JP5703557B2 - Additive for offset ink, varnish for offset ink, and ink composition for offset printing - Google Patents

Description

  The present invention is an additive which is an alkylene oxide adduct of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate, which can suitably adjust the emulsification suitability of the ink by adding to the printing ink for offset ink, The present invention relates to an offset ink varnish containing an additive and an offset printing ink composition containing the additive.

  In offset printing, dampening water is attached to a printing plate composed of an oleophilic part and a hydrophilic part, and water is attached to the hydrophilic part to inhibit the attachment of oil-based ink to a non-image area. This is a printing method in which ink is attached only to an oily portion to form an image line portion, and the ink is transferred to a blanket and then transferred again to paper or the like. In this method, the dampening water and the oil-based ink inevitably come into an emulsified state. At this time, if a large amount of dampening water is taken into the ink, there is insufficient water to cover the hydrophilic part of the printing plate, and the ink adheres to the part that should originally become the non-image area. The problem that will occur. On the other hand, when there is too little water emulsified in the ink, there arises a problem that water attached to the printing plate cannot be removed properly. In addition, when the stability of the emulsified state is low, problems such as separation of water and ink on the roller and problems of separation of water contained in the ink when restarting after interruption of printing occur. To do. Water separation is particularly problematic in offset newspaper printing. Also, if the ink viscosity changes greatly when the amount of emulsified water is changed, it becomes difficult to maintain the printing state. In order to prevent these problems from occurring, it is necessary to control the emulsification ability of the ink.

  As a method for controlling emulsification suitability of ink, a method of adding a compound having an alkylene oxide unit is known (for example, see Patent Documents 1 to 4). However, polyoxyethylene alkyl phenyl ether, which is relatively effective among the conventionally known emulsifiers for this purpose, is not sufficient, and it is known that biodegradation produces alkylphenols suspected of environmental hormones. It is necessary to solve these problems.

Japanese Patent Laid-Open No. 61-138777 JP 11-349880 A JP 2000-1643 A JP 2008-7592 A

  An object of the present invention is to provide an additive for offset ink, a varnish for offset ink, and an ink composition for offset printing that can suitably adjust the emulsification suitability of the ink and suppress printing trouble.

  As a result of intensive studies to solve the above problems, the present inventors have made an offset ink contain an additive which is an alkylene oxide adduct of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate. The present inventors have found that it is possible to impart the desired emulsification suitability and have reached the present invention.

ただし、Ｒ^１はアルキル基、Ｒ^２はＯ（ＣＨ_２ＣＨＲ^３Ｏ）_ｍＨ、Ｒ^３は水素原子またはアルキル基、ｍは１〜１００、ｎは０〜１００を示す。
（３）上記に記載のアルキルフェノールのアルキル基の炭素数が４〜９である前記（１）又は（２）のオフセットインキ用添加剤、
（４）上記に記載のアルキルフェノールがパラ−ｔ−オクチルフェノールである前記（３）のオフセットインキ用添加剤、
（５）アルキルフェノール及び／又は（ポリ）スチリルフェノールが（ポリ）スチリルフェノールであり、かつ（ポリ）スチリルフェノールの（ポリ）スチリル基のスチレン付加数が１〜４であって（ポリ）スチリルフェノールとホルムアルデヒド重縮合物のアルキレンオキシド付加物が下記一般式（１）を有する前記（１）のオフセットインキ用添加剤、

（ただし、Ｒ^１は（ポリ）スチリル基、Ｒ^２はＯ（ＣＨ_２ＣＨＲ^３Ｏ）_ｍＨ、Ｒ^３は水素原子またはアルキル基、ｍは１〜１００、ｎは０〜１００を示す。）
（６）上記に記載のアルキレンオキシドがエチレンオキシドである前記（１）〜（５）のオフセットインキ用添加剤、
（７）ＨＬＢが５以上１８未満である前記（１）〜（６）のオフセットインキ用添加剤、
（８）前記（１）〜（７）のいずれかのオフセットインキ用添加剤を含むオフセットインキ用ワニス、
（９）前記（１）〜（７）のいずれかのオフセットインキ用添加剤を含有するオフセット印刷用インキ組成物、
を提供する。 That is, the present invention
(1) an additive for offset ink, which is an alkylene oxide adduct of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate,
(2) The additive for offset ink of (1) above, wherein the alkylphenol and / or (poly) styrylphenol is an alkylphenol, and the alkylene oxide adduct of the alkylphenol and formaldehyde polycondensate has the following general formula (1):

