JP2020094136A - Active energy ray-curable offset ink, and printed matter - Google Patents

Abstract

To provide an active energy ray-curable offset ink which has rule crack resistance, scratch resistance and glossiness while using a plant-derived raw material.SOLUTION: An active energy ray-curable offset ink contains a (meth)acrylate monomer (A), a vegetable oil-modified (meth)acrylate (B), a wax (C), a photopolymerization initiator (D) and a binder resin (E).SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable offset ink using a plant-derived material, and a printed matter using the ink.

UV curable offset inks that cure with active energy rays are widely used in various fields such as book printing, art printing, sticker/label printing, business form printing, and package printing because of their instant curing characteristics.
In recent years, as the demand for environment-friendly products for the purpose of countermeasures against global warming and reduction of environmental load is increasing, plant-derived raw materials have been attracting attention as a means for reducing carbon dioxide emissions also in the field of offset ink. However, there are problems such as poor curing and poor gloss.

On the other hand, package printed matter requires the crease resistance of the printing ink coating film.
Ruled line cracking is a phenomenon in which, when a printed matter is assembled, the coating film is broken at the folds and the base material is exposed. The crease resistance correlates with the flexibility of the ink coating film, and if the flexibility is increased too much, curing failure tends to occur, and on the contrary, if the curing ability is increased too much, the flexibility tends to be impaired.
For example, an invention relating to a photocurable resin composition containing a dimethallyl phthalate-containing prepolymer using various ultraviolet curable monomers and epoxidized soybean oil acrylate has been made (for example, Patent Document 1).
Further, an invention relating to an active energy ray-curable ink composition using an acrylate monomer and a vegetable oil-modified (meth)acrylate has been made (for example, Patent Document 2).
However, these inventions cannot be said to have overcome the above problems, and the present invention maintains curability and flexibility while maintaining the basic performance required for active energy ray-curable offset inks such as scratch resistance and gloss. The present invention provides an active energy ray-curable offset ink characterized in that it also maintains resistance to creases by delicately controlling.

Patent 4134813 Patent 6237410

An object of the present invention is to provide an active energy ray-curable offset ink having both crack resistance, scratch resistance, and gloss while using a plant-derived raw material. Further, it is to provide a printed matter using the ink.

The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, contain a (meth)acrylate monomer, a vegetable oil-modified (meth)acrylate, a wax, a photopolymerization initiator, and a binder resin to prevent crease resistance. It was found that an active energy ray-curable offset ink having both properties, scratch resistance and gloss can be obtained, and the present invention has been completed.

That is, the present invention is characterized by containing a (meth)acrylate monomer (A), a vegetable oil modified (meth)acrylate (B), a wax (C), a photopolymerization initiator (D), and a binder resin (E). And an active energy ray-curable offset ink.

Further, in the present invention, the vegetable oil-modified (meth)acrylate (B) is an epoxidized soybean oil-modified acrylate, and the addition amount of the epoxidized soybean oil-modified acrylate is 5 to 25% by mass of the total amount of the ink. The present invention relates to a line curable offset ink.

Furthermore, the present invention provides that the (meth)acrylate monomer (A) comprises a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ditrimethylolpropane propane tetraacrylate, and trimethylolpropane ethene oxide modified triacrylate. The present invention relates to an active energy ray-curable offset ink in which one or more selected and the total amount of these added are 5 to 50 mass% of the total amount of the ink.

Furthermore, in the present invention, the wax (C) is any one selected from the group consisting of polyethylene wax, ethylene-propylene copolymer wax, tetrafluoroethylene resin wax, Fischer-Tropsch wax, and microcrystalline wax. The above is related to the active energy ray-curable offset ink in which the total amount of these waxes (C) added is 0.1 to 5 mass% of the total amount of the ink.

Further, in the present invention, the binder resin (E) is a diallyl orthophthalate polymer and/or a diallyl isophthalate polymer, and the total amount of the binder resin (E) is 5 to 25 mass% of the total amount of the ink. A curable offset ink.

Furthermore, the present invention relates to a printed matter having a cured product of the active energy ray-curable offset ink on a substrate.

By using the active energy ray-curable offset ink of the present invention, it is possible to provide an active energy ray-curable offset ink having both cracking resistance, scratch resistance, and gloss while using a plant-derived raw material. Furthermore, it is possible to provide a printed matter using the ink.

The active energy ray-curable offset ink of the present invention comprises a (meth)acrylate monomer (A), a vegetable oil-modified (meth)acrylate (B), a wax (C), a photopolymerization initiator (D), and a binder resin (E). By containing), the intended effect of the present invention is achieved.

