JP2007169464A - Lithographic printing ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing ink composition which has excellent scumming resistance, additional printability, inking property, setting property, and back-adhesion resistance. <P>SOLUTION: This lithographic printing ink composition is characterized by containing a rosin-modified phenolic resin as a binder resin and having a water content of 1 to 20% of ink on the rollers of an offset printing machine. The rosin-modified phenolic resin is obtained by adding and esterifying a di- to hexa-hydric alcohol with a rosin in a polyhydric alcohol OH value/rosin COOH value ratio of ≤1 in the presence of para-toluenesulfonic acid or an alkali metal or alkaline earth metal hydroxide as a catalyst. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  In the present invention, the water content of the ink on the roller of the offset printing machine is set to 1% to 20%, so that printing with water and lithographic printing excellent in excellent scumming property, fleshing property, setability and overprinting property is achieved. The present invention relates to a printing ink composition characterized by being an ink.

The printing method with water in printing is a method of obtaining printed matter by supplying ink to the image area and dampening water to the non-image area, but the ink form roller and the dampening water of the non-image area are in contact with each other. For this reason, when the ink on the ink roller is excessively emulsified with the fountain solution, quality accidents such as scumming and deterioration of the wearability often occur. Causes of excessive emulsification of the ink include raising the water dial due to background smudges in the non-image area and promoting emulsification by increasing the printing press temperature. The over-emulsified ink loses its adhesion to the paper and has a low viscoelasticity, resulting in a printed matter with deteriorated background stain and fleshing property, and further deteriorates the setting and drying properties on the paper.
None.

  An object of the present invention is a printing ink composition for water-containing lithographic printing, which is excellent in soiling property, fleshing property, setability, and backing property, with respect to the problems of the prior art. It is about.

  In order to solve the above-mentioned problems, the present inventors have used 2-6 valent polyhydric alcohols as binder resins, using paratoluenesulfonic acid or alkali metal or alkaline earth metal hydroxides as catalysts. By adding rosin-modified phenolic resin obtained by adding OH number of polyhydric alcohol / COOH number of rosin to rosin in the number of parts of 1 or less and esterifying it, the problem is solved I found out that I have completed this research.

 That is, the present invention provides a binder resin having a para-toluenesulfonic acid or a hydroxide of an alkali metal or alkaline earth metal as a catalyst, and a 2-6 valent polyhydric alcohol with respect to rosin. The water content of the ink on the roller of the offset printing press containing the rosin-modified phenolic resin obtained by adding and esterifying the OH number of the rosin in the number of parts where the COOH number of the rosin is 1 or less. It relates to a lithographic printing ink composition that is% -20%.

  The present invention also relates to the above lithographic printing ink composition, wherein the weight average molecular weight of the rosin-modified phenol resin having an OH number of polyhydric alcohol / COOH number of rosin of 1 or less is 10,000-150,000. .

  In the lithographic printing ink composition, the n-heptane tolerance of the rosin-modified phenolic resin having an OH number of polyhydric alcohol / COOH number of rosin of 1 or less is 1 to 40 ml. About.

  According to the present invention, it is possible to provide a printing ink composition for water-containing lithographic printing that is excellent in water-repellent printing, excellent stain resistance, fleshing property, setability, and backing properties.

  As the colorant used for obtaining the printing ink composition of the present invention, colorless or colored inorganic or organic pigments conventionally used in printing inks can be used. Specifically, inorganic pigments such as titanium dioxide, barium sulfate, calcium carbonate, magnetic iron oxide, organic pigments such as azo pigments, lake pigments, phthalocyanine pigments, isoindoline pigments, anthraquinone pigments, quinacrine pigments, And carbon black can be used. The content of the colorant in the printing ink composition is suitably about 3 to 40% by weight.

As the binder resin, para-toluenesulfonic acid or alkali metal or alkaline earth metal hydroxide as a catalyst, 2-6 valent polyhydric alcohol to rosin (OH number of polyhydric alcohol × A rosin-modified phenolic resin obtained by esterification reaction in the number of moles of polyhydric alcohol) / mol of rosin (hereinafter, OH number of polyhydric alcohol / COOH number of rosin) of 1 or less. Can be used. Examples of constituent materials of these resins include rosins, alkylphenols, polybasic acids, and polyhydric alcohols.
Specific examples of rosins include gum rosin, wood rosin, tall oil rosin, and mixtures.

Specific examples of the polybasic acid include phthalic acid, its anhydride, succinic acid or its anhydride, adipic acid or its anhydride, azelaic acid, sebacic acid and the like.
Specific examples of the polyhydric alcohol include glycerin, ethylene glycol, diethylene glycol, trimethylolpropane, triethylene glycol, polyethylene glycol, and pentaerythritol.

    Specific examples of the alkylphenol include coalic acid, paramethylphenol, paraethylphenol, paranormal propylphenol, paraisopropylphenol, paranormal butylphenol, paraisobutylphenol, para tertiary butylphenol, paranormal pentylphenol, paranormal nonylphenol, para Examples include alkylphenols such as normal dodecylphenol.

  The production method of the rosin-modified phenolic resin of the present invention is such that a phenol resin obtained by reacting rosins, paraalkylphenol and paraformaldehyde under a catalyst is reacted, and the OH number of polyhydric alcohol / COOH number of rosin) is 1. It can be obtained by adding polyhydric alcohol in the following parts and heating under an esterification catalyst such as paratoluenesulfonic acid or magnesium hydroxide. Moreover, it is preferable that the weight average molecular weights of the rosin modified phenol resin obtained are 10,000-150,000, and when it remove | deviates from this range, favorable printability may not be shown.

  Although content of binder resin is not specifically limited, The range of about 10 to 60 weight% is suitable in a printing ink composition, The said binder resin can use 2 or more types independently. In addition to the binder resin, the printing ink composition of the present invention may be used alone or in combination of two or more alkyd resins or petroleum resins as necessary.

By using the binder resin obtained by the above reaction, it is possible to obtain a printing ink composition which is excellent in background stain property, fleshing property, setting property and follow-up printing property in printing with water.
The water content of the ink on the roller of the printing machine needs to be 1 to 20%, and if it is out of this range, inconveniences such as poor soiling and poor reprinting will occur.

  In order to obtain the printing ink composition of the present invention, vegetable oils and / or vegetable oil esters and petroleum solvents can be used.

  Examples of the vegetable oil include soybean oil, linseed oil, cottonseed oil, safflower oil, tung oil, tall oil, dehydrated castor oil, canola oil, coconut oil, and other drying oils, semi-drying oils, and non-drying oils. The content of these vegetable oils is not particularly limited, but a range of about 10-60% by weight is appropriate in the printing ink composition, and these can be used alone or in combination of two or more.

  Examples of the fatty acid ester compound include monoalkyl esters or synthetic fatty acid esters of fatty acids derived from the above-mentioned drying oil, semi-drying oil, and non-drying oil. As the fatty acid monoester, a saturated and / or unsaturated fatty acid having 6 to 20 carbon atoms is preferable. Palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, eleostearin An acid etc. can be illustrated. The alcohol-derived alkyl group constituting the fatty acid ester preferably has 1 to 10 carbon atoms, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, tertiary butyl and 2-ethylhexyl. The content of these fatty acid esters is suitably in the range of about 10-60% by weight in the printing ink composition, and can be used alone or in combination of two or more.

Examples of the petroleum solvent include a crude oil-derived solvent (petroleum solvent) having an aromatic hydrocarbon content of 1% by weight or less, a petroleum solvent having an aniline point of 70 to 110 ° C. and a boiling point of 260 ° C. or more. Is preferred. When the aniline point is less than 70 ° C., the ability to dissolve the resin is too high, so that the viscosity of the ink becomes too low and the stain resistance is not sufficient. On the other hand, when the aniline point exceeds 110 ° C., the resin is poorly soluble, so that the fluidity of the ink is inferior, and as a result, only a printed matter with poor gloss and inking properties can be obtained. When the boiling point is less than 260 ° C., the amount of the solvent in the ink discharged on the printing machine is increased, and the ink is liable to accumulate on the rollers, plates and blankets due to the deterioration of the fluidity of the ink. .
The content of the petroleum solvent printing is suitably in the range of about 10-40% by weight in the printing ink composition.

  The n-heptane tolerance value of the rosin phenol resin used in the present invention needs to be 1 to 40 ml, and if it is out of this range, the ink setting property and fluidity are lowered, which is not preferable.

  Furthermore, in the printing ink composition of the present invention, a gelling agent, a pigment dispersant, a drier, a drying retarder, an antioxidant, a leveling aid, a friction resistance improver, and an anti-set-off agent are included as necessary. In addition, additives such as nonionic surfactants and polyhydric alcohols can be used as appropriate. Examples of gelling agents include trimethylolpropane-tris-β-N-aziridinylpropionate, azirine compounds such as pentaerythritolpropane-tris-β-N-aziridinylpropionate, glycerol polyglycidyl ether, Epoxy compounds such as methylolpropane polyglycidyl ether, aluminum chelate compounds such as ethyl acetoacetate aluminum diisoporooxide, aluminum trisethyl acetoacetate, aluminum isopropoxide, mono-sec-butoxyaluminum diisopropoxide, aluminum tri- Examples include aluminum alcoholates such as sec-butoxide.

  The printing ink composition of the present invention can be produced by a conventionally known method. As an example, a binder resin, a vegetable oil component, and a gelling agent as necessary are added to produce a varnish under cooking conditions of 190 ° C. for 1 hour. Next, for example, a color ink, a petroleum solvent, a vegetable oil component, a pigment dispersant or a pigment dispersion resin is added to the varnish, and a base for printing ink can be obtained by kneading with a bead mill or three rolls. I can do it. Subsequently, a vegetable oil component, a petroleum-based solvent, and other additives are added, and it can adjust to predetermined viscosity and can obtain a printing ink composition.

[Example]
EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited to these examples.

(Printing Resin Example A) In a reaction vessel, 1500 parts of gum rosin was previously reacted in a xylene solvent with 600 parts of paraoctylphenol and 400 parts of paraformaldehyde at 100 ° C. for 4 hours under a sodium hydroxide catalyst to remove water. A phenol resin was dropped at 150 ° C. and reacted for 2 hours. Further, 150 parts of pentaerythritol was added, and 1.5 parts of magnesium oxide was used as a catalyst, and the mixture was reacted at 250 ° C. for 7 hours to obtain a rosin-modified phenol resin having an OH / COOH = 0.89 normal heptane tolerance of 25 ml and a weight average molecular weight of 80000. A got.

(Printing Resin Example B) In a reaction vessel, 1500 parts of gum rosin was reacted in advance with 600 parts of paraoctylphenol and 400 parts of paraformaldehyde in a xylene solvent at 100 ° C. for 4 hours under a sodium hydroxide catalyst to remove water. A phenol resin was dropped at 150 ° C. and reacted for 2 hours. Further, 100 parts of glycerin was added, and 1.5 parts of p-toluenesulfonic acid was used as a catalyst and reacted at 250 ° C. for 7 hours, rosin-modified phenol having an OH / COOH = 0.66 normal heptane tolerance of 30 ml and a weight average molecular weight of 20000. Resin B was obtained.

(Printing Ink Resin Example C) In a reaction vessel, 1500 parts of gum rosin was previously reacted with 500 parts of para tert-butylphenol and 300 parts of paraformaldehyde in a xylene solvent at 100 ° C. for 4 hours under a sodium hydroxide catalyst. The phenol resin from which moisture was removed was dropped at 150 ° C. and reacted for 2 hours. Further, 80 parts of pentaerythritol was added, and 1.5 parts of paratoluenesulfonic acid was used as a catalyst and reacted at 250 ° C. for 12 hours, and rosin-modified phenol having an OH / COOH = 0.47 normal heptane tolerance of 7 ml and a weight average molecular weight of 70000. Resin C was obtained.

(Resin for Printing Ink Example D) In a reaction vessel, 1500 parts of gum rosin, 400 parts of paraoctylphenol, 100 parts of para tert-butylphenol and 300 parts of paraformaldehyde in advance in a xylene solvent at 100 ° C. under a sodium hydroxide catalyst. The phenol resin which made it react for 4 hours and removed water was dripped at 150 degreeC, and was made to react for 2 hours. Further, 80 parts of pentaerythritol was added, and 1.5 parts of calcium oxide was used as a catalyst, followed by reaction at 250 ° C. for 10 hours, rosin-modified phenol having OH / COOH = 0.47, normal heptane tolerance of 10 ml, and weight average molecular weight of 100,000. Resin D was obtained.

(Comparative Example E for printing ink) In a reaction vessel, 1500 parts of gum rosin was previously reacted in xylene solvent with 600 parts of paraoctylphenol and 400 parts of paraformaldehyde at 100 ° C. for 4 hours under a sodium hydroxide catalyst to remove moisture. The phenol resin was dropped at 150 ° C. and reacted for 2 hours. Further, 250 parts of pentaerythritol was added, and 1.5 parts of calcium oxide was used as a catalyst and reacted at 250 ° C. for 6 hours to obtain rosin-modified phenol having OH / COOH = 1.48, normal heptane tolerance of 45 ml, and weight average molecular weight of 20000. Resin E was obtained.

(Printing Resin Comparative Example F) In a reaction vessel, 1500 parts of gum rosin was reacted in advance with xylene solvent, 600 parts of para tert-butylphenol and 400 parts of paraformaldehyde at 100 ° C. for 2 hours under a sodium hydroxide catalyst. The phenol resin from which water was removed was dropped at 150 ° C. and reacted for 2 hours. Furthermore, 300 parts of pentaerythritol was added, 1.5 parts of calcium oxide was used as a catalyst, and the mixture was reacted at 250 ° C. for 10 hours to give OH / COOH = 2.6 normal heptane tolerance 5 ml, weight average molecular weight 160000 rosin-modified phenolic resin. Got F.

(Varnish Example A-C) Resin for printing ink Example A-C 45 parts Soybean oil 30 parts Nisseki AF Solvent 5 24.5 parts Aluminum chelate (aluminum diisoproxide monoethyl acetate) 0.5 parts Incubation was carried out at 190 ° C. for 1 hour to obtain varnish examples AC.

(Varnish Example D) Resin Example D for Printing Ink 45 parts Soybean oil 20 parts Nisseki AF Solvent 5 19.5 parts Soybean oil methyl ester, 0.5 parts of aluminum chelate (aluminum diisoproxide monoethyl acetate) The mixture was kept at 190 ° C. for 1 hour to obtain Varnish Example D.

(Varnish Comparative Example EF) Printing Ink Resin Example EF 45 parts Soybean Oil 30 parts Nisseki AF Solvent 5 24.5 parts Aluminum Chelate (Aluminum Diisoproxide Monoethyl Acetate) 0.5 part And kept at 190 ° C. for 1 hour to obtain Varnish Example EF.

[Production of printing ink composition]
Example 1-4
Varnish Examples AD and phthalocyanine blue (Toyo Ink Manufacturing Co., Ltd. LIONOL BLUE FG7330) were mixed in the formulation shown in Table 2 (the amount of each component is shown in parts, the same applies hereinafter), and a dispersion particle measuring instrument. Each grind meter was kneaded with 3 rolls until it became 7.5 microns or less with a grind meter. Subsequently, Nisseki AF solvent 6, a metal dryer, a drying inhibitor, and a compound were added to each ink base with the formulation shown in Table 2 and stirred to obtain Examples 1-4.

[Production of printing ink composition]
Comparative Example 1-2
Varnish Comparative Example E-F and Phthalocyanine Blue (Toyo Ink Manufacturing Co., Ltd. LIONOL BLUE FG7330) were mixed in the formulation shown in Table 2 (the amount of each component is shown in parts, the same applies hereinafter), and a dispersed particle measuring machine Each grind meter was kneaded with 3 rolls until it became 7.5 microns or less with a grind meter. Subsequently, Nisseki AF solvent 6, a metal dryer, a drying inhibitor, and a compound were added to each ink base in the formulation shown in Table 2 and stirred to obtain Comparative Example 1-2.

[Printing Evaluation Test] The printing ink compositions of Examples 1-4 and Comparative Example 1-2 were used with Komori Lithlon 20 printer at 10,000 sheets / hour using OK top coat paper 62.5 kg (manufactured), Was evaluated.

(Roller water content)
An optical fiber infrared process moisture meter IR-MF100 (manufactured by Chino Co., Ltd.) was attached to the copper roll in contact with the ink depositing roll, and the water content of the ink was measured when the water dial was changed from 1 to 8. .

(Soil dirt)
The dirty water dial when the water dial was changed from 8 to 1 was evaluated. A dirty ink with a low water dial is excellent in stain resistance.

(Reprintability)
With the water dial kept constant (water dial: 4), the number of passes through which dirt was generated while passing about 20,000 was evaluated. Inks with a large number of sheets are excellent in overprinting properties.

(Glossy)
The 60 ° -60 ° reflection gloss was measured with a gloss meter (manufactured by Murakami Color Research Laboratory Co., Ltd., digital gloss meter) for the solid portion of the printed matter of each printing ink composition printed with the water dial 6.

(Solid flesh)
The thickness of the solid portion of the printed material of each printing ink composition printed with the water dial 6 was visually evaluated.
3; Solid portion has no roughness 2; Solid portion roughness is moderate 1; Solid portion roughness is large

(Set property)
The set time of the solid portion of the printed material printed immediately after paper discharge printed with the water dial 6 was confirmed with an automatic setting tester (manufactured by Toyoe Seiko Co., Ltd.). .

(Backing property)
It printed with the water dial 6, and the backing property of the bottom of the pile of the printed material piled up 10,000 sheets was evaluated.
3; No backing 2; Medium backing 1; Many backing

[Evaluation Results] Table 3 and Table 4 show the results of the above evaluations on the offset printing ink compositions of Example 1-4 and Comparative Example 1-2.

(Figure 1)

Claims (3)

As binder resin, para-toluenesulfonic acid or alkali metal or alkaline earth metal hydroxide as catalyst, divalent to hexavalent polyhydric alcohol, OH number of polyhydric alcohol / rosin Lithographic printing having a water content of 1 to 20% on a roller of an offset printing press containing a rosin-modified phenolic resin obtained by adding an esterification reaction with a COOH number of 1 or less. Ink composition. The lithographic printing ink composition according to claim 1, wherein the weight average molecular weight of the rosin-modified phenolic resin having an OH number of polyhydric alcohol / COOH number of rosin of 1 or less is 10,000 to 150,000. N-heptane tolerance of rosin-modified phenolic resin whose OH number of polyhydric alcohol / COOH number of rosin is 1 or less (normal heptane was added dropwise at 25 ° C to a solution of 1 g of resin in 9 g of toluene. The lithographic printing ink composition according to claim 1 or 2, wherein a volume amount (ml) of normal heptane which becomes cloudy when it is applied is 1 to 40 ml.