However, ^{R 1} is an alkyl group, ^{R 2} is _{^{O (CH 2 CHR 3 O)}} m H, R 3 is a hydrogen atom or an alkyl group, m is 1 to 100, n represents 0-100.
(3) The additive for offset ink according to (1) or (2), wherein the alkyl group of the alkylphenol described above has 4 to 9 carbon atoms,
(4) The additive for offset ink according to (3), wherein the alkylphenol described above is para-t-octylphenol,
(5) Alkylphenol and / or (poly) styrylphenol is (poly) styrylphenol, and (poly) styrylphenol has a styrene addition number of (poly) styryl group of 1 to 4, and (poly) styrylphenol The additive for offset ink of (1) above, wherein the alkylene oxide adduct of formaldehyde polycondensate has the following general formula (1):

(However, R ¹ is a (poly) styryl group, R ² is O (CH ₂ CHR ³ O) _m H, R ³ is a hydrogen atom or an alkyl group, m is 1 to 100, and n is 0 to 100.)
(6) The additive for offset inks of (1) to (5) above, wherein the alkylene oxide described above is ethylene oxide,
(7) The additive for offset ink of (1) to (6) above, wherein the HLB is 5 or more and less than 18.
(8) Offset ink varnish containing the offset ink additive of any one of (1) to (7),
(9) Ink composition for offset printing containing the additive for offset ink according to any one of (1) to (7),
I will provide a.

  By using the alkylene oxide adduct of the alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate of the present invention as an additive for offset ink, an appropriate emulsified state can be maintained during printing.

ただし、Ｒ^１はアルキル基及び／又は（ポリ）スチリル基（（ポリ）スチリル基は、スチリル基及び／又はポリスチリル基として略したものである。）、Ｒ^２はＯ（ＣＨ_２ＣＨＲ^３Ｏ）_ｍＨ、Ｒ^３は水素原子またはアルキル基、ｍは１〜１００、ｎは０〜１００を示す。
入手の容易性及び効果の点から、Ｒ^１は炭素数４、８若しくは９のアルキル基又は平均の付加数が４個以下の（ポリ）スチリル基が好ましく、Ｒ^３は水素原子又はメチル基が好ましい。また、入手の容易性及び取り扱いやすさの観点から、ｎは０〜１０が好ましく、０〜５が特に好ましく、ｍは１〜８０が好ましく、１〜５０が特に好ましく、１〜２５が更に好ましい。ここで、ｎおよびｍは基本的には整数であるが化合物として分布を有する場合などには、整数でないことがあり、平均値として表示する。 The additive for offset ink used in the present invention may be an alkylene oxide adduct of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate, and for example, the one represented by the following general formula is preferable. .

However, R ¹ is an alkyl group and / or (poly) styryl group ((poly) styryl group is abbreviated as styryl group and / or polystyryl group), and R ² is O (CH ₂ CHR ³ O). _m H and R ³ represent a hydrogen atom or an alkyl group, m represents 1 to 100, and n represents 0 to 100.
From the standpoint of availability and effects, R ¹ is preferably an alkyl group having 4, 8, or 9 carbon atoms or a (poly) styryl group having an average addition number of 4 or less, and R ³ is a hydrogen atom or a methyl group. preferable. In addition, from the viewpoint of easy availability and ease of handling, n is preferably 0 to 10, particularly preferably 0 to 5, m is preferably 1 to 80, particularly preferably 1 to 50, and further preferably 1 to 25. . Here, n and m are basically integers, but when they have a distribution as a compound, they may not be integers and are displayed as average values.

  The HLB of the alkylene oxide adduct of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate used in the present invention is defined as Formula 1.

Formula 1
HLB = weight of added alkylene oxide / total weight × 20

  At this time, 5-18 are preferable for HLB. Moreover, when adding to the ink which lacks the amount of emulsified water and wanting to increase the amount of emulsified water, HLB of 6-15 is particularly preferable, and when the amount of emulsified water is too large to suppress emulsification, HLB of 9 to 17 is particularly preferable. .

  Commercially available alkylene oxide adducts of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate used in the present invention can be used.

  The content of the alkylene oxide adduct of the alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate of the present invention in the ink is preferably 0.01% by mass to 5% by mass, and 0.03% by mass with respect to the ink. -3 mass% is more preferable. When the amount is less than 0.01% by mass, the effect may not be sufficiently exhibited, and when the amount exceeds 5% by mass, emulsification suitability may not be controlled.

  The offset ink composition of the present invention comprises a drying accelerator (dryer), a drying inhibitor and the like in addition to the offset ink additive, binder resin, solvent, vegetable oil, and pigment of the present invention.

  As the pigment, an organic or inorganic pigment can be used. Examples thereof include titanium oxide, barium sulfate, acidic carbon black, neutral carbon black, azo pigment, lake pigment, phthalocyanine pigment, isoindoline pigment, anthraquinone pigment, and quinacridone pigment. The content of the pigment contained in the offset ink composition is preferably 10 to 30% by mass. If it is less than 10% by mass, coloring may be insufficient, and if it exceeds 30% by mass, it may be difficult to suppress aggregation of the pigment, resulting in insufficient ink fluidity. If necessary, extender pigments such as calcium carbonate can be used. The content of the extender is preferably less than 15% by mass. If it is 15% by mass or more, the ink fluidity and viscoelasticity may be adversely affected.

  Examples of the binder resin include rosin-modified phenol resins, petroleum resin-modified phenol resins, petroleum resins, alkyd resins, and oil-modified resins thereof.

  The rosin-modified phenolic resin is obtained by polycondensation of rosin with polyhydric alcohol, alkylphenol, aldehyde and, if necessary, petroleum resin.

  Examples of the rosin include rosins such as gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, polymerized rosin, and disproportionated rosin. Further, if necessary, they may be reinforced with α-β unsaturated carboxylic acids such as maleic anhydride, fumaric acid, acrylic acid and the like.

  The polymerized rosin is a rosin obtained by polymerizing rosin with a catalyst such as sulfuric acid, and is a mixture containing not only a dimer but also a monomer and a multimer of trimer or higher.

  The hydrogenated rosin is one in which unsaturated bonds are saturated by hydrogenating rosin.

  The above disproportionated rosin is obtained by transferring hydrogen between molecules by heating or the like to saturate the unsaturated bond of one molecule and at the same time unsaturate the other saturated bond.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, hexanediol, octanediol, nonanediol, and neopentylglycol. Examples include trihydric or higher alcohols such as dihydric alcohol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. These may be used alone or in combination. Among these, glycerin and / or pentaerythritol are preferable for the purpose of appropriately adjusting the molecular weight, melting point and the like of the resin. The amount of polyhydric alcohol used is preferably such that the hydroxyl group is 50 mol% to 250 mol% with respect to the acid group of the rosin used. If it is less than 50 mol%, it is difficult to proceed with polymerization sufficiently, and if it exceeds 250 mol%, the hydrophilicity of the produced resin may become too high.

  Examples of the alkylphenol include cresol, amylphenol, bisphenol A, parabutylphenol, paraoctylphenol, paranonylphenol, paradodecylphenol, dibutylphenol, and dimethylphenol. These may be used alone or in combination. Parabutylphenol, paraoctylphenol, and paranonylphenol are particularly preferable from the viewpoints of market price, availability, and binder resin performance.

  As said aldehyde, formaldehyde, such as formaldehyde, paraformaldehyde, and trioxane, acetaldehyde, propionaldehyde, etc. can be used. Among these, formaldehyde is particularly preferable from the viewpoint of reactivity and the like.

  The polycondensation can be carried out step by step as necessary. For example, resole prepared by reacting alkylphenol and aldehyde in advance in the presence of a basic catalyst and / or novolak resole prepared by reacting alkylphenol and aldehyde in advance in the presence of an acidic catalyst and further reacting in the presence of an aldehyde and a basic catalyst. Can be prepared by reacting with rosin and then with polyhydric alcohol. In addition, a rosin ester obtained by reacting rosin and a polyhydric alcohol is produced in advance, and resole obtained by reacting alkylphenol and aldehyde in the presence of a basic catalyst and / or alkylphenol and aldehyde in advance in the presence of an acidic catalyst, and further aldehyde It can also be produced by reacting novolak resole produced by reacting with rosin ester in the presence of a basic catalyst. Rosin, alkylphenol and aldehyde can be mixed and reacted, and then reacted with polyhydric alcohol.

  Examples of the basic catalyst used in the previously prepared resol or novolak resole include metal catalysts such as sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, and zinc oxide, ammonia, methylamine, dimethylamine, and diethylamine. And alkylamines such as trimethylamine, ethylamine, diethylamine and triethylamine, and alkanolamines such as ethanolamine, diethanolamine and triethanolamine. Moreover, paratoluenesulfonic acid etc. are mentioned as an acidic catalyst used for novolak resole.

  In the rosin-modified phenol resin, the use ratio of resole and / or novolak resole is preferably 15% by mass to 60% by mass, and particularly preferably 25% by mass to 50% by mass. If it is less than 15% by mass, the molecular weight of the resin becomes low, and when used as a binder resin, viscosity may be insufficient or misting may occur during printing. If it exceeds 60% by mass, the affinity between the binder resin and the solvent is remarkably increased, and drying at the time of printing may become too slow.

  Petroleum resin modified phenolic resin is a resole produced by reacting alkylphenol and aldehyde in advance in the presence of a basic catalyst and / or alkylphenol and aldehyde in advance in the presence of an acidic catalyst, and then reacting in the presence of an aldehyde and a basic catalyst. The novolak resole produced in this manner is reacted with petroleum resin and, if necessary, rosin and / or rosin ester.

  In the petroleum resin-modified phenol resin, the use ratio of resol and / or novolak resole is preferably 10% by mass to 70% by mass, and particularly preferably 15% by mass to 60% by mass. If it is less than 10% by mass, the molecular weight of the resin becomes low, and when used as a binder resin, viscosity may be insufficient or misting may occur during printing. When it exceeds 70% by mass, the affinity between the binder resin and the solvent is remarkably increased, and drying at the time of printing may become too slow.

  The production of the rosin-modified phenolic resin or petroleum resin-modified phenolic resin may be carried out in the absence of a solvent, and vegetable oils and solvents used for offset ink may be used as a reaction solvent if necessary. When carried out in a reaction solvent, it is possible to produce a resin having a composition that cannot be produced because the melt viscosity becomes too high unless a solvent is used. In this case, it is obtained as a resin solution of vegetable oils or solvents, that is, a varnish, and can be used for offset ink preparation without going through a dissolution step.

  Petroleum resin is a polymer produced from C5 fraction, C9 fraction, cyclopentadiene and dimer thereof produced from naphtha cracker. The raw materials are appropriately mixed and used in order to obtain necessary properties. As the polymerization method, thermal polymerization and cationic polymerization are well known, but a petroleum resin produced by any polymerization method may be used. The petroleum resin used as the raw material for the rosin-modified phenolic resin and the petroleum resin-modified phenolic resin preferably contains a double bond. Examples of the petroleum resin containing a double bond include those using a C5 fraction and / or cyclopentadiene and / or a dimer thereof as a part of the raw material. In this case, the C5 fraction and / or cyclopentadiene and / or dimer thereof is preferably contained in a total of 10% by mass or more. If it is less than 10% by mass, the reactivity may be poor. When it is not used as a raw material for a rosin-modified phenolic resin or a petroleum resin-modified phenolic resin but used as a binder resin, it is not always necessary to include a double bond. Therefore, the C5 fraction and / or cyclopentadiene and / or dimer thereof may be less than 10% by mass, and a hydrogenated petroleum resin in which a petroleum resin is hydrogenated to saturate double bonds and aromatics can be suitably used.

  Alkyd resins are resins obtained by reacting fats and oils such as animal and vegetable oils, polyhydric alcohols, polybasic acids and the like. There are also those using monoester, resin acid, petroleum resin, etc. in combination as required. Any alkyd resin may be contained as long as it can be suitably used as a binder resin.

  Examples of the vegetable oil include linseed oil, tung oil, soybean oil, safflower oil, cottonseed oil, dehydrated castor oil, canola oil, regenerated vegetable oil, and vegetable oils such as methyl ester, ethyl ester, propyl ester, and butyl ester. Examples include esters.

  Examples of the solvent contained in the offset ink composition of the present invention include n-paraffin solvents, isoparaffin solvents, naphthene solvents, aromatic solvents, olefin solvents and other petroleum solvents, light oil, spindle oil, machine oil, A cylinder oil, a turpentine oil, a mineral spirit etc. are mentioned.

  The binder resin contained in the offset ink composition of the present invention is once dissolved in vegetable oil and / or a solvent, and an antioxidant such as 2,6-di-tert-butyl-4-methylphenol is added as necessary. Or diluted with vegetable oil and / or solvent, or used for offset ink production as a varnish whose viscosity is adjusted with a gelling agent such as aluminum chelate. As described above, when the resin is produced in a vegetable oil and / or solvent and is produced by a method for obtaining a varnish, it can be used as it is or after it is adjusted for viscoelasticity for offset ink production. The ratio of the resins in the varnish is preferably 30% by mass to 65% by mass, and particularly preferably 35% by mass to 55% by mass. If it is less than 30% by mass, the varnish viscosity will be too low and it may be difficult to disperse when used for pigment dispersion. If it exceeds 65% by mass, the varnish viscosity will be too high and handling may be difficult.

  The content of the binder resin contained in the offset ink composition of the present invention in the offset ink is preferably 10% by mass to 50% by mass, and more preferably 15% by mass to 40% by mass. If it is less than 10% by mass, the viscosity of the ink is not sufficient, and at the same time, the pigment dispersion cannot be stabilized, causing problems such as aggregation. If it exceeds 50% by mass, the ink viscosity may become too high.

  The content of the vegetable oil and / or solvent contained in the offset ink composition of the present invention in the offset ink is the total amount excluding the other compositions. The ratio of vegetable oil to solvent may be changed according to the purpose. For example, in the case of a non-VOC ink characterized by not containing a solvent, only a vegetable oil is used without containing a solvent. For example, in the case of offset rotary printing ink that performs hot air drying, the amount of vegetable oil used is reduced and a large amount of solvent is used. In recent years, soybean oil ink has attracted attention as an environmentally friendly ink, and many offset rotary printing inks contain soybean oil or the like.

  As a drying accelerator (dryer) included in the offset ink composition of the present invention as necessary, a metal such as cobalt, manganese, lead, iron, and zinc and a carboxylic acid such as octylic acid, naphthenic acid, and neodecanoic acid are used. Metal soaps that are salts can be used.

  Hydroquinone, methoquinone, tert-butylhydroquinone and the like can be used as a drying inhibitor contained in the offset ink composition of the present invention as necessary.

  The additive for offset ink of the present invention may be added at any stage in ink production as long as it can be uniformly mixed with the ink. It may be added at the final stage of ink production, or may be added in advance at the stage of varnish production. It is also possible to add it to other resins to be used and use it as a varnish.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, these Examples do not limit this invention. In addition, "part" and "%" which are shown in the production examples, examples and comparative examples mean parts by mass and mass%.

Production example 1 of rosin ester used for varnish (production of rosin ester A)
In a stirrer, a Liebig cooler, and a separable flask equipped with a thermometer, 4000 parts of rosin was charged and dissolved by heating, 120 parts of maleic anhydride was added at 180 ° C., and the temperature was raised to 220 ° C. over 2 hours. Thereafter, 435 parts of pentaerythritol and 25 parts of zinc oxide were added, and the temperature was raised to 275 ° C. over 4 hours and then kept warm. The acid value was measured by sampling timely, and when it reached 25 mg KOH / g, the pressure was reduced at 60 hPa for 2 hours to obtain rosin ester A.

Production example 2 of rosin ester used for varnish (production of rosin ester B)
In a stirrer, a Liebig cooler, and a separable flask equipped with a thermometer, 4000 parts of rosin was charged and dissolved by heating, 120 parts of maleic anhydride was added at 180 ° C., and the temperature was raised to 220 ° C. over 2 hours. Thereafter, 290 parts of pentaerythritol, 132 parts of glycerin, and 26.4 parts of calcium hydroxide were added, and the temperature was raised to 275 ° C. over 4 hours and then kept warm. The acid value was measured by sampling at appropriate times, and when it reached 25 mgKOH / g, the pressure was reduced at 60 hPa for 2 hours to obtain rosin ester B.

Production Example 1 of Resol Solution Used for Varnish (Production of Resole Solution A)
A separable flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 2330 parts of paraoctylphenol, 722 parts of paraformaldehyde having an effective content of 92%, and 830 parts of AF Solvent No. 7 (manufactured by Nippon Oil Corporation) and heated to paraoctylphenol. Was dissolved. Thereafter, 11.6 parts of a 48% aqueous sodium hydroxide solution was added at 75 ° C., and the temperature was raised to 95 ° C. and maintained for 3 hours while appropriately adjusting to raise the temperature by exothermic reaction. Resol solution A was obtained by adding and mixing 830 parts of AF solvent No. 7.

Production Example 2 of Resol Solution Used for Varnish (Production of Resole Solution B)
Resole solution B was obtained in the same manner as resole solution A, except that AF solvent 7 was changed to toluene.

Production Example 1 of Varnish (Manufacture of Varnish A)
To a stirrer, a Liebig cooler, and a separable flask equipped with a thermometer, 800 parts of rosin ester A, 242 parts of soybean oil, and 451 parts of AF Solvent No. 7 were added and dissolved by heating under nitrogen. Thereafter, 840 parts of resole solution A was added dropwise over 2 hours while keeping the temperature at 220 ° C. Two hours after the end of the charging, the pressure was reduced at 300 hPa for 30 minutes. After returning to normal pressure with nitrogen, 1743 parts of the resulting solution was taken out into another flask, and then 527 parts of AF Solvent No. 7 was added. What was obtained by diluting 3.6-fold with AF Solvent 7 with 6.8 parts of 2,6-di-tert-butyl-4-methylphenol and kelope EP-12-10 (aluminum chelate, manufactured by Hope Pharmaceutical) at 130 ° C. 36 parts were added, heated to 160 ° C. over 30 minutes, kept for 1 hour, cooled to 100 ° C., and taken out to obtain varnish A.

Varnish Production Example 2 (Manufacture of Varnish B)
To a stirrer, a Liebig cooler, and a separable flask equipped with a thermometer, 800 parts of rosin ester A, 242 parts of soybean oil, and 451 parts of AF Solvent No. 7 were added and dissolved by heating under nitrogen. Thereafter, 840 parts of resole solution A was added dropwise over 2 hours while keeping the temperature at 220 ° C. Two hours after the end of the charging, the pressure was reduced at 300 hPa for 30 minutes. After returning to normal pressure with nitrogen, 1743 parts of the resulting solution was taken out into another flask, and then 487 parts of AF Solvent No. 7 was added. Add 6.8 parts of 2,6-di-tert-butyl-4-methylphenol at 130 ° C. and 36 parts of Kelope EP-12-10 (Hope Pharmaceutical) diluted 3.6-fold with AF Solvent 7 Then, the temperature was raised to 160 ° C. over 30 minutes, then kept for 1 hour, cooled to 120 ° C., 39 parts of ethylene oxide adduct of para-t-octylphenol formaldehyde polycondensate having an HLB of 10 was added, and varnish B was obtained. It was.

Production Example 3 of Varnish (Manufacture of Varnish C)
Same as Varnish B, except that instead of adding ethylene oxide adduct of para-t-octylphenol formaldehyde polycondensate with HLB of 10 instead of ethylene oxide adduct of para-t-octylphenol formaldehyde polycondensate with HLB of 16, Varnish C was obtained.

Varnish Production Example 4 (Manufacture of Varnish D)
In a separable flask equipped with a stirrer, a Liebig cooler, and a thermometer, 950 parts of rosin ester B was charged and heated to 230 ° C. and dissolved under nitrogen. While keeping the temperature, 214 parts of resole solution B was added over 1 hour, and kept warm for 1 hour. Next, 443 parts of soybean oil and 831 parts of AF Solvent No. 7 were added. After the temperature dropped by addition, the temperature was raised again to 230 ° C., and 427 parts of resole solution B was added over 1 hour 30 minutes. Two hours after the end of the charging, the pressure was reduced at 300 hPa for 30 minutes. After returning to normal pressure with nitrogen, take out 2005 parts into another flask, add 91 parts of AF Solvent No. 7, and 6.3 parts of 2,6-di-tert-butyl-4-methylphenol and cool to 130 ° C. did. 30 parts of B-50 (aluminum chelate, manufactured by Hope Pharmaceutical Co., Ltd.) was added, the temperature was raised to 160 ° C. in 30 minutes, held for 1 hour, and then cooled to 130 ° C. to obtain varnish D.

Varnish Production Example 5 (Production of Varnish E)
In a separable flask equipped with a stirrer, a Liebig cooler, and a thermometer, 950 parts of rosin ester B was charged and heated to 230 ° C. and dissolved under nitrogen. While keeping the temperature, 214 parts of resole solution B was added over 1 hour, and kept warm for 1 hour. Next, 443 parts of soybean oil and 831 parts of AF Solvent No. 7 were added. After the temperature dropped by addition, the temperature was raised again to 230 ° C., and 427 parts of resole solution B was added over 1 hour 30 minutes. Two hours after the end of the charging, the pressure was reduced at 300 hPa for 30 minutes. After returning to normal pressure with nitrogen, take out 2005 parts in another flask, add 55 parts of AF Solvent No. 7 and 6.3 parts of 2,6-di-tert-butyl-4-methylphenol and cool to 130 ° C. did. Add 30 parts of B-50 (manufactured by Hope Pharmaceutical Co., Ltd.), heat up to 160 ° C. in 30 minutes, hold for 1 hour, cool to 130 ° C., and add ethylene oxide to para-t-octylphenol formaldehyde polycondensate with HLB 10 Varnish E was obtained by adding 36.2 parts of the product.

Example 1 (Preparation of ink)
Varnish A 71 parts by mass, pigment (carbon black MA-7, manufactured by Mitsubishi Chemical Corporation) 18 parts by mass, solvent (AF Solvent No. 7, manufactured by Shin Nippon Oil Co., Ltd.) 20 parts by mass and additive for offset ink (para- Ethylene oxide adduct of t-octylphenol / formaldehyde polycondensate) 0.8 parts by mass were blended as shown in Table 1, and the blend was kneaded with a three-roll mill to obtain a printing ink.

Examples 2 to 11 (Preparation of ink)
A printing ink was obtained in the same manner as in Example 1 except that the types and amounts of additives for varnish and offset ink were changed as shown in Table 1.

Comparative Example 1 (Preparation of ink)
A printing ink was obtained in the same manner as in Example 4 except that the additive for offset ink was not used.

Comparative Example 2 (Preparation of ink)
A printing ink was obtained in the same manner as in Example 10 except that the additive for offset ink was not used.

Comparative Example 3 (Preparation of ink)
A printing ink was obtained in the same manner as in Example 1 except that the additive for offset ink in Example 1 was changed to an ethylene oxide adduct of para-t-octylphenol.

Comparative Example 4 (Preparation of ink)
A printing ink was obtained in the same manner as in Example 8 except that the additive for offset ink of Example 8 was changed to the ethylene oxide adduct of para-t-octylphenol.

  In Table 1, the type Oc of the additive for offset ink is an ethylene oxide adduct of para-t-octylphenol / formaldehyde polycondensate, and St is an ethylene oxide adduct of para-polystyrylphenol / formaldehyde polycondensate. Represents an ethylene oxide adduct of para-t-octylphenol. Moreover, the number of parts described in Table 1 is part by mass, and the number of parts of the additive for offset ink shown in parentheses in Table 1 is a value obtained by converting what was previously mixed into the varnish into a part by mass in the ink. .

Emulsification suitability test of printing ink The emulsification suitability test of printing ink was performed under the following conditions using a lithotronic emulsification tester (manufactured by Novocontrol).
Ink amount 25g
Temperature 40 ℃
Water addition speed 2 ml / min Stirring speed 1200 rpm
Conditioning before starting water addition 5 min. Gap between stirring blade and cup 1 mm
The Resotonic Emulsification Tester measures the torque applied to the stirring blade over time when water is added at a constant speed while stirring with the stirring blade of the same device while putting a certain amount of ink in the measuring cup. It is a device to do.
When water is added to the ink in the cup, there is a phenomenon that the torque decreases immediately after the start of the addition. The minimum torque value at this time is Tmin. Thereafter, the torque increases as the amount of water added increases. There are cases where the torque increases monotonously and reaches a maximum value and decreases at once, and there is a case where the torque has a maximum value and then gradually decreases.In either case, the added water is not mixed with the ink and the torque is reduced. The emulsification rate at the time when it decreases or becomes unstable is defined as the maximum emulsification rate. The maximum emulsification rate is shown by the following formula.
Maximum emulsification rate (%) = addition amount of water / ink amount × 100
At this time, the maximum value or maximum value of the torque is defined as Tmax. A small change in torque due to the addition of water is preferred because it indicates a small change in the printing press. The torque ratio shown by the following formula is used as a guide for this change.
Torque ratio = Tmax / Tmin
The torque ratio is preferably 2 or less. In the judgment column of Table 2, “◯” is described in the case of 2 or less, and “x” is described in the case of exceeding 2.

  The amount of emulsified water was measured by adding water to 30% with the same apparatus and conditions to stop the emulsified ink, and a small amount of emulsified ink was placed on the slide glass, the cover glass was pressed, and the water dispersion state was observed with an optical microscope. A fine and uniform particle was judged good. The results are shown in Table 2 as ◯ when uniform, and x otherwise.

  As is apparent from the results shown in Table 2, the printing ink (Example) containing an alkylphenol and / or (poly) styrylphenol and an alkylene oxide adduct of formaldehyde polycondensate has a small torque ratio to a change in the emulsification rate, and The emulsification state was uniform and showed good emulsification ability. However, printing inks that do not contain an alkylene oxide adduct of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate or paraffin instead of an alkylene oxide adduct of alkylphenol and / or (poly) styrylphenol and formaldehyde polycondensate. -The printing ink (comparative example) containing the ethylene oxide adduct of octylphenol was the result that the emulsified state was not uniform or the torque ratio with respect to the change in the emulsification rate was large.

Claims (8)

An offset printing ink varnish comprising an additive for offset ink, which is an alkylene oxide adduct of alkylphenol or (poly) styrylphenol and formaldehyde polycondensate. A alkylphenols or (poly) styryl phenol alkylphenols, alkylene oxide adducts of alkylphenol and formaldehyde polycondensate offset ink additive according to claim 1, characterized in that having the following general formula (1) An ink varnish for offset printing, comprising:

However, ^{R 1} is an alkyl group, ^{R 2} is ^{_{O (CH 2 CHR 3 O)}} mH, R 3 is a hydrogen atom or an alkyl group, m is 1 to 100, n represents 0-100. The offset varnish for ink for offset printing characterized by containing the additive for offset inks of Claim 1 or 2 characterized by the carbon number of the alkyl group of the said alkylphenol being 4-9. 4. The offset printing ink varnish comprising the offset ink additive according to claim 3, wherein the alkylphenol is para-t-octylphenol. The alkylphenol or (poly) styrylphenol is (poly) styrylphenol, and the (poly) styrylphenol has a (poly) styryl group having a styrene addition number of 1 to 4, and (poly) styrylphenol and formaldehyde polycondensate The offset varnish for ink for offset printing comprising the additive for offset ink according to claim 1, wherein the alkylene oxide adduct has the following general formula (1).

However, ^{R 1} is (poly) styryl group, ^{R 2} is ^{_{O (CH 2 CHR 3 O)}} mH, R 3 is a hydrogen atom or an alkyl group, m is 1 to 100, n represents 0-100. 6. The offset printing ink varnish comprising the offset ink additive according to any one of claims 1 to 5, wherein the alkylene oxide is ethylene oxide. HLB is 5 or more and less than 18, The offset printing ink varnish characterized by containing the additive for offset inks as described in any one of Claims 1-6 characterized by the above-mentioned. An ink composition for offset printing comprising the additive for offset ink according to any one of claims 1 to 7.