The (meth)acrylate monomer (A) used in the active energy ray-curable offset ink of the present invention will be described. In the present invention, “(meth)acrylate” means one or both of acrylate and methacrylate, and “(meth)acrylic compound” means one or both of acrylic compound and methacrylic compound.
Examples of the (meth)acrylate monomer (A) include monofunctional (meth)acrylate, polyfunctional (meth)acrylate, and polymerizable oligomer.

Examples of monofunctional (meth)acrylates include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and hexadecyl. (Meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (Meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate and the like can be mentioned.

Examples of the bifunctional or higher functional (meth)acrylate include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. ) Acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclo Decanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate Di(meth)acrylate of dihydric alcohol such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, neopentyl glycol 1 mol Di(meth)acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide, di(meth)acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, tri Trivalent or higher polyvalent poly(meth)acrylates such as methylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol poly(meth)acrylate. Poly(meth)acrylate of alcohol, tri(meth)acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of glycerin, and 3 mol or more of ethylene oxide or propylene oxide per 1 mol of trimethylolpropane. Of polyoxyalkylene polyol such as di- or tri-(meth)acrylate of triol obtained by adding bisphenol A and di-(meth)acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A. (Meth)acrylate etc. are mentioned.

As the polymerizable oligomer, amine-modified polyether acrylate, amine-modified epoxy acrylate, amine-modified aliphatic acrylate, amine-modified polyester acrylate, amine-modified acrylate such as amino (meth)acrylate, polyester (meth)acrylate, polyether (meth) Examples thereof include acrylate, polyolefin (meth)acrylate, polystyrene (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate and the like.

Among them, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, which are difunctional or higher functional (meth)acrylates (sometimes abbreviated as DPHA), ditrimethylolpropane tetraacrylate (sometimes abbreviated as DTMPTA), tri The trimethylolpropane ethylene oxide adduct tri(meth)acrylate, which is a tri(meth)acrylate of triol obtained by adding 3 mol or more of ethylene oxide to 1 mol of methylolpropane, while maintaining good scratch resistance, said vegetable oil The combination with the modified (meth)acrylate (B) is more preferable in that "crease resistance" can be suppressed. Typical examples of the trimethylolpropane ethylene oxide adduct tri(meth)acrylate include trimethylolpropane ethylene oxide (EO) modified (n≈3) triacrylate.
Any one or more selected from the group consisting of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA), ditrimethylolpropane tetraacrylate (DTMPTA), and trimethylolpropane ethylene oxide modified triacrylate described above. The total amount of the (meth)acrylate monomer (A) is preferably in the range of 5 to 50% by mass of the total amount of the ink, more preferably 10 to 45% by mass, and further preferably 30 to 45% by mass.

In the present invention, the use of vegetable oil-modified (meth)acrylate (B) using a plant-derived raw material in the active energy ray-curable offset ink of the present invention brings about effects such as reduction of carbon dioxide emission.
In the present invention, the acrylate monomer that is the vegetable oil-modified (meth)acrylate (B) and is also the acrylate monomer (A) means that the acrylate monomer (B) is not the vegetable oil-modified (meth)acrylate (A). Yes).

Among the vegetable oil-modified (meth)acrylates (B), epoxidized vegetable oil-modified acrylates are preferable.

Examples of the epoxidized vegetable oil, which is a reaction raw material of the epoxidized vegetable oil-modified acrylate, include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized castor oil, epoxidized palm oil, epoxidized cottonseed oil, and epoxidized camellia oil. , Epoxidized olive oil, epoxidized corn oil, epoxidized coconut oil, and epoxidized safflower oil. These can be used alone or in combination of two or more.
Among these epoxidized vegetable oils, those selected from epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, and epoxidized castor oil are preferable, and epoxidized soybean oil is particularly preferable.
Specific examples of the epoxidized soybean oil include PHOTOMER3005 (manufactured by IGM Resins BV), EB860, EB5848 (manufactured by Daicel Ornex Co., Ltd.), MIRAMER PE3130 (manufactured by MIWON), and LAROMER EA9101 (BASF). Manufactured by K.K.), CN111 (manufactured by SARTOMER), etc., and these may be used alone, or may be used in combination of two or more kinds as appropriate.

