative examples of organopolysiloxanes used in the present invention are shown by the following average composition formulas (I) to (IV).

In the above formula, m is a number on average from 0 to 100, and n is on average from 1 to 50.
o) number, l is an average number of 0 to 1, R represents a substituent such as an unsubstituted or substituted alkyl group, alkoxy group, aromatic group, etc. Preferred examples are methyl group, phenyl M, It is a building group.

G represents a mixture of substituent A and substituent B shown above; preferred examples of substituent A are x = 5, a = 3-10, b = 1-6, a/a,
b=0.75-1.00, R'=hydrogen atom or methyl group.

Preferred examples of substituent B are y-==3, R″ is C11H23, C13■■27, C
15H3□, C17H355C11'211C13H2
5-C1! '1H29) C17H331C1'lH3
F) C, 7H edition, or Z29 or 10, R'// is CH3, C2H5, C
31(.

It is.

In addition, as mentioned in the reference section, the meaning that the organopolysiloxane used in the present invention contains at least one substituent A and B in one molecule means, for example, the above average composition formula (
In the formula where Il is rewritten (in the formula, X+Y-=n, A and B each represent substituent A1 and substituent B), it tends to seem necessary that X and Y are 1 or more, For example, even if the composition is X = 0.5 Y = 0.5, X and Y are statistical numbers, and in the molecule X =
1, Y=D17) and f7) X=0. Y=1, x=
1, Y=1 exists with a very high probability.

Among these, those with x=1 and y=o and those with X=0 and Y=1 are not components of the present invention, but those with X=1 and y=1 are components of the present invention, and x=i those of y=o and X=O,
Since it has been confirmed that the component with Y=1 does not have any disadvantageous effect on the present invention, the component with Y=0.5 and Y=0.
5, ie n=1, are also compounds according to the invention.

Specific compound examples are shown below.

The proportion of the organopolysiloxane of the present invention contained in the ink composition varies somewhat depending on its type and other components of the ink composition, but is generally in the range of 1 to 70% by weight, preferably 6 to 50% by weight. It can be changed as appropriate.

The ink composition of the present invention can be sufficiently mixed with a solvent, diluent, etc., by adding, for example, a usual vehicle for ink compositions, the above-mentioned organopolysiloxane, a colorant, and other auxiliary agents as necessary. or a composition obtained by mixing them. Of course, the organopolysiloxane of the present invention can also be added to a commercially available printing ink.

In the above composition, vehicles for the ink composition include drying oils, synthetic drying oils, natural or processed jet fats such as rosin, copal, tanzuru, shellac, hardened rosins, and rosin esters, phenolic resins, and rosin-modified phenols. Resin, 100% phenolic resin, maleic acid resin,
Alkyd resin, petroleum resin, vinyl resin, acrylic resin,
polyamide resin, epoxy resin, amino alkyd resin,
Synthetic resins such as polyurethane 4/T1 resin, aminosynth resin, cellulose derivatives such as nitrocellulose and ethyl cellulose, and other materials such as glue, casein, dextrin, f-in, etc. can be used, and as the coloring agent, for example, Inorganic or organic pigments used in conventional ink compositions can be used.

Further, as the additives, for example, wax, grease, lT1' bedding agent, stabilizer, desiccant, auxiliary desiccant, thickener, dispersant, filling agent, and other known additives may be used. I can do it.

Ink of the present invention? In preparing the 111 product,
The organopolysiloxane, the vehicle for the ink composition, and other additives as necessary are uniformly mixed or kneaded by a conventional method such as a roll mill method, a ball mill method, an attritor method, or a Sun IS mill method. Bye.

The aforementioned organopolysiloxane mixed with or reacted with a resin or oil that is miscible with the siloxane can be used as an additive in ordinary commercially available inks or the ink composition of the present invention. Particularly good results are obtained when

In the ink additive of the present invention, the term "admixture" refers to a mixture of the siloxane and resin or oil that is homogeneously mixed together as a blend without substantially chemically reacting, and the reactant refers to: It means that the functional groups of the siloxane and the functional groups of the resin or oil have at least partially chemically reacted to form a homogeneous mixture or reactant. but,
As the functional group of the above siloxane, the previously defined substituents (
Its properties are improved by reaction with HL resin or oil.
It's not something to lose. That is, the substituent G of the above siloxane
must also be included in the form of the additive of the present invention.

The ink additive of the present invention is based on a mixture or reaction product of the above-mentioned organopolysiloxane and a resin or oil that is miscible with the siloxane. Organopolysiloxanes such as those described above may be used as such in ink compositions (e.g. commercially available ink products) or ink manufacturing formulations comprising conventional printing ink vehicles, colorants and other optional additives. It will become clear from the Examples described below that there is a difference in the effect of the present invention between when the ink is added and when it is added as an ink additive.

The ink additive of the present invention is sufficiently miscible with any ink composition when producing ink by adding it to a normal ink composition (commercially available) or to a mixture during ink production. It has been found that it has the advantage of being able to

As the resin or oil used in the ink additive of the present invention, those known as vehicles for ink compositions as described below can be used, and depending on the type of organopolysiloxane having a hydrophilic group, they may be sufficiently mixed. 1) All you have to do is choose something that you can do.

The ink additives of the present invention are not limited to simply mixed compositions, but also include alkyd resins, aminoalkyd resins, phenolic resins, rosin liquid phenolic resins, epoxy resins, and acrylic resins as described in the above-mentioned patent publications. , 41
It can be used as a reaction product of a resin or oil that is modified by heating a monomer oil or the like and an organopolysiloxane.

Ink additives obtained under reaction conditions of 100 to 200°C for 1 to 5 hours are particularly preferred;
It is desirable to avoid reactions at temperatures higher than C or higher as much as possible. The amount of the organopolysiloxane to be used relative to the resin or oil is arbitrary, but 6 to 60% by weight is generally preferred.

The proportion of the ink additive of the present invention contained in the printing ink composition varies somewhat depending on the type and other components of the ink composition, but generally O81 to 70% by weight, preferably 0.5 to 60 jl(- It can be changed as appropriate within a range of 957%.

The ink additives of the present invention can be used in addition to commercially available printing inks, or can be used in the production of printing inks.

Vehicles for ink compositions containing the ink additive of the present invention include drying oils, synthetic drying oils, rosins, copal,
Natural or processed products such as tamples, shellac, hardened rosin, rosin esters (I'+1 fat, phenolic resin, rosin-modified phenolic resin, 100% phenol l11'
11 fat, maleic acid fat, alkyd resin, petroleum resin, vinyl (H1 fat, acrylic (S11 fat, polyamide resin,
Synthetic resins such as epoxy resins, amino alkylene resins, polyurethane resins, aminosilast resins, cellulose conductors such as nitrocellulose and ethyl cellulose, and other materials such as glue, casein, dextrin, and zein can be used. As the colorant, for example, those used in conventional ink compositions such as inorganic or organic pigments can be used. The ink containing the ink 5 (compound 5) (compound 11) and the ink additive can be applied to any lithographic printing plate that is used for offset printing using dampening water, regardless of the type of stone used. Also, a wide range of types of 7i+tL water can be used, including not only regular water but also conventional additives such as desensitizers, buffers, preservatives, moistening agents, etc. For example, gum arabic, carboxymethyl cellulose, sodium alginate, polyvinylpyrrolidone, polyvinylimidazole, polyvinyl methyl ether, etc.; QH (water-maleic acid copolymer, Carboxymethyl star hexaalginate ammonium, cellulose alginate, methyl cellulose, sulfates (sodium sulfate, ammonium sulfate, etc.), phosphoric acid, nitric acid, zinc acid, tannins and salts thereof, containing two or more hydroxy groups polyol compounds (polyethylene glycol, ethylene glycol, fluoropylene gellicol, glycerol, diethylene glycol, hexylene glycol, etc.); ),
Polyacrylic dian, ammonium dichromate, chromium alum, alginate propylene glycol ester, aminopolycarboxylic acid salts (ethylenediaminetetraacetic acid sodium salt, etc.), inorganic colloids (colloidal silica, etc.)
, surfactant, etc., or two or more Z can be added.

In addition, water-miscible organic solvents such as methanol, dimethylformamide, and dioxane and liquid i! A small amount of a coloring agent such as phthalocyanine dye, malachite green, or ultramarine may be added with particular consideration to the illumination quality and appearance.

The present invention will be explained below using typical examples, but the present invention is not limited in any way.

Example 1 An ink containing silicone-modified alkytoy ItJ fat as an ink additive was prepared by A, B, and Dick.
350 CD (Product name of offset printing machine manufactured by Nee, Bee, Dick) While supplying the following dampening water to the lithographic printing machine, press Silver Master (lithographic printing plate manufactured by Mitsubishi Paper Industries, Ltd. using the silver complex diffusion transfer method). When printing was carried out using ink (A) containing 195 product names of silicone-modified alkyd (195 product names of Even after printing , o o o sheets or more, there was no background smudge, good printed matter with high ink density was obtained, and no ink emulsification was observed at all.On the other hand,
The following compound (b) as organopolysiloxane
When ink (B) made in the same manner as ink (A) except for using rt is used, emulsification occurs with 0 or more sheets, causing background smudges, and the lifting of ink (B) Furthermore, only printed matter with low ink density was obtained on the stand.

・Carbon black for prescription printing ink 200 Phthalocyanine blue 50 Rosin-modified phenolic resin 200 Silicone-modified alkyd resin (al) 200 Linseed oil 100 High boiling point solvent (No. 0 trubene l-H) 200 Wax compound 40 Naphthene 1 ~ Cobalt 1 ~ (Metal d゛2' crawl W7.5
%) 10 total 1,000 parts of the above mixture was uniformly kneaded using three rolls to form ink (A). I was.

The above mixture was reacted at 150° C. for 2 hours to obtain a silicone-modified alkyd resin (al).

[Formulation and manufacturing method of ink (B)]

It was produced in exactly the same manner as ink (A) except that the following compound (b) was used instead of the exemplified compound (ro) of ink (A).

Compound (b) Example 2 It is possible to manufacture an ink using disazo yellow carmine 6B and 7 talocyanine blue as the normal phase in the ink (A) of Example 1, but colored ink tends to cause background stains. It was confirmed that the lithographic printing plate described above could also produce good printing without any of these defects.

Example 6 The alkyd resin used in the ink (A) of Example 1 and the exemplary compound (6) were mixed in advance at room temperature to prepare an ink additive composition, and the silicone-modified alkyd resin (al
) was used instead of. Same result as ink (A)
and the ink additive of the present invention does not necessarily have a force ll i, W
It was confirmed that there is no inhalation that is a 6-reactant.

Example 4 Exemplary compound (3) used in the production of silicone-modified Al-Todo (al) was converted into Exemplary compound (1), (2),
When Example 1 was repeated in exactly the same manner except for replacing (4) or (5), the same results as ink (A) were obtained. Kaisho 50-71410, Kaisho 50-
□゛11mi is described in Publication No. 71411, etc., and these can be referred to.

Example 5 When printing was carried out in the same manner as in Example 1 using the following ink, the same results as ink (A, ) of Example 1 were obtained.

0 Prescription method of the above rosin-modified phenolic resin FES (a2) Linseed oil 700 Total 1,000 parts A mixture consisting of the above composition was reacted at 150°C for 6 hours to obtain the ink additive of the present invention.

In place of exemplified compound (2), other exemplified compounds (1) and (
Similar results were obtained when using 5).

For the method of producing silicone-modified vegetable oil, please refer to the detailed description of /) in JP-A-51-21906 and JP-A-51-21907.

Example 6 An ink obtained by adding 10 layers of the ink additive of the present invention used in Examples 1 to 5 to seven commercially available ink compositions with different ink tack values and colors and thoroughly kneading the mixture and a commercially available ink without the additive. When printing was performed using the following, results similar to those obtained in Example 1 were obtained in both cases.

Example 7 Example 6 was repeated using a commercially available PS plate and a printing plate using zinc oxide, using respective dedicated dampening waters. A remarkable difference was observed in all planographic printing plates.

Example 8 When printing was performed using an ink prepared by adding 2% by weight of exemplified compound (1) or (4) to a commercially available ink composition and thoroughly kneading the mixture, and an ink without the additive, the same results as in Example 6 were obtained. was gotten.

Agent Akira Asamura

Claims (1)

[Scope of Claims] , (1) A lithographic printing ink composition containing an organopolysiloxane, wherein the organopolysiloxane contained in one molecule contains the following formulas A and 2. B
An ink composition for lithographic printing using dampening water, characterized in that it contains at least one of each of two types of substituents. 2A; -CxHzXO(CH2CH2O)a, (CH2CH
O)1. , R'CH3 (in the formula, X is an integer of 0 to 4, a is an average number of 1 to 50,
b represents an average number of 0 to 50, and R' represents a hydrogen atom, an alkyl group, or an acyl group. ) 2B; 〃 -CyH2yOCR or 1 -CH2C-0R'1' z! 1 (In the formula, y represents an integer of 0 to 4, R" and R"' represent a saturated or unsaturated hydrocarbon having 1 to 60 carbon atoms not containing a terminal unsaturated bond, and 2 represents an integer of 2 to 60. ) An ink additive of a mixture or reaction product of an organopolysiloxane and a resin or oil having miscible properties with respect to the siloxane, wherein the organopolysiloxane has the following formula A in one molecule. A lithographic printing ink additive using dampening water, characterized in that it contains at least one of each of the two substituents 2 and 2B. 2A; -CxI(2xO(CH2CH20Chaos(CH3CHO)
bR'1 CH3 (wherein, )2B; -CyH2yOCR" or 1 -C2I(27SC-OT(' 1 (in the formula, y is an integer of 0 to 4, R" and R/// are 1 carbon number not containing a terminal unsaturated bond) ~60 saturated or unsaturated hydrocarbons, 2 represents an integer from 2 to 60.)