WO2018181155A1 - Dispersant composition for printing ink - Google Patents

Dispersant composition for printing ink Download PDF

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Publication number
WO2018181155A1
WO2018181155A1 PCT/JP2018/012097 JP2018012097W WO2018181155A1 WO 2018181155 A1 WO2018181155 A1 WO 2018181155A1 JP 2018012097 W JP2018012097 W JP 2018012097W WO 2018181155 A1 WO2018181155 A1 WO 2018181155A1
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WIPO (PCT)
Prior art keywords
printing ink
composition
carbon atoms
copolymer
dispersant
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PCT/JP2018/012097
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French (fr)
Japanese (ja)
Inventor
石橋洋一
Original Assignee
花王株式会社
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Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201880014152.3A priority Critical patent/CN110366583B/en
Publication of WO2018181155A1 publication Critical patent/WO2018181155A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder

Definitions

  • the present invention relates to a dispersant for printing ink, a printing ink composition, and a method for producing a dispersant for printing ink.
  • Gravure printing, offset printing, flexographic printing, and the like are known as printing methods, and printing inks suitable for each are used.
  • the ink contains a solvent such as an organic solvent or water.
  • a solvent for gravure printing ink aromatic solvents such as toluene, xylene and benzene, and non-aromatic solvents such as ethyl acetate and isopropyl alcohol have been used.
  • Toluene has heretofore been favorably used because of its high solubility in resins and additives used in inks and appropriate drying properties during printing.
  • Japanese Patent Application Laid-Open No. 2009-138115 discloses an amidation or esterification product of a copolymer of an olefin and an unsaturated dibasic acid, wherein the amidation rate or esterification rate with respect to the unsaturated dibasic acid is 10 to 60 mol%.
  • Dispersant composition in oil for electronic materials containing at least one dispersant selected from a certain one and a non-aromatic organic solvent having a solubility parameter of 8.5 to 22 (cal / cm 3 ) 1/2 Is used to obtain a dispersion in oil of a powder for electronic materials such as carbon black.
  • Japanese Patent Publication No. 41-17852 discloses that fine particles are dispersed in a non-aqueous solvent such as a dye or pigment by using an amidated product of a copolymer of an olefin and an unsaturated dibasic acid. Yes.
  • the present invention has a sufficient dispersion performance for a colorant even when a non-aromatic organic solvent having little influence on the environment is used, and even if the ink is dried, it is easily dispersed when mixed with the organic solvent again. And a dispersant composition for printing inks that provides a printing ink with excellent dispersibility after storage.
  • the present invention relates to an amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof (a), an acetate ester (b1) and a lower group. It is related with the dispersing agent composition for printing inks containing mixed organic solvent (b) with alcohol (b2).
  • the present invention also provides: Printing ink powder, An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a); Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2);
  • the present invention relates to a printing ink composition containing
  • the present invention also provides: A step of obtaining a copolymer by reacting an olefin and an unsaturated dibasic acid in a reaction solvent containing an acetate ester (b1) and a lower alcohol (b2), and the copolymer having 6 to 10 carbon atoms. A step of amidating with an amine having the following branched alkyl group to obtain an amidated product of the copolymer;
  • the present invention relates to a method for producing a dispersant composition for printing ink.
  • the present invention also relates to an amidated product of an olefin / unsaturated dibasic acid copolymer with an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof (a), and an acetate ester (b1).
  • the present invention relates to the use of a composition containing a mixed organic solvent (b) of an alcohol and a lower alcohol (b2) as a dispersant for printing ink.
  • the present invention also includes a powder for printing ink, An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a); Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2); Relates to the use of a composition containing as a printing ink.
  • an amidation product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof (a), component (a), acetate ester (b1) Is described as component (b1), lower alcohol (b2) as component (b2), and the mixed organic solvent (b) as component (b).
  • a non-aromatic organic solvent having little influence on the environment it has a sufficient dispersion performance with respect to the colorant, and even when the ink is dried, it is easily dispersed when mixed with the organic solvent again.
  • a dispersant composition for printing ink that provides a printing ink having excellent dispersibility after storage, for example, after storage for a long time at a high temperature.
  • the printing ink when performing gravure printing, the printing ink is dried and consolidated on the roll of the gravure printing machine, and while the roll is rotating, the consolidated product falls from the roll, and the newly supplied printing ink
  • the printing ink powder can be easily redispersed in the printing ink even if it is mixed into the printing ink. , Work efficiency and printing ink quality can be maintained.
  • the component (a) is an amidated product of an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof, of a copolymer of an olefin and an unsaturated dibasic acid.
  • the component (a) functions as a dispersant for printing ink powder.
  • the olefin constituting the component (a) is preferably an olefin having 3 to 12 carbon atoms from the viewpoint of obtaining good dispersion performance, more preferably at least one selected from the group consisting of diisobutylene and isobutylene, and diisobutylene. Is more preferable.
  • the unsaturated dibasic acid constituting the component (a) is preferably an aliphatic unsaturated dibasic acid having 4 to 6 carbon atoms from the viewpoint of obtaining good dispersion performance, and maleic anhydride, maleic acid and itaconic acid. At least one selected from the group consisting of is more preferable, and at least one selected from the group consisting of maleic anhydride and maleic acid is more preferable.
  • the ratio of the olefin and the unsaturated dibasic acid as the constituent monomer of the component (a) is preferably a molar ratio of olefin / unsaturated dibasic acid of 0.25 or more, more preferably from the viewpoint of obtaining good dispersion performance. Is 0.40 or more, more preferably 0.50 or more, and preferably 4 or less, more preferably 2.5 or less, still more preferably 2.0 or less.
  • the amidation product of the copolymer of the olefin and unsaturated dibasic acid of component (a) is a copolymer of olefin and unsaturated dibasic acid, and an amine having a branched alkyl group having 6 to 10 carbon atoms.
  • the amine used here is an amine having a branched alkyl group having 6 to 10 carbon atoms, and a primary amine having a branched alkyl group having 6 to 10 carbon atoms is preferable. Specific examples include isohexylamine, 2-ethylhexylamine, isooctylamine, and isodecylamine. These amines can be used alone or in combination of two or more.
  • the branched alkyl group of the amine is preferably a branched alkyl group having 8 to 10 carbon atoms.
  • the amidation rate (vs. unsaturated dibasic acid) of the amidated product as component (a) is preferably more than 60 mol% from the viewpoint of obtaining good dispersion performance and good solubility in component (b). More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, Preferably it is 150 mol% or less, More preferably, it is 120 mol% or less, More preferably, it is 110 mol% or less.
  • this amidation rate can be calculated based on the charged mol% of the raw material at the time of (a) component manufacture. When the amidation rate exceeds 200 mol%, it is presumed that a free amidated product is present.
  • the amidated product of the copolymer of olefin and unsaturated dibasic acid may be a salt.
  • the salt can be obtained by neutralization with an amine, betaine or the like.
  • the salt is preferably an imidazoline salt, and more preferably a salt of an imidazoline compound represented by the following formula (1).
  • R 1 is a hydrocarbon group having 7 to 21 carbon atoms
  • R 2 is a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • examples of the hydrocarbon group for R 1 include an alkyl group and an alkenyl group.
  • the carbon number of R 1 is preferably 8 or more, more preferably 10 or more, and preferably 22 or less, more preferably 20 or less.
  • examples of the divalent hydrocarbon group for R 2 include an alkylene group.
  • the number of carbon atoms in R 2 is preferably 1 or more, and is preferably 4 or less.
  • the degree of neutralization is preferably 50 mol% or more, more preferably 60 mol%, and preferably 100 mol% or less, more Preferably it is 90 mol% or less.
  • the weight average molecular weight of the amidated compound as component (a) is preferably 700 or more, more preferably 3000 or more, from the viewpoint of obtaining good dispersion performance and good solubility in a non-aromatic organic solvent. More preferably, it is 5000 or more, preferably 500,000 or less, more preferably 300,000 or less, and still more preferably 100,000 or less.
  • the weight average molecular weight of the amidation product of the component (a) in this specification is a value measured by GPC (gel permeation chromatography, converted to polystyrene) under the following conditions.
  • a polymerization initiator can be used when producing the copolymer.
  • the polymerization initiator include organic peroxides, azo series, etc. Among them, organic peroxides are preferable, and specifically, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates. Peroxyesters, and more specifically, benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, and the like.
  • the amount of the polymerization initiator used is preferably at least 0.1 mol%, more preferably at least 0.3 mol%, still more preferably from the viewpoint of obtaining a good polymerization rate and dispersion performance. 0.5 mol% or more, and preferably 20 mol% or less, more preferably 10 mol% or less, and further preferably 5 mol% or less.
  • the polymerization initiator may be added for the purpose of further improving the polymerization rate of the copolymer in the aging step after completion of the polymerization.
  • the amount used is preferably 0.01 mol% or more and 0.1 mol% or less (vs. unsaturated dibasic acid).
  • a mixture containing unreacted olefin, unsaturated dibasic acid and the like together with the component (a) in a range that does not inhibit the effect of the present invention may be used as a feedstock for the component (a).
  • the component (a) is preferably a salt of the amide compound, more preferably an imidazoline salt of the amidated product.
  • the mixed organic solvent of component (b) used in the present invention is a non-aromatic organic solvent in consideration of the environment, and from the viewpoint of improving the solubility of component (a), A mixed organic solvent of acetate and (b2) component lower alcohol is used.
  • the printing ink dispersant composition of the present invention is suitably used for preparing a printing ink composition in the form of a so-called oil-dispersed slurry.
  • Examples of the acetic acid ester of the component (b1) include acetic acid esters having 2 to 6 carbon atoms in total, and specifically include ethyl acetate, propyl acetate, butyl acetate and the like.
  • the component (b1) is preferably at least one selected from the group consisting of ethyl acetate and butyl acetate.
  • Examples of the lower alcohol as the component (b2) include alcohols having 2 to 6 carbon atoms, and specific examples include isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol and the like.
  • the component (b2) is preferably at least one selected from the group consisting of isopropyl alcohol and n-butyl alcohol.
  • Component (b) is a mass ratio of the content of component (b1) and the content of component (b2) from the viewpoint of obtaining good dispersion performance and good solubility of component (a) in component (b).
  • (B1) / (b2) is preferably 0.01 or more, more preferably 0.25 or more, still more preferably 0.45 or more, still more preferably 0.8 or more, and preferably 100 or less, more preferably Is 99 or less, more preferably 50 or less, even more preferably 9 or less, and still more preferably 3 or less.
  • the dispersant composition for printing ink of the present invention may contain an organic solvent other than the component (b), but the proportion of the component (b) in the total organic solvent is preferably 10% by mass or more. It is preferably 30% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.
  • the dispersant composition for printing ink of the present invention preferably has a low water content. More preferably, it is substantially free of water.
  • “substantially does not contain water” means that the content of water in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.
  • the mass ratio (a) / (b) between the content of the component (a) and the content of the component (b) is preferably 0 from the viewpoint of improving dispersibility.
  • the dispersant composition for printing ink of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and the component (a).
  • the component (a) Preferably it is 80 mass% or less, More preferably, it is 60 mass% or less, More preferably, it contains 40 mass% or less.
  • the printing ink dispersant composition of the present invention can contain higher alcohols, fatty acids, fatty acid esters, fatty amines and the like as optional components.
  • the dispersant composition for printing inks of this invention can use (b) component as a solvent of a printing ink composition as it is, depending on a composition, printing ink is added to the dispersant composition for printing inks of this invention.
  • the printing ink composition of the present invention can be obtained simply by mixing the powder for use.
  • the dispersant composition for printing ink of the present invention can be used as a vehicle for printing ink and its solvent, and further as a solvent for printing ink composition.
  • the printing ink composition of the present invention is preferably a liquid from the viewpoint of improving the miscibility with printing ink powders or other organic solvents.
  • the present invention provides the use of a composition containing the component (a) and the component (b) as a dispersant for printing ink.
  • the matters described in the printing ink composition of the present invention can be appropriately applied to the composition according to this use.
  • the printing ink composition of the present invention contains a printing ink powder, the component (a), and the component (b). Specific examples and preferred embodiments of the component (a) and the component (b) are the same as those of the dispersant composition for printing ink of the present invention.
  • Examples of the powder for printing ink include a colorant and an inorganic powder other than the colorant.
  • Examples of the colorant include pigments.
  • various inorganic pigments and organic pigments generally used in printing ink can be used.
  • the inorganic pigment for example, colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, satin white, zinc white, silica, calcium carbonate, kaolin, clay,
  • Examples include extender pigments such as barium sulfate, aluminum hydroxide and talc, aluminum pastes containing aluminum particles surface-treated with acrylic resin, and pearl pigments such as mica whose surfaces are coated with titanium oxide, tin oxide and zirconium oxide.
  • organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
  • inorganic powder other than the colorant include calcium phosphate, zinc phosphate, bentonite, ferrite, alumina, magnesium oxide, white carbon, cement, gypsum, titanate, and silicate.
  • the printing ink powder preferably contains a colorant.
  • the colorant is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 9% by mass or more, and preferably 50 mass% or less, More preferably, it contains 30 mass% or less.
  • the inorganic powder other than the colorant in the printing ink powder is preferably 10% by mass. More preferably, it is 20% by mass or more, more preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less.
  • the printing ink composition of the present invention is preferably 1 part by mass or more, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the printing ink powder. More preferably, it is 5 parts by mass or more and preferably 30 parts by mass or less, more preferably 20 parts by mass or less.
  • the printing ink composition of the present invention contains the component (b) preferably 80% by mass or more, more preferably 85% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less.
  • composition of the printing ink composition of the present invention can be variously set.
  • the content of each component can be set as follows, for example.
  • -Colorant In composition Preferably it is 7 mass% or more and 30 mass% or less.
  • component With respect to 100 mass parts of colorant Preferably it is 0.5 mass part or more and 30 mass parts or less.
  • component Composition Medium preferably 40% by mass or more and 92.5% by mass or less
  • the average particle diameter of dispersed particles at 25 ° C. is preferably 3 ⁇ m or less, more preferably 2.5 ⁇ m or less, and as an example, the vicinity is preferably 2 ⁇ m.
  • the lower limit of the average particle size is preferably 1.1 ⁇ m or more.
  • an average particle diameter is measured by the method described in the Example.
  • the printing ink composition of the present invention can contain a binder, a plasticizer, and the like.
  • the binder include ethyl cellulose, acrylic, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, or a mixture thereof.
  • the plasticizer include dioctyl phthalate, adipic acid, phosphate ester, glycol and the like.
  • the viscosity of the printing ink composition of the present invention can be set according to the printing method.
  • the viscosity at 25 ° C. is preferably 0.5 mPa ⁇ s or more and 20 mPa ⁇ s or less.
  • the group derived from the unsaturated dibasic acid constituting the component (a) of the present invention is adsorbed on the printing ink powder
  • the group derived from the olefin constituting the component (a) of the present invention is presumed to improve the dispersion stability of the printing ink powder by dissolving and diffusing in the organic solvent.
  • the printing ink composition of the present invention is preferably an oil-dispersed slurry.
  • a usual slurrying method can be used.
  • a method of adding a printing ink powder to the printing ink dispersant composition of the present invention and stirring and mixing a method of adding the printing ink dispersant composition of the present invention to a printing ink powder and stirring and mixing Methods and the like.
  • a method of stirring and mixing for example, a generally used stirring device such as a high-speed disperser, a homomixer, or a ball mill can be used.
  • the dispersant composition for printing ink of the present invention is added to the ore or coarse particles of the printing ink powder and pulverized.
  • a method of slurrying can be performed.
  • a generally used wet pulverizer such as a bead mill can be used for the method of slurrying simultaneously with pulverization.
  • the present invention provides use of a composition containing a powder for printing ink, the component (a), and the component (b) as a printing ink.
  • a composition containing a powder for printing ink, the component (a), and the component (b) as a printing ink.
  • the matters described in the dispersant composition for printing ink and the printing ink composition of the present invention can be appropriately applied to the composition according to this use.
  • the present invention comprises a step of reacting an olefin and an unsaturated dibasic acid in a reaction solvent containing an acetate ester (b1) and a lower alcohol (b2) to obtain a copolymer; and A step of amidating with an amine having a branched alkyl group of 6 to 10 to obtain an amidated product of the copolymer;
  • the manufacturing method of the dispersing agent composition for printing inks which has this is provided.
  • the amidated product of the copolymer is the component (a).
  • the reaction solvent containing the component (b1) and the component (b2) can be used as the component (b) of the printing ink dispersant composition as it is.
  • the matters described in the dispersant composition for printing ink of the present invention and the printing ink composition of the present invention can be applied to the method for producing the dispersant composition for printing ink of the present invention.
  • the manufacturing method of the dispersing agent composition for printing inks of this invention can have the process of neutralizing the amidation product of the said copolymer with the imidazoline compound of said Formula (1).
  • the present invention also provides: Printing ink powder, An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a); Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2); A method for producing a printing ink composition is provided.
  • the dispersant composition for printing ink of the present invention containing the component (a) and the component (b) can be used.
  • a composition can be adjusted by adding (b1) component and / or (b2) component as needed.
  • the matters described in the dispersant composition for printing ink of the present invention and the printing ink composition of the present invention can be applied to the method for producing the printing ink composition.
  • Example Production Example 1 In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel, maleic anhydride (Mitsui Chemicals Co., Ltd.) 70.6 g, ethyl acetate (Sinochem Japan Co., Ltd.) 32.5 g And 32.5 g of isopropyl alcohol (hereinafter abbreviated as IPA) (manufactured by JX Energy Co., Ltd.), heated to 93 ° C.
  • IPA isopropyl alcohol
  • a neutralized product of maleic anhydride / diisobutylene copolymer amidated product with oleylethylimidazoline was obtained.
  • Table 1 shows the amidation rate of the neutralized product of the present amidated product, the weight average molecular weight (value measured by the above method, the same applies hereinafter), the solvent used during synthesis, the neutralizing agent, and the degree of neutralization.
  • oleylhydroxyethyl imidazoline is a compound in which R 1 in the formula (1) is an oleyl group and R 2 is an ethylene group. The reaction product obtained by this method was directly used as a dispersant for printing ink.
  • Production Examples 2 to 4 and Comparative Production Examples 1 to 8 A reaction product containing an amidated product or a neutralized product or an esterified product thereof as shown in Table 1 was obtained in the same manner as in Production Example 1 except that the production conditions were as shown in Table 1. The obtained reaction product was used as a dispersant for printing ink as it was.
  • mol% is mol% relative to the unsaturated dibasic acid.
  • the amidated product of the copolymer is the component (a), and the solvent used in the synthesis is the component (b).
  • Examples 1 to 4 and Comparative Examples 1 to 9 A printing ink composition was prepared using the printing ink dispersant composition of Table 1 and a comparative dispersant, and the following evaluations were performed. The results are shown in Table 2.
  • dispersibility (I) (dispersibility immediately after preparation) A 100 mL screw tube was charged with 4 g of carbon black having an average particle diameter of 24 nm (MA100 manufactured by Mitsubishi Chemical Corporation), a solvent, a dispersant composition for printing inks shown in Table 1, or a comparative dispersant.
  • the comparative dispersant was Lubrizol 24000 (polyethyleneimine dispersant, manufactured by Lubrizol). Further, as the dispersant for printing ink in Table 1 and the comparative dispersant, those prepared by diluting with the same solvent as used at the time of synthesis and having a solid content of 30% by mass were used.
  • the amount of solids can be considered to be the amount of copolymer amidated or esterified or salt.
  • a mixed organic solvent having a mass ratio of ethyl acetate / IPA of 1/1 was used as the solvent. Then, it processed for 3 hours with the ultrasonic dispersion apparatus B1510 made from Branson, and prepared the slurry. This was made into the printing ink composition. The amount of the solvent was adjusted so that the carbon black concentration in the printing ink composition was 10% by mass.
  • a printing ink composition was prepared in which the amount of the dispersant composition for printing ink or the comparative dispersant was 8, 10, or 12% by mass (vs.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The Present invention relates to a dispersant composition which contains: (a) an amidated product formed from amines or a salt thereof, the amidated product being a copolymer of an olefin and an unsaturated dibasic acid and having a branched chain alkyl group having 6-10 carbon atoms; and (b) a mixed organic solvent of (b1) an acetate ester and (b2) a lower alcohol.

Description

印刷インキ用分散剤組成物Dispersant composition for printing ink
　本発明は、印刷インキ用分散剤組成物、印刷インキ組成物及び印刷インキ用分散剤組成物の製造方法に関する。 The present invention relates to a dispersant for printing ink, a printing ink composition, and a method for producing a dispersant for printing ink.
背景技術
　印刷方式には、グラビア印刷、オフセット印刷、フレキソグラフィー印刷などが知られており、それぞれに適した印刷インキが用いられている。通常、インキは、有機溶剤や水などの溶剤を含有している。例えば、グラビア印刷用インキの溶剤としては、トルエン、キシレン、ベンゼン等の芳香族系溶剤や、酢酸エチル、イソプロピルアルコール等のような非芳香族系溶剤が使用されてきた。トルエンは、インキに使用される樹脂や添加剤に対する高い溶解性、印刷時の適切な乾燥性等のために、従来、好んで使用されてきた。しかしながら、労働安全衛生法の改正により、トルエンの濃度規制が強化され、そのための環境改善への対応からインキ中の溶剤組成の見直しが迫られており、トルエンを使用しないインキ、例えば、酢酸エチル、イソプロピルアルコールを用いたインキの需要が高まっている。 BACKGROUND ART Gravure printing, offset printing, flexographic printing, and the like are known as printing methods, and printing inks suitable for each are used. Usually, the ink contains a solvent such as an organic solvent or water. For example, as a solvent for gravure printing ink, aromatic solvents such as toluene, xylene and benzene, and non-aromatic solvents such as ethyl acetate and isopropyl alcohol have been used. Toluene has heretofore been favorably used because of its high solubility in resins and additives used in inks and appropriate drying properties during printing. However, due to the revision of the Industrial Safety and Health Law, the concentration control of toluene has been strengthened, and the review of the solvent composition in the ink has been urged from the response to the environmental improvement for that purpose, and ink that does not use toluene, such as ethyl acetate, The demand for inks using isopropyl alcohol is increasing.
　特開２００９－１３８１１５号公報には、オレフィンと不飽和二塩基酸との共重合体のアミド化物又はエステル化物で、不飽和二塩基酸に対するアミド化率又はエステル化率が１０～６０モル％であるものから選ばれる少なくとも１種の分散剤と、溶解度パラメーターが８．５～２２（ｃａｌ／ｃｍ３）１／２の非芳香族系有機溶剤とを含有する電子材料用油中分散剤組成物を用いて、カーボンブラックなどの電子材料用粉体の油中分散体を得ることが記載されている。
　また、特公昭４１－１７８５２号公報には、オレフィンと不飽和二塩基酸との共重合体のアミド化物を用いて、染料や顔料などの非水溶媒中に微粒子を分散させることが開示されている。 Japanese Patent Application Laid-Open No. 2009-138115 discloses an amidation or esterification product of a copolymer of an olefin and an unsaturated dibasic acid, wherein the amidation rate or esterification rate with respect to the unsaturated dibasic acid is 10 to 60 mol%. Dispersant composition in oil for electronic materials containing at least one dispersant selected from a certain one and a non-aromatic organic solvent having a solubility parameter of 8.5 to 22 (cal / cm 3 ) 1/2 Is used to obtain a dispersion in oil of a powder for electronic materials such as carbon black.
Japanese Patent Publication No. 41-17852 discloses that fine particles are dispersed in a non-aqueous solvent such as a dye or pigment by using an amidated product of a copolymer of an olefin and an unsaturated dibasic acid. Yes.
発明の概要
　本発明は、環境に影響の少ない非芳香族系有機溶剤を用いても着色剤に対する充分な分散性能を有し、インキが乾燥しても有機溶剤に再度混合した際に容易に分散し、且つ保存後の分散性に優れた印刷インキが得られる印刷インキ用分散剤組成物を提供する。 SUMMARY OF THE INVENTION The present invention has a sufficient dispersion performance for a colorant even when a non-aromatic organic solvent having little influence on the environment is used, and even if the ink is dried, it is easily dispersed when mixed with the organic solvent again. And a dispersant composition for printing inks that provides a printing ink with excellent dispersibility after storage.
　本発明は、オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）とを含有する、印刷インキ用分散剤組成物に関する。 The present invention relates to an amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof (a), an acetate ester (b1) and a lower group. It is related with the dispersing agent composition for printing inks containing mixed organic solvent (b) with alcohol (b2).
　また、本発明は、
　印刷インキ用粉体と、
　オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
　酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
を含有する、印刷インキ組成物に関する。 The present invention also provides:
Printing ink powder,
An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a);
Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2);
The present invention relates to a printing ink composition containing
　また、本発明は、
　オレフィンと不飽和二塩基酸とを、酢酸エステル（ｂ１）と低級アルコール（ｂ２）とを含む反応溶媒中で反応させて共重合体を得る工程、及び
　前記共重合体を、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンでアミド化して前記共重合体のアミド化物を得る工程、
を有する、印刷インキ用分散剤組成物の製造方法に関する。 The present invention also provides:
A step of obtaining a copolymer by reacting an olefin and an unsaturated dibasic acid in a reaction solvent containing an acetate ester (b1) and a lower alcohol (b2), and the copolymer having 6 to 10 carbon atoms. A step of amidating with an amine having the following branched alkyl group to obtain an amidated product of the copolymer;
The present invention relates to a method for producing a dispersant composition for printing ink.
　また、本発明は、オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）とを含有する組成物の、印刷インキ用分散剤としての使用に関する。 The present invention also relates to an amidated product of an olefin / unsaturated dibasic acid copolymer with an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof (a), and an acetate ester (b1). The present invention relates to the use of a composition containing a mixed organic solvent (b) of an alcohol and a lower alcohol (b2) as a dispersant for printing ink.
　また、本発明は、印刷インキ用粉体と、
　オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
　酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
を含有する組成物の、印刷インキとしての使用に関する。 The present invention also includes a powder for printing ink,
An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a);
Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2);
Relates to the use of a composition containing as a printing ink.
　以下、オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）を（ａ）成分、酢酸エステル（ｂ１）を（ｂ１）成分、低級アルコール（ｂ２）を（ｂ２）成分、前記混合有機溶剤（ｂ）を（ｂ）成分として説明する。 Hereinafter, an amidation product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof (a), component (a), acetate ester (b1) Is described as component (b1), lower alcohol (b2) as component (b2), and the mixed organic solvent (b) as component (b).
　本発明によれば、環境に影響の少ない非芳香族系有機溶剤を用いても着色剤に対する充分な分散性能を有し、インキが乾燥しても有機溶剤に再度混合した際に容易に分散し、且つ保存後、例えば高温、長期間の保存後の分散性に優れた印刷インキが得られる印刷インキ用分散剤組成物が提供される。例えば、グラビア印刷をする場合、グラビア印刷機のロール上で印刷インキが乾燥固結し、ロールが回転している間に本固結物がロールから落下して、新たに供給される印刷インキ中に混入するような事態が生じても、本発明の印刷インキ用分散剤組成物を用いて調製された印刷インキ組成物であれば、印刷インキ用粉体は容易に印刷インキに再分散するため、作業効率や印刷インキの品質を維持できる。 According to the present invention, even if a non-aromatic organic solvent having little influence on the environment is used, it has a sufficient dispersion performance with respect to the colorant, and even when the ink is dried, it is easily dispersed when mixed with the organic solvent again. In addition, there is provided a dispersant composition for printing ink that provides a printing ink having excellent dispersibility after storage, for example, after storage for a long time at a high temperature. For example, when performing gravure printing, the printing ink is dried and consolidated on the roll of the gravure printing machine, and while the roll is rotating, the consolidated product falls from the roll, and the newly supplied printing ink In the case of a printing ink composition prepared using the printing ink dispersant composition of the present invention, the printing ink powder can be easily redispersed in the printing ink even if it is mixed into the printing ink. , Work efficiency and printing ink quality can be maintained.
発明を実施するための形態
〔印刷インキ用分散剤組成物〕
　（ａ）成分は、オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩である。（ａ）成分は、印刷インキ用粉体の分散剤として機能する。 MODE FOR CARRYING OUT THE INVENTION [Dispersant composition for printing ink]
The component (a) is an amidated product of an amine having a branched alkyl group having 6 to 10 carbon atoms, or a salt thereof, of a copolymer of an olefin and an unsaturated dibasic acid. The component (a) functions as a dispersant for printing ink powder.
　（ａ）成分を構成するオレフィンとしては、良好な分散性能を得る観点から、炭素数３以上１２以下のオレフィンが好ましく、ジイソブチレン及びイソブチレンからなる群から選ばれる少なくとも１種がより好ましく、ジイソブチレンが更に好ましい。 The olefin constituting the component (a) is preferably an olefin having 3 to 12 carbon atoms from the viewpoint of obtaining good dispersion performance, more preferably at least one selected from the group consisting of diisobutylene and isobutylene, and diisobutylene. Is more preferable.
　（ａ）成分を構成する不飽和二塩基酸としては、良好な分散性能を得る観点から、炭素数４以上６以下の脂肪族不飽和二塩基酸が好ましく、無水マレイン酸、マレイン酸及びイタコン酸からなる群から選ばれる少なくとも１種がより好ましく、無水マレイン酸及びマレイン酸からなる群から選ばれる少なくとも１種が更に好ましい。 The unsaturated dibasic acid constituting the component (a) is preferably an aliphatic unsaturated dibasic acid having 4 to 6 carbon atoms from the viewpoint of obtaining good dispersion performance, and maleic anhydride, maleic acid and itaconic acid. At least one selected from the group consisting of is more preferable, and at least one selected from the group consisting of maleic anhydride and maleic acid is more preferable.
　（ａ）成分の構成モノマーとしてのオレフィンと不飽和二塩基酸の割合は、良好な分散性能を得る観点から、オレフィン／不飽和二塩基酸のモル比が、好ましくは０．２５以上、より好ましくは０．４０以上、更に好ましくは０．５０以上、そして、好ましくは４以下、より好ましくは２．５以下、更に好ましくは２．０以下である。 The ratio of the olefin and the unsaturated dibasic acid as the constituent monomer of the component (a) is preferably a molar ratio of olefin / unsaturated dibasic acid of 0.25 or more, more preferably from the viewpoint of obtaining good dispersion performance. Is 0.40 or more, more preferably 0.50 or more, and preferably 4 or less, more preferably 2.5 or less, still more preferably 2.0 or less.
　（ａ）成分のオレフィンと不飽和二塩基酸との共重合体のアミド化物は、オレフィン及び不飽和二塩基酸の共重合体と、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンとを反応させることにより得ることができる。ここで用いられるアミンは、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンであり、炭素数６以上１０以下の分岐鎖アルキル基を有する１級アミンが好ましい。具体的には、イソヘキシルアミン、２－エチルヘキシルアミン、イソオクチルアミン、イソデシルアミン等が挙げられる。これらのアミンは１種又は２種以上を混合して用いることができる。当該アミンが有する前記分岐鎖アルキル基は、好ましくは炭素数８以上１０以下の分岐鎖アルキル基である。 The amidation product of the copolymer of the olefin and unsaturated dibasic acid of component (a) is a copolymer of olefin and unsaturated dibasic acid, and an amine having a branched alkyl group having 6 to 10 carbon atoms. Can be obtained by reacting. The amine used here is an amine having a branched alkyl group having 6 to 10 carbon atoms, and a primary amine having a branched alkyl group having 6 to 10 carbon atoms is preferable. Specific examples include isohexylamine, 2-ethylhexylamine, isooctylamine, and isodecylamine. These amines can be used alone or in combination of two or more. The branched alkyl group of the amine is preferably a branched alkyl group having 8 to 10 carbon atoms.
　（ａ）成分であるアミド化物のアミド化率（対不飽和二塩基酸）は、良好な分散性能、及び（ｂ）成分への良好な溶解性を得る観点から、好ましくは６０モル％超、より好ましくは７０モル％以上、更に好ましくは８０モル％以上、そして、好ましくは１５０モル％以下、より好ましくは１２０モル％以下、更に好ましくは１１０モル％以下である。
　尚、このアミド化率は、（ａ）成分製造時の原料の仕込みモル％に基づいて算出できる。アミド化率が、２００モル％を超える場合は、遊離アミド化物が存在するものと推察される。 The amidation rate (vs. unsaturated dibasic acid) of the amidated product as component (a) is preferably more than 60 mol% from the viewpoint of obtaining good dispersion performance and good solubility in component (b). More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, Preferably it is 150 mol% or less, More preferably, it is 120 mol% or less, More preferably, it is 110 mol% or less.
In addition, this amidation rate can be calculated based on the charged mol% of the raw material at the time of (a) component manufacture. When the amidation rate exceeds 200 mol%, it is presumed that a free amidated product is present.
　オレフィンと不飽和二塩基酸との共重合体のアミド化物は、塩であってもよい。塩は、アミン、ベタイン等で中和して得ることができる。塩は、イミダゾリン塩が好ましく、下記式（１）のイミダゾリン化合物の塩がより好ましい。 The amidated product of the copolymer of olefin and unsaturated dibasic acid may be a salt. The salt can be obtained by neutralization with an amine, betaine or the like. The salt is preferably an imidazoline salt, and more preferably a salt of an imidazoline compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔式中、Ｒ１は炭素数７以上２１以下の炭化水素基、Ｒ２は炭素数１以上５以下の２価の炭化水素基である。〕 [Wherein, R 1 is a hydrocarbon group having 7 to 21 carbon atoms, and R 2 is a divalent hydrocarbon group having 1 to 5 carbon atoms. ]
　前記式（１）中、Ｒ１の炭化水素基は、アルキル基、アルケニル基が挙げられる。また、Ｒ１の炭素数は、好ましくは８以上、より好ましくは１０以上、そして、好ましくは２２以下、より好ましくは２０以下である。Ｒ２の２価の炭化水素基は、アルキレン基が挙げられる。Ｒ２の炭素数は、好ましくは１以上、そして、好ましくは４以下である。 In the formula (1), examples of the hydrocarbon group for R 1 include an alkyl group and an alkenyl group. The carbon number of R 1 is preferably 8 or more, more preferably 10 or more, and preferably 22 or less, more preferably 20 or less. Examples of the divalent hydrocarbon group for R 2 include an alkylene group. The number of carbon atoms in R 2 is preferably 1 or more, and is preferably 4 or less.
　オレフィンと不飽和二塩基酸との共重合体のアミド化物が塩である場合、中和度は、好ましくは５０モル％以上、より好ましくは６０モル％、そして、好ましくは１００モル％以下、より好ましくは９０モル％以下である。 When the amidation product of the copolymer of olefin and unsaturated dibasic acid is a salt, the degree of neutralization is preferably 50 mol% or more, more preferably 60 mol%, and preferably 100 mol% or less, more Preferably it is 90 mol% or less.
　（ａ）成分である、前記アミド化物の重量平均分子量は、良好な分散性能、及び非芳香族系有機溶剤への良好な溶解性を得る観点から、好ましくは７００以上、より好ましくは３０００以上、更に好ましくは５０００以上、そして、好ましくは５０万以下、より好ましくは３０万以下、更に好ましくは１０万以下である。なお、本明細書における（ａ）成分のアミド化物の重量平均分子量は、下記条件のＧＰＣ（ゲルパーミエーションクロマトグラフィー、ポリスチレン換算）で測定した値である。
　カラム：α－Ｍ＋α－Ｍ（東ソー株式会社製）
　カラム温度：４０℃
　検出器：ＲＩ
　溶離液：６０ｍｍｏｌ／Ｌリン酸、５０ｍｍｏｌ／Ｌ臭化リチウム、ＤＭＦ溶剤
　流速：１．０ｍＬ／ｍｉｎ
　注入量：０．１ｍＬ
　標準：ポリスチレン The weight average molecular weight of the amidated compound as component (a) is preferably 700 or more, more preferably 3000 or more, from the viewpoint of obtaining good dispersion performance and good solubility in a non-aromatic organic solvent. More preferably, it is 5000 or more, preferably 500,000 or less, more preferably 300,000 or less, and still more preferably 100,000 or less. In addition, the weight average molecular weight of the amidation product of the component (a) in this specification is a value measured by GPC (gel permeation chromatography, converted to polystyrene) under the following conditions.
Column: α-M + α-M (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI
Eluent: 60 mmol / L phosphoric acid, 50 mmol / L lithium bromide, DMF solvent Flow rate: 1.0 mL / min
Injection volume: 0.1 mL
Standard: Polystyrene
　本発明では共重合体の重合率の向上並びに好ましい重量平均分子量を得る観点から、共重合体を製造する際に重合開始剤を使用できる。重合開始剤は、有機過酸化物、アゾ系等が挙げられ、このうち有機過酸化物が好ましく、具体的にはパーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステルが挙げられ、更に具体的には過酸化ベンゾイル、過酸化ラウロイル、ｔ－ブチルパーオキシ－２－エチルヘキサノエート等が挙げられる。
　重合開始剤の使用量（対不飽和二塩基酸）は、良好な重合率並びに分散性能を得る観点から、好ましくは０．１モル％以上、より好ましくは０．３モル％以上、更に好ましくは０．５モル％以上、そして、好ましくは２０モル％以下、より好ましくは１０モル％以下、更に好ましくは５モル％以下である。
　重合開始剤は重合終了後の熟成工程において共重合体の重合率を更に向上させる目的で添加しても良い。その際の使用量は０．０１モル％以上０．１モル％以下（対不飽和二塩基酸）が好ましい。 In the present invention, from the viewpoint of improving the polymerization rate of the copolymer and obtaining a preferred weight average molecular weight, a polymerization initiator can be used when producing the copolymer. Examples of the polymerization initiator include organic peroxides, azo series, etc. Among them, organic peroxides are preferable, and specifically, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates. Peroxyesters, and more specifically, benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, and the like.
The amount of the polymerization initiator used (relative to the unsaturated dibasic acid) is preferably at least 0.1 mol%, more preferably at least 0.3 mol%, still more preferably from the viewpoint of obtaining a good polymerization rate and dispersion performance. 0.5 mol% or more, and preferably 20 mol% or less, more preferably 10 mol% or less, and further preferably 5 mol% or less.
The polymerization initiator may be added for the purpose of further improving the polymerization rate of the copolymer in the aging step after completion of the polymerization. The amount used is preferably 0.01 mol% or more and 0.1 mol% or less (vs. unsaturated dibasic acid).
　本発明では、（ａ）成分と共に未反応のオレフィンや不飽和二塩基酸等を本発明の効果を阻害しない範囲で含有する混合物を、（ａ）成分の供給原料として用いてもよい。 In the present invention, a mixture containing unreacted olefin, unsaturated dibasic acid and the like together with the component (a) in a range that does not inhibit the effect of the present invention may be used as a feedstock for the component (a).
　（ａ）成分は、前記アミド化合物の塩が好ましく、前記アミド化物のイミダゾリン塩がより好ましい。 The component (a) is preferably a salt of the amide compound, more preferably an imidazoline salt of the amidated product.
　本発明に用いられる（ｂ）成分の混合有機溶剤は、環境への配慮から、非芳香族系有機溶剤であり、また、（ａ）成分の溶解性を向上させる観点から、（ｂ１）成分の酢酸エステルと（ｂ２）成分の低級アルコールとの混合有機溶剤が用いられる。本発明の印刷インキ用分散剤組成物は、いわゆる油中分散型スラリーの形態の印刷インキ組成物の調製に好適に用いられる。 The mixed organic solvent of component (b) used in the present invention is a non-aromatic organic solvent in consideration of the environment, and from the viewpoint of improving the solubility of component (a), A mixed organic solvent of acetate and (b2) component lower alcohol is used. The printing ink dispersant composition of the present invention is suitably used for preparing a printing ink composition in the form of a so-called oil-dispersed slurry.
　（ｂ１）成分の酢酸エステルとしては、総炭素数２以上６以下の酢酸エステルが挙げられ、具体的には、酢酸エチル、酢酸プロピル、酢酸ブチル等が挙げられる。（ｂ１）成分は、酢酸エチル及び酢酸ブチルからなる群から選ばれる少なくとも１種が好ましい。
　また、（ｂ２）成分の低級アルコールとしては、炭素数２以上６以下のアルコールが挙げられ、具体的には、イソプロピルアルコール、ｎ－プロピルアルコール、イソブチルアルコール、ｎ－ブチルアルコール等が挙げられる。（ｂ２）成分は、イソプロピルアルコール及びｎ－ブチルアルコールからなる群から選ばれる少なくとも１種が好ましい。 Examples of the acetic acid ester of the component (b1) include acetic acid esters having 2 to 6 carbon atoms in total, and specifically include ethyl acetate, propyl acetate, butyl acetate and the like. The component (b1) is preferably at least one selected from the group consisting of ethyl acetate and butyl acetate.
Examples of the lower alcohol as the component (b2) include alcohols having 2 to 6 carbon atoms, and specific examples include isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol and the like. The component (b2) is preferably at least one selected from the group consisting of isopropyl alcohol and n-butyl alcohol.
　（ｂ）成分は、良好な分散性能、及び（ａ）成分の（ｂ）成分への良好な溶解性を得る観点から、（ｂ１）成分の含有量と（ｂ２）成分の含有量の質量比（ｂ１）／（ｂ２）が、好ましくは０．０１以上、より好ましくは０．２５以上、更に好ましくは０．４５以上、より更に好ましくは０．８以上、そして、好ましくは１００以下、より好ましくは９９以下、更に好ましくは５０以下、より更に好ましく９は以下、より更に好ましくは３以下である。 Component (b) is a mass ratio of the content of component (b1) and the content of component (b2) from the viewpoint of obtaining good dispersion performance and good solubility of component (a) in component (b). (B1) / (b2) is preferably 0.01 or more, more preferably 0.25 or more, still more preferably 0.45 or more, still more preferably 0.8 or more, and preferably 100 or less, more preferably Is 99 or less, more preferably 50 or less, even more preferably 9 or less, and still more preferably 3 or less.
　本発明の印刷インキ用分散剤組成物は、（ｂ）成分以外の有機溶剤を含有してもよいが、全有機溶剤中、（ｂ）成分の占める割合は、好ましくは１０質量％以上、より好ましくは３０質量％以上、更に好ましくは７０質量％以上、そして、好ましくは１００質量％以下であり、１００質量％であってもよい。
　また、本発明の印刷インキ用分散剤組成物は、水の含有量が少ないものが好ましい。更に好ましくは、水を実質的に含有しないものが好ましい。ここで、「水を実質的に含有しない」とは、組成物中の水の含有量が好ましくは５質量％以下、より好ましくは３質量％以下、更に好ましくは１質量％以下であることをいう。 The dispersant composition for printing ink of the present invention may contain an organic solvent other than the component (b), but the proportion of the component (b) in the total organic solvent is preferably 10% by mass or more. It is preferably 30% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.
The dispersant composition for printing ink of the present invention preferably has a low water content. More preferably, it is substantially free of water. Here, “substantially does not contain water” means that the content of water in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. Say.
　本発明の印刷インキ用分散剤組成物は、分散性向上の観点から、（ａ）成分の含有量と（ｂ）成分の含有量との質量比（ａ）／（ｂ）が、好ましくは０．１以上、より好ましくは０．２以上、更に好ましくは０．３以上、そして、好ましくは０．９以下、より好ましくは０．７以下、更に好ましくは０．５以下である。 In the dispersant composition for printing ink of the present invention, the mass ratio (a) / (b) between the content of the component (a) and the content of the component (b) is preferably 0 from the viewpoint of improving dispersibility. 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 0.9 or less, more preferably 0.7 or less, still more preferably 0.5 or less.
　本発明の印刷インキ用分散剤組成物は、分散性向上の観点から、（ａ）成分を、好ましくは１０質量％以上、より好ましくは１５質量％以上、更に好ましくは２０質量％以上、そして、好ましくは８０質量％以下、より好ましくは６０質量％以下、更に好ましくは４０質量％以下含有する。 From the viewpoint of improving dispersibility, the dispersant composition for printing ink of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and the component (a). Preferably it is 80 mass% or less, More preferably, it is 60 mass% or less, More preferably, it contains 40 mass% or less.
　本発明の印刷インキ用分散剤組成物は、任意成分として、高級アルコール、脂肪酸、脂肪酸エステル、脂肪アミンなどを含有することができる。 The printing ink dispersant composition of the present invention can contain higher alcohols, fatty acids, fatty acid esters, fatty amines and the like as optional components.
　なお、本発明の印刷インキ用分散剤組成物は、（ｂ）成分をそのまま印刷インキ組成物の溶剤として用いることができるため、組成によっては、本発明の印刷インキ用分散剤組成物に印刷インキ用粉体を混合するだけで、本発明の印刷インキ組成物を得ることができる。例えば、本発明の印刷インキ用分散剤組成物は、印刷インキ用ビヒクルやその溶剤、更には、印刷インキ組成物用溶剤等として使用することができる。 In addition, since the dispersant composition for printing inks of this invention can use (b) component as a solvent of a printing ink composition as it is, depending on a composition, printing ink is added to the dispersant composition for printing inks of this invention. The printing ink composition of the present invention can be obtained simply by mixing the powder for use. For example, the dispersant composition for printing ink of the present invention can be used as a vehicle for printing ink and its solvent, and further as a solvent for printing ink composition.
　本発明の印刷インキ組成物は、印刷インキ用粉体又は他の有機溶剤との混合性の向上の観点から、液体であることが好ましい。 The printing ink composition of the present invention is preferably a liquid from the viewpoint of improving the miscibility with printing ink powders or other organic solvents.
　本発明は、前記（ａ）成分と、前記（ｂ）成分とを含有する組成物の、印刷インキ用分散剤としての使用を提供する。この使用に係る組成物には、本発明の印刷インキ組成物で述べた事項を適宜適用できる。 The present invention provides the use of a composition containing the component (a) and the component (b) as a dispersant for printing ink. The matters described in the printing ink composition of the present invention can be appropriately applied to the composition according to this use.
〔印刷インキ組成物〕
　本発明の印刷インキ組成物は、印刷インキ用粉体と、前記（ａ）成分と、前記（ｂ）成分とを含有する。（ａ）成分、及び（ｂ）成分の具体例及び好ましい態様は、本発明の印刷インキ用分散剤組成物と同じである。 [Printing ink composition]
The printing ink composition of the present invention contains a printing ink powder, the component (a), and the component (b). Specific examples and preferred embodiments of the component (a) and the component (b) are the same as those of the dispersant composition for printing ink of the present invention.
　印刷インキ用粉体としては、着色剤、着色剤以外の無機粉体が挙げられる。
　着色剤は、顔料が挙げられる。顔料としては、印刷インキで一般的に用いられている各種無機顔料、有機顔料等が使用できる。無機顔料としては、例えば、酸化チタン、ベンガラ、アンチモンレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛、サチンホワイト、亜鉛華、等の有色顔料、シリカ、炭酸カルシウム、カオリン、クレー、硫酸バリウム、水酸化アルミニウム、タルク等の体質顔料、アクリル樹脂で表面処理したアルミニウム粒子を含有するアルミペースト、表面に酸化チタンと酸化スズと酸化ジルコニウムとがコーティングされたマイカ等のパール顔料を挙げることができる。有機顔料としては、例えば、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等を挙げることができる。
　また、着色剤以外の無機粉体としては、リン酸カルシウム、リン酸亜鉛、ベントナイト、フェライト、アルミナ、酸化マグネシウム、ホワイトカーボン、セメント、石膏、チタン酸塩、珪酸塩等が挙げられる。 Examples of the powder for printing ink include a colorant and an inorganic powder other than the colorant.
Examples of the colorant include pigments. As the pigment, various inorganic pigments and organic pigments generally used in printing ink can be used. As the inorganic pigment, for example, colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, satin white, zinc white, silica, calcium carbonate, kaolin, clay, Examples include extender pigments such as barium sulfate, aluminum hydroxide and talc, aluminum pastes containing aluminum particles surface-treated with acrylic resin, and pearl pigments such as mica whose surfaces are coated with titanium oxide, tin oxide and zirconium oxide. Can do. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
Examples of the inorganic powder other than the colorant include calcium phosphate, zinc phosphate, bentonite, ferrite, alumina, magnesium oxide, white carbon, cement, gypsum, titanate, and silicate.
　印刷インキ用粉体は、着色剤を含むことが好ましい。本発明の印刷インキ組成物は、良好な分散性が得られる観点から、着色剤を、好ましくは５質量％以上、より好ましくは７質量％以上、更に好ましくは９質量％以上、そして、好ましくは５０質量％以下、より好ましくは３０質量％以下含有する。 The printing ink powder preferably contains a colorant. In the printing ink composition of the present invention, from the viewpoint of obtaining good dispersibility, the colorant is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 9% by mass or more, and preferably 50 mass% or less, More preferably, it contains 30 mass% or less.
　また、本発明の印刷インキ組成物が、印刷インキ用粉体として着色剤以外の無機粉体を含有する場合、印刷インキ用粉体中、着色剤以外の無機粉体を、好ましくは１０質量％以上、より好ましくは２０質量％以上、更に好ましくは３０質量％以上、そして、好ましくは７０質量％以下、より好ましくは６０質量％以下含有する。 Further, when the printing ink composition of the present invention contains an inorganic powder other than the colorant as the printing ink powder, the inorganic powder other than the colorant in the printing ink powder is preferably 10% by mass. More preferably, it is 20% by mass or more, more preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less.
　本発明の印刷インキ組成物は、良好な分散性が得られる観点から、（ａ）成分を、印刷インキ用粉体１００質量部に対し、好ましくは１質量部以上、より好ましくは２質量部以上、更に好ましくは５質量部以上、そして、好ましくは３０質量部以下、より好ましくは２０質量部以下含有する。 From the viewpoint of obtaining good dispersibility, the printing ink composition of the present invention is preferably 1 part by mass or more, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the printing ink powder. More preferably, it is 5 parts by mass or more and preferably 30 parts by mass or less, more preferably 20 parts by mass or less.
　本発明の印刷インキ組成物は、（ｂ）成分を、好ましくは８０質量％以上、より好ましくは８５質量％以上、そして、好ましくは９５質量％以下、より好ましくは９０質量％以下含有する。 The printing ink composition of the present invention contains the component (b) preferably 80% by mass or more, more preferably 85% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less.
　本発明の印刷インキ組成物の組成は種々設定できるが、例えば、グラビア印刷用インキ組成物であれば、各成分の含有量は、例えば、以下の通りとすることができる。
・着色剤　組成物中、好ましくは７質量％以上３０質量％以下
・（ａ）成分　着色剤１００質量部に対して、好ましくは０．５質量部以上３０質量部以下
・（ｂ）成分　組成物中、好ましくは４０質量％以上９２．５質量％以下 The composition of the printing ink composition of the present invention can be variously set. For example, in the case of an ink composition for gravure printing, the content of each component can be set as follows, for example.
-Colorant In composition, Preferably it is 7 mass% or more and 30 mass% or less. (A) component With respect to 100 mass parts of colorant, Preferably it is 0.5 mass part or more and 30 mass parts or less. (B) component Composition Medium, preferably 40% by mass or more and 92.5% by mass or less
　本発明の印刷インキ組成物は、２５℃での分散粒子の平均粒径が、好ましくは３μｍ以下、より好ましくは２．５μｍ以下であり、一例として、２μｍ近傍が好ましい。平均粒径の下限値は、１．１μｍ以上が好ましい。尚、平均粒径は、実施例に記載した方法で測定する。 In the printing ink composition of the present invention, the average particle diameter of dispersed particles at 25 ° C. is preferably 3 μm or less, more preferably 2.5 μm or less, and as an example, the vicinity is preferably 2 μm. The lower limit of the average particle size is preferably 1.1 μm or more. In addition, an average particle diameter is measured by the method described in the Example.
　本発明の印刷インキ組成物は、バインダー、可塑剤等を含有することができる。バインダーとしては例えば、エチルセルロース、アクリル、ポリビニルブチラール、ポリビニルアセタール、ポリビニルアルコール、ポリオレフィン、ポリウレタン、ポリスチレン、あるいはこれらの混合物等が挙げられる。可塑剤としては例えば、フタル酸ジオクチル、アジピン酸、リン酸エステル、グリコール等が挙げられる。 The printing ink composition of the present invention can contain a binder, a plasticizer, and the like. Examples of the binder include ethyl cellulose, acrylic, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, or a mixture thereof. Examples of the plasticizer include dioctyl phthalate, adipic acid, phosphate ester, glycol and the like.
　また、本発明の印刷インキ組成物の粘度も、印刷方式に応じて設定することができる。例えば、グラビア印刷用インキ組成物であれば、２５℃の粘度は、好ましくは０．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下である。 Also, the viscosity of the printing ink composition of the present invention can be set according to the printing method. For example, in the case of an ink composition for gravure printing, the viscosity at 25 ° C. is preferably 0.5 mPa · s or more and 20 mPa · s or less.
　本発明の印刷インキ組成物の、分散安定化のメカニズムは明らかではないが、本発明の（ａ）成分を構成する不飽和二塩基酸から誘導される基が印刷インキ用粉体に吸着し、本発明の（ａ）成分を構成するオレフィンから誘導される基が有機溶剤中に溶解拡散することにより、印刷インキ用粉体の分散安定化が向上するものと推察される。 Although the mechanism of dispersion stabilization of the printing ink composition of the present invention is not clear, the group derived from the unsaturated dibasic acid constituting the component (a) of the present invention is adsorbed on the printing ink powder, The group derived from the olefin constituting the component (a) of the present invention is presumed to improve the dispersion stability of the printing ink powder by dissolving and diffusing in the organic solvent.
　本発明の印刷インキ組成物は、油中分散型スラリーであることが好ましい。本発明の印刷インキ組成物を得る方法としては、通常のスラリー化の方法を用いることができる。例えば本発明の印刷インキ用分散剤組成物に印刷インキ用粉体を添加して撹拌、混合する方法、印刷インキ用粉体に本発明の印刷インキ用分散剤組成物を加えて撹拌、混合する方法等が挙げられる。撹拌、混合する方法としては、例えば高速ディスパーサー、ホモミキサー、ボールミル等一般に用いられる撹拌装置を使用することができる。
　また、印刷インキ用粉体の顔料又は粗粒子を粉砕と同時にスラリー化する場合には、印刷インキ用粉体の鉱石又は粗粒子に本発明の印刷インキ用分散剤組成物を添加して、粉砕と同時にスラリー化する方法等を行うこともできる。粉砕と同時にスラリー化する方法には、ビーズミル等一般に用いられる湿式粉砕機を使用することが出来る。 The printing ink composition of the present invention is preferably an oil-dispersed slurry. As a method for obtaining the printing ink composition of the present invention, a usual slurrying method can be used. For example, a method of adding a printing ink powder to the printing ink dispersant composition of the present invention and stirring and mixing, a method of adding the printing ink dispersant composition of the present invention to a printing ink powder and stirring and mixing Methods and the like. As a method of stirring and mixing, for example, a generally used stirring device such as a high-speed disperser, a homomixer, or a ball mill can be used.
When the pigment or coarse particles of the printing ink powder are slurried at the same time as pulverization, the dispersant composition for printing ink of the present invention is added to the ore or coarse particles of the printing ink powder and pulverized. At the same time, a method of slurrying can be performed. A generally used wet pulverizer such as a bead mill can be used for the method of slurrying simultaneously with pulverization.
　本発明は、印刷インキ用粉体と、前記（ａ）成分と、前記（ｂ）成分とを含有する組成物の、印刷インキとしての使用を提供する。この使用に係る組成物には、本発明の印刷インキ用分散剤組成物及び印刷インキ組成物で述べた事項を適宜適用できる。 The present invention provides use of a composition containing a powder for printing ink, the component (a), and the component (b) as a printing ink. The matters described in the dispersant composition for printing ink and the printing ink composition of the present invention can be appropriately applied to the composition according to this use.
〔印刷インキ用分散剤組成物又は印刷インキ組成物の製造方法〕
　本発明は、オレフィンと不飽和二塩基酸とを、酢酸エステル（ｂ１）と低級アルコール（ｂ２）とを含む反応溶媒中で反応させて共重合体を得る工程、及び
　前記共重合体を、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンでアミド化して前記共重合体のアミド化物を得る工程、
を有する、印刷インキ用分散剤組成物の製造方法を提供する。 [Dispersant composition for printing ink or method for producing printing ink composition]
The present invention comprises a step of reacting an olefin and an unsaturated dibasic acid in a reaction solvent containing an acetate ester (b1) and a lower alcohol (b2) to obtain a copolymer; and A step of amidating with an amine having a branched alkyl group of 6 to 10 to obtain an amidated product of the copolymer;
The manufacturing method of the dispersing agent composition for printing inks which has this is provided.
　上記製造方法においては、前記共重合体のアミド化物は、（ａ）成分である。（ｂ１）成分と（ｂ２）成分とを含む反応溶媒はそのまま印刷インキ用分散剤組成物の（ｂ）成分とすることができる。
　本発明の印刷インキ用分散剤組成物や本発明の印刷インキ組成物で述べた事項は、本発明の印刷インキ用分散剤組成物の製造方法に適用できる。
　本発明の印刷インキ用分散剤組成物の製造方法は、前記共重合体のアミド化物を、前記式（１）のイミダゾリン化合物で中和する工程を有することができる。 In the above production method, the amidated product of the copolymer is the component (a). The reaction solvent containing the component (b1) and the component (b2) can be used as the component (b) of the printing ink dispersant composition as it is.
The matters described in the dispersant composition for printing ink of the present invention and the printing ink composition of the present invention can be applied to the method for producing the dispersant composition for printing ink of the present invention.
The manufacturing method of the dispersing agent composition for printing inks of this invention can have the process of neutralizing the amidation product of the said copolymer with the imidazoline compound of said Formula (1).
　また、本発明は、
　印刷インキ用粉体と、
　オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
　酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
を混合する、印刷インキ組成物の製造方法を提供する。 The present invention also provides:
Printing ink powder,
An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a);
Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2);
A method for producing a printing ink composition is provided.
　上記製造方法においては、（ａ）成分及び（ｂ）成分を含有する本発明の印刷インキ用分散剤組成物を用いることができる。その場合、必要に応じて、（ｂ１）成分及び／又は（ｂ２）成分を添加して組成を調整することができる。本発明の印刷インキ用分散剤組成物や本発明の印刷インキ組成物で述べた事項は、この印刷インキ組成物の製造方法に適用できる。 In the above production method, the dispersant composition for printing ink of the present invention containing the component (a) and the component (b) can be used. In that case, a composition can be adjusted by adding (b1) component and / or (b2) component as needed. The matters described in the dispersant composition for printing ink of the present invention and the printing ink composition of the present invention can be applied to the method for producing the printing ink composition.
実施例
製造例１
　攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えた反応容器に無水マレイン酸（三井化学（株）製）７０．６ｇ、酢酸エチル（シノケム・ジャパン（株）製）３２．５ｇ及びイソプロピルアルコール（以下ＩＰＡと略記）（ＪＸエネルギー（株）製）３２．５ｇを仕込み、窒素気流下で９３℃に加熱後、この温度を維持しながら、８５質量％ジイソブチレン（丸善石油化学（株）製）の酢酸エチルとＩＰＡ混合溶液９５．０ｇ及び重合開始剤として２質量％パーブチルＯ（日油社製、ｔ－ブチルパーオキシ－２－エチルヘキサノエート）の酢酸エチルとＩＰＡ混合溶液７４．０ｇをそれぞれ別の滴下ロートから１．５時間かけて滴下し重合反応を行った。滴下終了１５分後に２質量％パーブチルＯの酢酸エチルとＩＰＡ混合溶液３．０ｇを一括で添加し、その後、９３℃で９時間熟成し、重合反応を完結させた。反応終了後、冷却し、６５℃に保持しながら２－エチルヘキシルアミン（広栄化学工業（株）製）９３．０ｇを滴下ロートから１時間かけて滴下しアミド化反応を行った。滴下終了後、６５℃で２時間熟成した。その後、冷却し、４０℃に保持しながら中和剤であるオレイルヒドロキシエチルイミダゾリン（（株）八代製）１８５．５ｇを滴下ロートから１．５時間かけて滴下し中和反応を行った。滴下終了後、４０℃で１時間熟成し、反応を完結させ、無水マレイン酸／ジイソブチレン共重合体アミド化物のオレイルエチルイミダゾリンによる中和物を得た。本アミド化物の中和物のアミド化率、重量平均分子量（前記方法により測定した値、以下同じ）、合成時の使用溶剤、中和剤及び中和度を表１に示す。なお、オレイルヒドロキシエチルイミダゾリンは、式（１）中のＲ１がオレイル基、Ｒ２がエチレン基の化合物である。
　この方法により得られた反応生成物を、そのまま印刷インキ用分散剤組成物とした。 Example Production Example 1
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel, maleic anhydride (Mitsui Chemicals Co., Ltd.) 70.6 g, ethyl acetate (Sinochem Japan Co., Ltd.) 32.5 g And 32.5 g of isopropyl alcohol (hereinafter abbreviated as IPA) (manufactured by JX Energy Co., Ltd.), heated to 93 ° C. under a nitrogen stream, and maintained at this temperature, 85 mass% diisobutylene (Maruzen Petrochemical ( 95.0 g of a mixed solution of ethyl acetate and IPA, and 2 wt% perbutyl O (manufactured by NOF Corporation, t-butylperoxy-2-ethylhexanoate) as a polymerization initiator 74.0 g was added dropwise from a separate dropping funnel over 1.5 hours to conduct a polymerization reaction. 15 minutes after the completion of dropping, 3.0 g of a 2 mass% perbutyl O ethyl acetate and IPA mixed solution was added all at once, and then aged at 93 ° C. for 9 hours to complete the polymerization reaction. After completion of the reaction, the mixture was cooled and 93.0 g of 2-ethylhexylamine (manufactured by Guangei Chemical Industry Co., Ltd.) was dropped from the dropping funnel over 1 hour while maintaining the temperature at 65 ° C. to carry out an amidation reaction. After completion of dropping, the mixture was aged at 65 ° C. for 2 hours. Then, while cooling and maintaining at 40 ° C., 185.5 g of oleylhydroxyethylimidazoline (manufactured by Yatsushiro Co., Ltd.) as a neutralizing agent was dropped from the dropping funnel over 1.5 hours to carry out a neutralization reaction. After completion of the dropwise addition, the mixture was aged for 1 hour at 40 ° C. to complete the reaction, and a neutralized product of maleic anhydride / diisobutylene copolymer amidated product with oleylethylimidazoline was obtained. Table 1 shows the amidation rate of the neutralized product of the present amidated product, the weight average molecular weight (value measured by the above method, the same applies hereinafter), the solvent used during synthesis, the neutralizing agent, and the degree of neutralization. In addition, oleylhydroxyethyl imidazoline is a compound in which R 1 in the formula (1) is an oleyl group and R 2 is an ethylene group.
The reaction product obtained by this method was directly used as a dispersant for printing ink.
製造例２～４、比較製造例１～８
　製造条件を表１の通りとする以外は製造例１と同様にして、表１に示すアミド化物もしくはその中和物又はエステル化物を含む反応生成物を得た。得られた反応生成物は、そのまま印刷インキ用分散剤組成物とした。
　尚表１中、イタコン酸は磐田化学工業（株）製、イソブチレンは（株）クラレ社製、オレイルアミン、ステアリルアミン、ｎ－オクチルアミンは花王（株）製、ｎ－ブチルアミン、ｎ－デシルアミン、２－エチルヘキシルアルコール、プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）、メチルイソブチルケトン（ＭＩＢＫ）、トルエン、メチルエチルケトン（ＭＥＫ）、キシレンは和光純薬工業（株）製、イソヘキシルアミン、イソオクチルアミン、イソデシルアミン、イソペンチルアミン、イソドデシルアミン、ステアリルエチルイミダゾリン、ラウリルエチルイミダゾリンは東京化成工業（株）製である。 Production Examples 2 to 4 and Comparative Production Examples 1 to 8
A reaction product containing an amidated product or a neutralized product or an esterified product thereof as shown in Table 1 was obtained in the same manner as in Production Example 1 except that the production conditions were as shown in Table 1. The obtained reaction product was used as a dispersant for printing ink as it was.
In Table 1, itaconic acid is manufactured by Iwata Chemical Industry Co., Ltd., isobutylene is manufactured by Kuraray Co., Ltd., oleylamine, stearylamine, and n-octylamine are manufactured by Kao Corporation, n-butylamine, n-decylamine, 2 -Ethylhexyl alcohol, propylene glycol methyl ether acetate (PGMEA), methyl isobutyl ketone (MIBK), toluene, methyl ethyl ketone (MEK), xylene are manufactured by Wako Pure Chemical Industries, Ltd., isohexylamine, isooctylamine, isodecylamine, Isopentylamine, isododecylamine, stearylethylimidazoline, and laurylethylimidazoline are manufactured by Tokyo Chemical Industry Co., Ltd.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１中、モル％は、いずれも不飽和二塩基酸に対するモル％である。
　表１中、製造例１～４では、共重合体のアミド化物が（ａ）成分、合成時の使用溶剤が（ｂ）成分である。 In Table 1, mol% is mol% relative to the unsaturated dibasic acid.
In Table 1, in Production Examples 1 to 4, the amidated product of the copolymer is the component (a), and the solvent used in the synthesis is the component (b).
実施例１～４、比較例１～９
　表１の印刷インキ用分散剤組成物と比較の分散剤とを用いて印刷インキ組成物を調製し、以下の評価を行った。結果を表２に示した。 Examples 1 to 4 and Comparative Examples 1 to 9
A printing ink composition was prepared using the printing ink dispersant composition of Table 1 and a comparative dispersant, and the following evaluations were performed. The results are shown in Table 2.
（１）分散性の評価（Ｉ）（調製直後の分散性）
　１００ｍＬのスクリュー管に、平均粒径が２４ｎｍのカーボンブラック（三菱化学（株）製ＭＡ１００）４ｇ、溶剤、表１の印刷インキ用分散剤組成物又は比較の分散剤を仕込んだ。ここで、比較の分散剤は、ルブリゾール２４０００（ポリエチレンイミン系分散剤、ルブリゾール社製）であった。また、表１の印刷インキ用分散剤組成物と比較の分散剤は、それぞれ、合成時に使用した溶剤と同じ溶剤で希釈して固形分３０質量％に調製したものを使用した。表１の印刷インキ用分散剤組成物については、固形分の量は、共重合体のアミド化物もしくはエステル化物又は塩の量であるとみなすことができる。なお、比較の分散剤では、溶剤は、酢酸エチル／ＩＰＡの質量比が１／１の混合有機溶剤を用いた。
　その後、ブランソン社製の超音波分散装置Ｂ１５１０で３時間処理を行い、スラリーを調製した。これを印刷インキ組成物とした。印刷インキ組成物におけるカーボンブラック濃度が１０質量％となるように溶剤の量を調製した。
　印刷インキ用分散剤組成物又は比較の分散剤の添加量が、８、１０、又は１２質量％（対カーボンブラック（固形分換算））の印刷インキ組成物を用意した。
　各分散剤添加量の印刷インキ組成物について、調製直後に、堀場製作所社製のレーザー散乱粒度分布計ＬＡ－９２０を用いて、２５℃における印刷インキ組成物のカーボンブラックの平均粒径を測定した。結果を表２に示す。
　尚、印刷インキ組成物は、各分散剤添加量において平均粒径が２μｍ以下であるものを分散性が良好であるとした。 (1) Evaluation of dispersibility (I) (dispersibility immediately after preparation)
A 100 mL screw tube was charged with 4 g of carbon black having an average particle diameter of 24 nm (MA100 manufactured by Mitsubishi Chemical Corporation), a solvent, a dispersant composition for printing inks shown in Table 1, or a comparative dispersant. Here, the comparative dispersant was Lubrizol 24000 (polyethyleneimine dispersant, manufactured by Lubrizol). Further, as the dispersant for printing ink in Table 1 and the comparative dispersant, those prepared by diluting with the same solvent as used at the time of synthesis and having a solid content of 30% by mass were used. For the printing ink dispersant composition of Table 1, the amount of solids can be considered to be the amount of copolymer amidated or esterified or salt. In the comparative dispersant, a mixed organic solvent having a mass ratio of ethyl acetate / IPA of 1/1 was used as the solvent.
Then, it processed for 3 hours with the ultrasonic dispersion apparatus B1510 made from Branson, and prepared the slurry. This was made into the printing ink composition. The amount of the solvent was adjusted so that the carbon black concentration in the printing ink composition was 10% by mass.
A printing ink composition was prepared in which the amount of the dispersant composition for printing ink or the comparative dispersant was 8, 10, or 12% by mass (vs. carbon black (in terms of solid content)).
For the printing ink composition with each dispersant added amount, immediately after preparation, the average particle size of carbon black of the printing ink composition at 25 ° C. was measured using a laser scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd. . The results are shown in Table 2.
A printing ink composition having an average particle diameter of 2 μm or less at each dispersant addition amount was regarded as having good dispersibility.
（２）分散性の評価（II）（再分散性）
　（１）で得られた印刷インキ組成物を、アドバンテック社製減圧乾燥機ＶＯ－３２０で８０℃、２４時間で減圧乾燥を行い、溶剤を完全に除去した。その後、再度、酢酸エチル／ＩＰＡの質量比が１／１の混合有機溶剤を加えてカーボンブラック濃度１０質量％に調整し、超音波分散装置で１時間分散処理を行い、カーボンブラックを再分散させた印刷インキ組成物を得た。次いで（１）と同様に印刷インキ組成物のカーボンブラックの平均粒径を測定した。結果を表２に示す。
　尚、印刷インキ組成物は、各分散剤添加量において平均粒径が２μｍ以下であるものを再分散性が良好であるとした。 (2) Evaluation of dispersibility (II) (Redispersibility)
The printing ink composition obtained in (1) was dried under reduced pressure at 80 ° C. for 24 hours with a vacuum dryer VO-320 manufactured by Advantech, and the solvent was completely removed. Thereafter, a mixed organic solvent having a mass ratio of ethyl acetate / IPA of 1/1 is added again to adjust the carbon black concentration to 10% by mass, and dispersion treatment is performed for 1 hour with an ultrasonic dispersing device to redisperse the carbon black. A printing ink composition was obtained. Next, the average particle diameter of carbon black of the printing ink composition was measured in the same manner as (1). The results are shown in Table 2.
A printing ink composition having an average particle size of 2 μm or less at each dispersant addition amount was regarded as having good redispersibility.
（３）分散性の評価（III）（保存後の分散性）
　（２）で得られた印刷インキ組成物を、ヤマト社製乾燥機ＤＫ６００中に５０℃、７日間静置した。その後、（１）と同様に印刷インキ組成物のカーボンブラックの平均粒径を測定した。結果を表２に示す。
　尚、印刷インキ組成物は、各分散剤添加量において平均粒径が２μｍ以下であるものを分散性が良好であるとし、２μｍを超える場合は、２μｍにより近いものの方がより分散性が良好であるとした。 (3) Evaluation of dispersibility (III) (dispersibility after storage)
The printing ink composition obtained in (2) was allowed to stand at 50 ° C. for 7 days in a dryer DK600 manufactured by Yamato. Thereafter, the average particle size of carbon black of the printing ink composition was measured in the same manner as in (1). The results are shown in Table 2.
The printing ink composition has a good dispersibility when the average particle size is 2 μm or less at each dispersant addition amount, and when it exceeds 2 μm, the closer to 2 μm, the better the dispersibility. It was supposed to be.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (15)

  1. 　オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）とを含有する、印刷インキ用分散剤組成物。 An amidated product of an olefin / unsaturated dibasic acid copolymer with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a), an acetate ester (b1) and a lower alcohol (b2) And a mixed organic solvent (b). A dispersant composition for printing inks.
  2. 　前記アミド化物の塩が、下記式（１）のイミダゾリン化合物の塩である、請求項１記載の印刷インキ用分散剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     〔式中、Ｒ１は炭素数７以上２１以下の炭化水素基、Ｒ２は炭素数１以上５以下の２価の炭化水素基である。〕     The dispersant composition for printing ink according to claim 1, wherein the salt of the amidated product is a salt of an imidazoline compound represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     [Wherein, R 1 is a hydrocarbon group having 7 to 21 carbon atoms, and R 2 is a divalent hydrocarbon group having 1 to 5 carbon atoms. ]
  3. 　酢酸エステル（ｂ１）が、酢酸エチル及び酢酸ブチルからなる群から選ばれる少なくとも１種であり、低級アルコール（ｂ２）が、イソプロピルアルコール及びｎ－ブチルアルコールからなる群から選ばれる少なくとも１種である請求項１又は２記載の印刷インキ用分散剤組成物。 The acetate ester (b1) is at least one selected from the group consisting of ethyl acetate and butyl acetate, and the lower alcohol (b2) is at least one selected from the group consisting of isopropyl alcohol and n-butyl alcohol. Item 3. A dispersant composition for printing inks according to item 1 or 2.
  4. 　オレフィンが、ジイソブチレン及びイソブチレンからなる群から選ばれる少なくとも１種である請求項１～３に記載の印刷インキ用分散剤組成物。 The printing ink dispersant composition according to claim 1, wherein the olefin is at least one selected from the group consisting of diisobutylene and isobutylene.
  5. 　不飽和二塩基酸が、無水マレイン酸、マレイン酸及びイタコン酸からなる群から選ばれる少なくとも１種である請求項１～４に記載の印刷インキ用分散剤組成物。 The dispersant composition for printing inks according to claim 1, wherein the unsaturated dibasic acid is at least one selected from the group consisting of maleic anhydride, maleic acid and itaconic acid.
  6. 　（ａ）の含有量と（ｂ）の含有量との質量比（ａ）／（ｂ）が０．１以上０．９以下である、請求項１～５いずれかに記載の印刷インキ用分散剤組成物。 The dispersion for printing ink according to any one of claims 1 to 5, wherein the mass ratio (a) / (b) of the content of (a) to the content of (b) is 0.1 or more and 0.9 or less. Agent composition.
  7. 　（ａ）を分散剤組成物中１０質量％以上８０質量％以下含有する、請求項１～６いずれかに記載の印刷インキ用分散剤組成物。 The dispersant composition for printing ink according to any one of claims 1 to 6, wherein (a) is contained in the dispersant composition in an amount of 10% by mass to 80% by mass.
  8. 　（ｂ１）の含有量と（ｂ２）の含有量の質量比（ｂ１）／（ｂ２）が０．０１以上１００以下である、請求項１～７いずれかに記載の印刷インキ用分散剤組成物。 The printing ink dispersant composition according to any one of claims 1 to 7, wherein a mass ratio (b1) / (b2) of the content of (b1) to the content of (b2) is 0.01 or more and 100 or less. .
  9. 　印刷インキ用粉体と、
    　オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
    　酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
    を含有する、印刷インキ組成物。     Printing ink powder,
    An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a);
    Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2);
    A printing ink composition containing
  10. 　印刷インキ用粉体が着色剤である、請求項９記載の印刷インキ組成物。 The printing ink composition according to claim 9, wherein the printing ink powder is a colorant.
  11. 　印刷インキ用粉体１００質量部に対して、（ａ）を１質量部以上３０質量部以下含有する、請求項９又は１０記載の印刷インキ組成物。 The printing ink composition according to claim 9 or 10, wherein (a) is contained in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the printing ink powder.
  12. 　オレフィンと不飽和二塩基酸とを、酢酸エステル（ｂ１）と低級アルコール（ｂ２）とを含む反応溶媒中で反応させて共重合体を得る工程、及び
    　前記共重合体を、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンでアミド化して前記共重合体のアミド化物を得る工程、
    を有する、印刷インキ用分散剤組成物の製造方法。     A step of obtaining a copolymer by reacting an olefin and an unsaturated dibasic acid in a reaction solvent containing an acetate ester (b1) and a lower alcohol (b2), and the copolymer having 6 to 10 carbon atoms. A step of amidating with an amine having the following branched alkyl group to obtain an amidated product of the copolymer;
    A process for producing a dispersant composition for printing inks.
  13. 　前記共重合体のアミド化物を、下記式（１）のイミダゾリン化合物で中和する工程を有する、請求項１２記載の印刷インキ用分散剤組成物の製造方法。
    Figure JPOXMLDOC01-appb-C000002
     〔式中、Ｒ１は炭素数７以上２１以下の炭化水素基、Ｒ２は炭素数１以上５以下の２価の炭化水素基である。〕     The manufacturing method of the dispersing agent composition for printing inks of Claim 12 which has the process of neutralizing the amidation thing of the said copolymer with the imidazoline compound of following formula (1).
    Figure JPOXMLDOC01-appb-C000002
     [Wherein, R 1 is a hydrocarbon group having 7 to 21 carbon atoms, and R 2 is a divalent hydrocarbon group having 1 to 5 carbon atoms. ]
  14. 　オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）とを含有する組成物の、印刷インキ用分散剤としての使用。 An amidated product of an olefin / unsaturated dibasic acid copolymer with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a), an acetate ester (b1) and a lower alcohol (b2) And a composition containing a mixed organic solvent (b) as a dispersant for printing ink.
  15. 　印刷インキ用粉体と、
    　オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
    　酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
    を含有する組成物の、印刷インキとしての使用。     Printing ink powder,
    An amidated product of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt thereof (a);
    Mixed organic solvent (b) of acetate (b1) and lower alcohol (b2);
    Use of a composition containing as a printing ink.
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