As a result, the epoxidized soybean oil-modified acrylate having excellent flexibility, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate having poor flexibility (DPHA), ditrimethylolpropane tetraacrylate (DTMPTA), trimethylolpropane ethylene oxide. By using the modified triacrylate and the like in an appropriate amount range, it is possible to balance the film strength and flexibility of the ink coating film, and to maintain the crease resistance and scratch resistance.

In the active energy ray-curable offset ink of the present invention, scratch resistance can be maintained by adding the wax (C) even if the cured film has a slightly insufficient film strength. Examples of the wax (C) include waxes such as polyolefin wax, paraffin wax, Fischer-Tropsch wax, carnauba wax, beeswax, microcrystalline wax, polyethylene oxide wax, amide wax, coconut oil fatty acid and soybean oil fatty acid. it can.
Among them, polyolefin wax, Fischer-Tropsch wax, and microcrystalline wax are preferable, and specific examples of the polyolefin wax include polyethylene wax (SHAMROCK TECNOLOGIE, S-394-N1 etc.) and ethylene-propylene copolymer wax (SHAMLOCK TECNOLOGIE. , S-381-N1, etc.), tetrafluoroethylene resin wax (KTL-4N, etc., manufactured by Kitamura Co., Ltd.), and specific examples of Fischer-Tropsch wax include SASOL WAX SPRAY 30, microsold by SASOL. Specific examples of the crystallin wax include LUVAX-2191 manufactured by Nippon Seiro Co., Ltd., which is preferable.
The polyethylene wax, the ethylene-propylene copolymer wax, the tetrafluoroethylene resin wax, the Fischer-Tropsch wax, and the microcrystalline wax may be used alone or in combination.
The total amount of these waxes added is preferably 0.1 to 5% by mass of the total amount of ink, and if 0.1% by mass or more, scratch resistance tends to be retained, and if 5% by mass or less, glossiness is obtained. Tends to be retained.

The active energy ray-curable offset ink of the present invention can be formed into a cured coating film by printing on a substrate and then irradiating with active energy rays.
The active energy rays are ultraviolet rays, electron rays, α rays, β rays, and ionizing radiation such as γ rays, but specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, Ultraviolet light emitting diode (UV-LED), carbon arc, xenon lamp, high pressure mercury lamp for copying, medium or high pressure mercury lamp, ultra high pressure mercury lamp, electrodeless lamp, metal halide lamp, ultraviolet light using natural light etc., or scanning type, curtain Examples of the electron beam include electron beam accelerators of the type:

When ultraviolet rays are used as the active energy rays, examples of the photopolymerization initiator (D) to be added include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators.
Examples of the intramolecular cleavage type photopolymerization initiator include acetophenone compounds of diethoxyacetophenone; 1-[4-(phenylthio)-,2-(O-benzoyloxime)], 1-[9-ethyl-6. Oxime-based compounds such as -(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 3,6-bis(2-methyl-2-morpholinopropanonyl)- Carbazole compounds such as 9-butylcarbazole, benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2 -(Dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-methyl-2-morpholino((4-methylthio)phenyl)propan-1-one , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone and other aminoalkylphenones Compounds: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl -Acylphosphine oxide compounds such as pentylphosphine oxide; benzyl, methylphenylglyoxy ester and the like.

Further, as the hydrogen abstraction type photopolymerization initiator, a photopolymerization initiator such as a benzophenone compound, a thioxanthone compound, an aminobenzophenone compound may be used. These photopolymerization initiators can be used alone or in combination of two or more kinds.

The total content of the photopolymerization initiator (D) is preferably in the range of 3 to 20% by mass with respect to the total amount of the ink. If it is 3% by mass or more, sufficient curability can be obtained, and if it is 20% by mass or less, it is possible to suppress dissolution in the (meth)acrylate monomer and impair the fluidity.

Examples of the binder resin (E) used in the active energy ray-curable offset ink of the present invention include polyurethane resin, amino resin, phenol resin, polyamide, cellulose derivative, fluororesin, diallyl phthalate resin, vinyl resin, polyolefin and natural rubber. Examples include derivatives, acrylic resins, ketone aldehyde condensation resins, epoxy resins, polyesters, polystyrenes, alkyd resins, rosin-modified alkyd resins, and linseed oil-modified alkyd resins. May be.
Among them, diallyl phthalate resin is preferable, and it is particularly useful for imparting emulsification resistance and printability in long run.
Examples of the diallyl phthalate resin include diallyl orthophthalate (manufactured by Daiso Doap A Daiso) and diallyl isophthalate (manufactured by Daiso Isodap Daiso).
In the active energy ray-curable offset ink of the present invention, the content of the diallyl phthalate resin is preferably 5 to 25% by mass, more preferably 5 to 20% by mass of the total amount of the ink.
When the content of the diallyl phthalate resin is 5% by mass or more, sufficient ink viscosity can be obtained, and problems such as dot gain and stains on printing tend to be suppressed. On the other hand, when the content of the diallyl phthalate resin is 25% by mass or less, sufficient printability can be imparted without significantly impairing the fluidity of the ink.

The active energy ray-curable offset ink of the present invention may further contain a photosensitizer, an antioxidant, a polymerization inhibitor, a silicon-based additive, a pigment, a dye and the like, if necessary.

As the pigment, a known and commonly used inorganic pigment or organic pigment can be used.

Examples of the inorganic pigment include iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method.
For example, Raven 14, Raven 450, Raven 860 Ultra, Raven 1035, Raven 1040, Raven 1060 Ultra, Raven 1080 Ultra, Raven 1180, Raven 1255 (above, manufactured by BIRLA ARBON), Regal 250R, Regal 400R, Regal 330R, Regal 660R, Mogul. L (above, manufactured by Cabot Corporation), MA7, MA8, MA11 (above, manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be used, and these may be used alone or in appropriate combination of two or more kinds. Good.

As the organic pigment, for example, quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ansanthuron pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, Examples thereof include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These pigments can be used alone or in combination of two or more kinds.

Specific examples of the pigment used in the yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.

Further, specific examples of pigments used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, 269, etc. C. I. Pigment Violet 19 and the like.

In addition, specific examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15, 15:3, 15:4, 16, 22, 60, 63, 66 and the like.

The printing base material used in the active energy ray-curable offset ink of the present invention is not particularly limited, and examples thereof include catalogs, posters, leaflets, CD jackets, direct mail, pamphlets, cosmetics and beverages, pharmaceuticals, toys, devices, etc. It can be used for high-quality paper, coated paper, art paper, imitation paper, paper such as thin paper and cardboard, and various synthetic papers used for printing packages and the like.
Polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, There is no particular problem with films or sheets such as polycarbonate, cellophane, aluminum foil, and other various substrates conventionally used as printing substrates.
Moreover, you may use it for other base materials, such as a metal base material, a glass base material, a paper base material, a wood base material, and a fibrous base material.

The production of the active energy ray-curable offset ink described in the present invention is similar to the conventional active energy ray-curable offset ink, the extender pigment, (meth)acrylate monomer, vegetable oil modified (meth)acrylate, binder resin, wax, It is produced by mixing a photopolymerization initiator, a pigment, other additives and the like with stirring and mixing with a mixer or the like, and kneading with a dispersing machine such as a three-roll mill or a bead mill.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following examples, "parts" means "parts by mass" and "%" means "% by mass".

In this example, the weight average molecular weight (Mw) is a value measured using a gel permeation chromatograph (GPC) under the following conditions.

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Tosoh Corp. Guard Column H _XL- H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector; RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Solvent tetrahydrofuran
Flow rate 1.0 ml/min Standard; polystyrene sample; 0.4% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)

(Example 1: Preparation of active energy ray-curable offset black ink (1))
55 parts of Aronix M-400 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, manufactured by Toagosei Co., Ltd.) as an acrylate monomer, and PHOTOMER3005 (IGM Resins) which is an epoxidized soybean oil modified acrylate as a vegetable oil acrylate. B.V.) 5 parts,
10 parts of Daiso Dup A (manufactured by Daiso Co.) which is a diallyl isophthalate resin as a binder resin, 2 parts of S-381-N1 (manufactured by SHAMROCK TECHNOLOGIE) as an ethylene-propylene copolymer wax, and .alpha.- as a photopolymerization initiator. Aminoalkylphenone-based photopolymerization initiator Omnirad 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, number average molecular weight 279.4, IGM Resins BV Company. 8 parts by mass, 5 parts by weight of 4,4′-bisdimethylaminobenzophenone (“EAB-SS” manufactured by Daido Kasei Kogyo Co., Ltd.), which is an alkylaminobenzophenone compound, are mixed at 60° C. for 3 hours, and then carbon black. After adding 15 parts of Raven 1060 powder (manufactured by BIRLA CARBON) and stirring with a mixer (single-screw dissolver), the mixture was kneaded using a three-roll mill and the active energy ray-curable offset black ink (1 ) Got.

(Examples 2 to 23: Preparation of active energy ray-curable offset black inks (2) to (23))
Active energy ray-curable offset black inks (2) to (23) were obtained in the same procedure as in Example 1 except that the compositions and blending amounts shown in Tables 1 to 3 were changed.

(Comparative Examples 1 to 4: Preparation of active energy ray curable offset black inks (H1) to (H4))
Active energy ray-curable offset black inks (H1) to (H4) were obtained in the same procedure as in Example 1 except that the compositions and blending amounts shown in Table 4 were changed.

The following evaluations were carried out using the active energy ray-curable offset black inks obtained in the above Examples and Comparative Examples.

[Evaluation item 1: Scratch resistance]
The active energy ray-curable offset black ink that was created was uniformly spread on a rubber roll and a metal roll of the RI tester using a simple color spreader (RI tester, Hoei Seiko Co., Ltd.) and 0.10 ml of ink. Color is spread evenly on the surface of cardboard (UF coat manufactured by UF Materia Co., Ltd., tsubo 350g/m ² ) at a black density of 1.8 (measured by X-Rite “SpectroEye” densitometer). Then, a printed matter was produced.
The printed matter obtained by the above method was irradiated with ultraviolet rays (UV) to cure the ink film. A water-cooled UV-LED (center emission wavelength 385 nm±5 nm UV-LED output 50%) and a UV irradiation device (manufactured by Eye Graphics Co.) equipped with a belt conveyor were used, the printed matter was placed on the conveyor, and directly below the LED (irradiation). The distance of 9 cm) was passed at 150 m/min. Immediately after curing, the cured coating film of each cured product was rubbed with a nail to visually evaluate the scratch resistance in the following five stages.
(Evaluation criteria)
5: No scratches were generated by nail scratches, and the curability was the best.
4: A slight scratch is slightly seen by scratching the nail.
3: There are scratches on the scratches, but it is at a usable level.
2: Claw scratches were generated, and it cannot be said that the curability is sufficient.
1: Scratch easily occurs with nail scratches, and the curability is the worst.

[Evaluation item 2: Crease resistance]
A cured coating immediately after UV irradiation of a printed matter on which an active energy ray-curable offset black ink was spread was bent at an angle of 180° in the opposite direction to the printed surface by the same procedure as the scratch resistance evaluation test. The state of the surface was visually confirmed and visually evaluated according to the following 5 grades.
(Evaluation criteria)
5: No cracks occur.
4: The raw material of the base is exposed in an area range of less than 1 to 25% of the entire bent portion.
3: The exposure of the base material can be seen in the area range of 25% or more and less than 50% of the entire bent portion, but it is at a usable level.
2: The base material is exposed in an area range of 50% or more and less than 75% of the entire bent portion.
1: The bent portion is entirely whitened.

[Evaluation item 3: gloss]
UV irradiation of the printed product with active energy ray-curable offset black ink applied, and the gloss value of the printed surface after curing is measured with a 60° gloss meter (manufactured by BYK Garder GmbH) in the same procedure as the scratch resistance evaluation test. Then, the evaluation was made according to the following 5 grades. The higher the value, the better the gloss.
(Evaluation criteria)
5: The gloss value is 75 or more.
4: Gloss value is 60 or more and less than 75.
3: The gloss value is 50 or more and less than 60, which is a usable level.
2: The gloss value is 40 or more and less than 50.
1: The gloss value is less than 40.

The respective evaluation results of the active energy ray-curable offset black ink are shown below.

表１〜４の数値は質量％である。各表に示す諸原料及び略語を以下に示す。
・アロニックスＭ−４００：ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合物 （ＤＰＨＡ）、東亜合成（株）社製
・アロニックスＭ−４０８：ジトリメチロールプロパンテトラアクリレート（ＤＴＭＰＴＡ）、東亜合成（株）社製
・アロニックスＭ−３５０：トリメチロールプロパンエチレンオキサイド変性トリアクリレート、東亜合成（株）社製
・ＰＨＯＴＯＭＥＲ３００５：エポキシ化大豆油変性アクリレート、ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製
・ダイソーダップＡ：ジアリルオルトフタレート樹脂、平均重量分子量５．５万、（株）大阪ソーダ社製
・ダイソーイソダップ：ジアリルイソフタレート樹脂、平均重量分子量５万、（株）大阪ソーダ社製
・ラーベン１０６０パウダー：カーボンブラック、ＢＩＲＬＡ ＣＡＲＢＯＮ社製
・Ｓ−３８１−Ｎ１：エチレン−プロピレン共重合体ワックス、ＳＨＡＭＲＯＣＫ ＴＥＣＮＯＬＯＧＩＥ社製
・Ｓ−３９４−Ｎ１：ポリエチレンワックス、ＳＨＡＭＲＯＣＫ ＴＥＣＮＯＬＯＧＩＥ社製
・ＫＴＬ−４Ｎ：４フッ化エチレン樹脂ワックス、（株）喜多村社製
・ＳＡＳＯＬ ＷＡＸ ＳＰＲＡＹ ３０：フィッシャー・トロプシュワックス、ＳＡＳＯＬ社製
・ＬＵＶＡＸ−２１９１：マイクロクリスタリンワックス、日本精蝋（株）社製
・Ｏｍｎｉｒａｄ ９０７：α−アミノアルキルフェノン系光重合開始剤、２−メチル−１−[４−（メチルチオ）フェニル]−２−モルフォリノプロパン−１−オン、ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製
・ＥＡＢ−ＳＳ：４，４’−ビス−（ジエチルアミノ）ベンゾフェノン、大同化成（株）社製

The numerical values in Tables 1 to 4 are% by mass. The raw materials and abbreviations shown in each table are shown below.
-Aronix M-400: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA), manufactured by Toagosei Co., Ltd.-Aronix M-408: ditrimethylolpropane tetraacrylate (DTMPTA), Toagosei Co., Ltd. Aronix M-350: trimethylolpropane ethylene oxide modified triacrylate, manufactured by Toagosei Co., Ltd. PHOTOMER3005: epoxidized soybean oil modified acrylate, IGM Resins B.A. V. Manufactured by Daiso Dup-A: diallyl orthophthalate resin, average weight molecular weight 55,000, manufactured by Osaka Soda Co., Ltd.-Daiso Isodap: diallyl isophthalate resin, average weight molecular weight 50,000, manufactured by Osaka Soda Co., Ltd. -Raven 1060 powder: carbon black, manufactured by BIRLA CARBON-S-381-N1: ethylene-propylene copolymer wax, manufactured by SHAMROCK TECNOLOGIE-S-394-N1: polyethylene wax, manufactured by SHAMROCK TECNOLOGIE-KTL-4N: Polytetrafluoroethylene wax, manufactured by Kitamura Co., Ltd.-SASOL WAX SPRAY 30: Fischer-Tropsch wax, manufactured by SASOL-LUVAX-2191: Microcrystalline wax, manufactured by Nippon Seiro Co., Ltd.- Omnirad 907: α- Aminoalkylphenone-based photopolymerization initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, IGM Resins B.A. V. Manufactured by EAB-SS: 4,4′-bis-(diethylamino)benzophenone, manufactured by Daido Kasei Co., Ltd.

The active energy ray-curable offset ink of the present invention has a result of having both crack resistance, scratch resistance, and gloss while using a plant-derived raw material.

The active energy ray offset ink of the present invention and printed matter printed using the ink are used for paper container packaging such as food, beverage, sanitary, cosmetics, toys, equipment, pharmaceuticals, and books, leaflets, posters, catalogs, cards. -Widely applicable to commercial printing applications such as direct mail, pamphlets, CD jackets, sticker labels, etc.

Claims (6)

Active energy ray curable type containing (meth)acrylate monomer (A), vegetable oil modified (meth)acrylate (B), wax (C), photopolymerization initiator (D) and binder resin (E) Offset ink.
The active energy according to claim 1, wherein the vegetable oil-modified (meth)acrylate (B) is an epoxidized soybean oil-modified acrylate, and the addition amount of the epoxidized soybean oil-modified acrylate is 5 to 25% by mass of the total amount of the ink. Line hardening type offset ink.
The (meth)acrylate monomer (A) is any one selected from the group consisting of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate, and trimethylolpropane ethylene oxide modified triacrylate. It is above, and the total amount of these addition amounts is 5 to 50 mass% of the total amount of the ink, The active energy ray-curable offset ink according to claim 1.
The wax (C) is any one or more selected from the group consisting of polyethylene wax, ethylene-propylene copolymer wax, tetrafluoroethylene resin wax, Fischer-Tropsch wax, and microcrystalline wax, and these waxes The active energy ray-curable offset ink according to any one of claims 1 to 3, wherein the total amount of the ink added is 0.1 to 5 mass% of the total amount of the ink.
The activity according to claims 1 to 4, wherein the binder resin (E) is a diallyl orthophthalate resin and/or a diallyl isophthalate resin, and the total amount of the binder resin (E) is 5 to 25 mass% of the total amount of the ink. