JPH066687B2 - Method for producing active energy ray-curable printing ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Object of the Invention" (Field of Industrial Application) The present invention relates to an active energy ray-curable printing ink and a method for producing the same, and more specifically, it is cured by irradiation with ultraviolet rays or electron beams. Moreover, the present invention relates to an active energy ray-curable printing ink having excellent printability.

(Prior Art) In recent years, a curable printing ink using active energy rays has been extensively researched and put into practical use. These consist of compounds having radical-polymerizable double bonds (monomers and prepolymers) and, if necessary, radical polymerization initiators, pigments, etc. As prepolymers, alkyd acrylate, polyester acrylate, epoxy acrylate, urethane modified Acrylate and the like, and as the monomer, bisphenol A alkylene oxide adduct diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate, alkylphenol alkylene oxide adduct monoacrylate, etc. Was used.

However, when these inks are used in printing inks such as offset inks, the emulsification flow during emulsification is poorer than that of oil-based inks (oxidation polymerization type inks), the ink viscosity is low, and stains and halftone dots are reproduced during printing. There was a tendency for deterioration of sex to occur. In order to solve the above problems, oil-based inks are generally called gelling agents and metal soap and aluminum alcoholate are added to an oil-based vehicle (oxidation polymerization type) in an amount of 0.1 to 0.1%.
5 wt% was added and the reaction was carried out at 15 to 250 ° C. However, when these are used in an active energy ray-curable printing ink and reacted at 120 ° C. or higher, thermal polymerization is generally easy. Also, the effect is small even if the reaction is carried out at 120 ° C or lower.
Therefore, the actual situation is that the active energy ray-curable printing ink is not necessarily satisfactory in terms of emulsion fluidity and ink viscosity.

“Structure of the Invention” (Means for Solving Problems) The present invention has been conducted as a result of earnest research to improve these drawbacks.
In order to solve the above problems, the inventors have invented an active energy ray-curable printing ink and a method for producing the same.

That is, in the present invention, 0.1 to 5% by weight of metal soap or aluminum alcoholate is added to a mixture of a non-radical-reactive resin that is solid at room temperature and is selected from alkyd resins and eponester resins and dissolved in a monomer.
After heating to 0 to 120 ° C., 0.1 to 3 wt% of organic titanate or organic zirconate is added to the total amount of the ink, and a monomer or radical polymerization initiator is added if necessary, active energy. The present invention relates to a method for producing a line curable printing ink.

In the present invention, the metal soap is a long-chain fatty acid salt of a non-alkali metal, and the metal includes aluminum, calcium, magnesium, barium, lithium, zinc, etc., but aluminum is often used. For example, metal soaps include aluminum (mono, di, or tri) octate, aluminum (mono, di, or tri) stearate, calcium dioctate, calcium distearate, lead stearate, zinc distearate, magnesium distearate. Rate, barium stearate, lithium stearate, aluminum oxide octate shown in the following (1), aluminum oxide stearate shown in the following (2), and the like.

Examples of the aluminum alcoholate include (a) ethyl acetoacetate aluminum diisopropylate, (b)
Monobutoxy aluminum diisopropylate, (C)
Euleracetoacetate aluminum diisopropylate, (d) Cyclic aluminum oxide isopropylate, (e) Aluminum trisacetylacetonate, (f) Aluminum-mono-acetylacetonate bis (ethylacetoacetonate) isopropanol,
Examples include (to) aluminum dibutoxyside monoethyl acetoacetate and (h) aluminum diisopropoxide monoethyl acetate.

The room-temperature solid non-radical-reactive alkyd resin of the present invention is obtained by reacting a polyol with a monobasic acid at 180 to 260 ° C., and then performing a crosslinking reaction with a polycarboxylic acid.

The polyol compound is a compound having two or more hydroxyl groups, such as ethylene glycol,
Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, pentyl glycol, neopentyl glycol, hexanediol,
Glycerin, diglycerin, trimethylolpropane,
Ditrimethylolpropane, trimethylolethane, ditrimethylolethane, tetramethylolmethane, dipentaerythritol, polycyclopentadiene diallyl alcohol copolymer, spiroglycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct , Bisphenol F propylene oxide adduct (the number of moles of alkylene oxide added is usually 1 to 2 mol per 1 hydroxyl group of bisphenol), water-added bisphenol A, water-added bisphenol F, and the like.

Examples of the monovalent carboxylic acid having no radical polymerizable double bond include formic acid, acetic acid, propionic acid, butyric acid, valerianic acid, trimethylacetic acid, caproic acid, n-heptanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, coconut oil. Aliphatic carboxylic acids such as fatty acids, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, phenylacetic acid, halogenated benzoic acid, anisic acid, benzoylbenzoic acid, There are aromatic carboxylic acids such as naphthoic acid, rosin, and water-added rosin. Further, there is an esterified product of the above-mentioned divalent carboxylic acid and an esterified product in which a monohydric alcohol or one alcoholic hydroxyl group remains.

As the monohydric alcohol, methyl alcohol, ethyl alcohol, propyl alcohol, allyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, capryl alcohol,
Decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and other aliphatic alcohols, benzyl alcohol, phenol, alkylphenol alkylene oxide adducts, and other aromatic alcohols, cyclohexanol, rosin alcohol, water-added rosin alcohol, etc. Can be mentioned. The esterified product having one alcoholic hydroxyl group left is the esterified product with the monovalent carboxylic acid described above.

Further, polyvalent carboxylic acid, that is, an organic compound having two or more carboxyl groups means oxalic acid, malonic acid, succinic acid, alkylsuccinic acid, glutaric acid, maleic acid or their acid anhydrides, fumaric acid, adipic acid. , Pimelic acid, suberic acid, azelaic acid, sebacic acid, OSK-
DASL-12, OSK-DASL-20, OSK-D
ASB-12, OSK-DASB-20, OSK-DA
UL-20, OSK-DAUB-20 (OSK series is a long-chain dibasic acid of Okamura Oil Co., Ltd.), fatty acid dicarboxylic acids such as linseed oil fatty acid and tung oil fatty acid, and dimer acid, o
-Phthalic acid, non-added o-phthalic acid, hymic acid, methylhymic acid, diphenic acid, trimellitic acid, pyromellitic acid, naphthalic acid, benzophenonetetracarboxylic acid and their acid anhydrides, isophthalic acid, terephthalic acid, Hemimellitic acid, trimesic acid, prenitic acid, melophanoic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, homophthalic acid, o. m. Examples thereof include aromatic polycarboxylic acids such as p-phenylenediacetic acid and o-phenyleneacetic acid-β-propionic acid, and dimer acid of rosin.

The room temperature solid non-radical reactive eponester resin of the present invention is obtained by reacting an epoxy compound and a monobasic acid at 180 to 260 ° C. in the presence of an amine catalyst. As the monobasic acid, a fatty acid having 6 or more carbon atoms is preferable.

The epoxy compound is a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a linear aliphatic epoxy resin, an alicyclic epoxy resin or the like having one or more epoxy groups in one molecule.

Examples of the glycidyl ether type epoxy resin include bisphenol A diglycidyl ether and bisphenol A di-
β-methyl glycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether and glycidyl ether obtained by adding them, and glycidyl ε-caprolactone compound of the glycidyl ether compound, and alkylene oxide adduct of bisphenol A, S or F Examples include ethers, (alkyl) phenol novolac glycidyl ethers, glycol polyglycidyl ethers of polyalkylenes, and epoxy urethane resins. As the glycidyl ester type epoxy resin, there are dibasic acid diglycidyl ester such as phthalic acid, adipic acid and dimer acid, and tribasic acid triglycidyl ester such as trimellitic acid. Further, examples of the glycidyl amine type epoxy resin include triglycidyl isocyanate. Examples of linear aliphatic epoxy resins include epoxidized polybutadiene, epoxidized soybean oil, and epoxidized linseed oil, and examples of alicyclic epoxies include 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate, bis ( 3,4 epoxy, cyclohexyl) and the like.

Examples of the monomer in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl. (Meta)
Acrylate, capryl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth)
Monofunctional monomers such as acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate of alkylene oxide adduct of alkylphenol, and cyclohexyl (meth) acrylate can be mentioned. Furthermore, as a bifunctional or higher functional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Di (meta)
Acrylate, tripropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypiparyl hydroxypyvale Todi (meth) acrylate, hexanediol di (meth) acrylate, (di)
Glycerin tri (meth) acrylate, diglycerine alkylene oxide tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane alkylene oxide tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate
Acrylate, ditrimethylol propane alkylene oxide tetra (meth) acrylate, trimethylol ethane tri (meth) acrylate, ditrimethylol ethane tri (meth) acrylate, trimethylol ethane alkylene oxide tri (meth) acrylate, ditrimethylol ethane alkylene oxide tetro (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, dihydroxybenzene alkylene oxide di (meth) acrylate , Trihydroxybenzene alkylene oxide di (meth) acrylate, Bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth)
Examples thereof include acrylate, water-added bisphenol A alkylene oxide adduct di (meth) acrylate, and water-added bisphenol F alkylene oxide adduct di (meth) acrylate. Other examples include lactone adduct monomers. That is, polyethylene glycol polylactonate di (meth) acrylate, polypropylene glycol polylactonate di (meth) acrylate, alkylene glycol polylactonate di (meth) acrylate, glycerin polylactonate tri (meth) acrylate, diglycerin polylactonate Each polyol such as tetra (meth) acrylate, trimethylolpropane polylactonate tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol polylactonate tetra (meth) acrylate, dipentaerythritol polylactonate hexaacrylate Lactonate polyacrylate. The lactone of the above monomer is γ
-Butyrolactone A compound containing a functional group -CO-O- of an ester such as 8-valerolactone or ε-caprolactone in the ring.

The organic titanate is an alkoxy type, an acylate type or the like, and examples thereof include tetraisopropyl titanate, tetra n-butyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium lactate ethyl ester and the like. is there.

The organic zirconate is zirconium-tetrabutoxide, zirconium acetylacetone, ethyl zirconium acetoacetate, acetylacetone zirconium butoxide, ethyl acetoacetate zirconium butoxide and the like.

The reaction of the mixture of metal soap or aluminum alcoholate, the non-radical reactive resin and the monomer is 80 to 120 ° C.
Do it for 1-2 hours under blowing air. 0.1 to 5% by weight, preferably 0.5 to 3% by weight, of metal soap or aluminum alcoholate is used with respect to 100% by weight of the mixture of the non-radical-reactive resin and the monomer. Further, it is desirable to dissolve it in a solvent such as methyl ethyl ketone or toluene before adding.

In the use of the printing ink of the present invention, when the active energy ray is ultraviolet light, it is necessary to add a photosensitizer, that is, a radical polymerization initiator (also a radical polymerization accelerator), benzoin, benzoin methyl ether, Benzoin sensitizers such as benzoin ethyl ether, benzoin isopropyl ether, α-acrylbenzoin,
Benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, o-
Aryl ketone sensitizers such as methyl benzoylbenzoate and acetophenone, 4,4-bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate, p
Examples thereof include dialkylaminoarylketone sensitizers such as dimethylaminoacetophenone, and polycyclic carbonyl sensitizers such as thioxanthone, xanthone and halogen substitution products thereof, and these can be used alone or in an appropriate combination. These photosensitizers are incorporated in the composition in an amount of 1
Although it can be used in the range of ˜30 wt%, it is preferably in the range of 0 to 15 wt%.

The organic titanate and the organic zirconate are dispersed in the printing ink at room temperature or by heating at the time of making the ink by a conventional method such as a three-roll mill or a ball mill. The amount of addition of organic titanate and organic zirconium is 0.1% by weight (preferably 0.5% by weight) to about 100% by weight of the ink.
3% by weight is desirable. If it is less than 0.1% by weight, the effect is weak, and if it is more than 3% by weight, the storage stability of the printing ink is deteriorated.

The present invention will be described below with reference to production examples and examples. In the examples, “part” means part by weight.

[Example of prepolymer production]

Production Example 1 272 parts of pentaerythritol, coconut oil fatty acid 286
Parts, 915 parts of o-benzoylbenzoic acid, 267 parts of methylhymic acid anhydride, and 75 parts of xylol were charged into a 4-necked flask equipped with a stirrer, reacted at 200 ° C. under a nitrogen gas stream, and an acid value of 4 was reached in about 10 hours. Since it became less than 0.5, the solvent was removed and then cooled to 100 ° C., and 1 part of hydroquinone and trimethylolpropane triacrylate 70 under an air stream were used.
Add 0 parts and stir for about 30 minutes to dissolve. This is designated as prepolymer a.

Production Example 2 Epicoat 1004 (epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) 1600 parts, 840 parts oleic acid; Steberite (hydrogenated rosin manufactured by Rika Hercules Co., Ltd.) 660
Parts, triethylenediamine 3 parts, and xylol 150 parts were charged in a 4-necked flask equipped with a stirrer, and the mixture was stirred under a nitrogen stream for 150
After reacting at 1 ° C for 1 hour, the temperature was gradually raised and reacted at 260 ° C for 8 hours, the acid value became 5, so the solvent was removed, then cooled to 100 ° C, and 5 parts of hydroquinone while blowing air, 2000 parts of ABPE-4 (diacrylate of bisphenol A 4 mol ethylene oxide adduct) was charged and dissolved in 1 hour. This is prepolymer b
And

Example The prepolymer obtained in Production Example was placed in a 4-necked flask equipped with a stirrer, and the metal soap or aluminum alcoholate described in Table 1 below was blown with air at 100 ° C. As the solvent, and after the reaction, the mixture is reacted at 120 ° C. for 2 hours, and after desolvation,
Pumped out.

Metal soap B: Calcium distearate Metal soap B: Aluminum oxide octoate Aluminum alcoholate C: Ethyl acetate Aluminum diisopropylate Aluminum alcoholate Ni: Oleyl acetoacetate aluminum diisopropylate Aluminum alcoholate F: Aluminum trisacetylacetonate [Organic titanate, Addition of Organic Zirconate] After mixing the prepolymer, monomer, radical polymerization initiator, hydroquinone and pigment shown in Table-2, organic titanate or organic zirconate is added at room temperature on three rolls, immediately kneaded and dispersed. Let

Organic titanate α: Tetraisopropyl titanate Organic titanate β: Titanium acetylacetonate Organic zirconate γ: Zirconium tetrabutoxide Organic zirconate δ: Acetylacetone zirconium butoxide Monomer TMPTA: Trimethylolpropane triacrylate Monomer ABPE-4: Bisphenol A (4 mol) Ethyl Renoxide adduct diacrylate Radical initiator: 4,4-bis (diethylamino) zophenone / benzophenone = 2/5 Pigment: Fines red F2B: Toyo Ink Mfg. Co., Ltd. Red pigment Comparative Examples 1 to 4 shown in Table-2 For each of the samples of Examples 5 to 11, the tack value, the flow value before and after emulsification, the Δflow value, and the ink viscosity were measured and shown in Table 3.

Tack value: Water temperature 30 ° C, room temperature 25 ° C, measured by incometer
It was measured at a speed of 400 rpm.

Emulsification: Take about 20 g of ink in a small can, mix emulsified water (added water of 0.5% Max liquid (trade name of dampening water manufactured by Zoji Printing Co., Ltd.) in a saturated state, and mix it with a homomixer at about 1000 rpm at about 1000 rpm. Two
It was emulsified by rotating for a minute.

Flow value: The circular spread of the ink after 60 seconds was represented by the radius length with a parallel plate viscometer (measurement temperature 25 ° C.).

Viscosity: Measured at 25 ° C. with a cone and plate viscometer.

Comparative Examples 1-3 and Example 1 of the ink composition shown in Table-2
The samples of Nos. 5 to 5 were printed with KORD Heidenberg, and stains on non-image areas and halftone dot reproducibility during printing were measured.
It was shown to.

Halftone dot reproducibility: When printing is in a steady state on a printed material with solid and 50% halftone dots, adjust the solid density to a density value of 1.2 (measured with a reflection densitometer) and print 50% halftone dots. The density value of is measured and the ratio to the solid density is expressed as 5
A value close to 0% is good.

"Effect of the invention" The active energy ray-curable printing ink of the present invention has good fluidity after emulsification and high ink viscosity before and after emulsification as compared with conventionally known printing inks, and further has good printing effect. Have.

Claims (1)

[Claims] 1. A metal soap or aluminum alcoholate is added in an amount of 0.1 to 5% by weight to a mixture of a non-radical-reactive resin, which is solid at room temperature and is selected from alkyd resins and eponester resins, dissolved in a monomer.
After heating to 0 ° C., 0.1 to 3% by weight of organic titanate or organic zirconate is added to the total amount of the ink, and a monomer or a radical polymerization initiator is added if necessary, active energy ray curing. Method for producing printing ink.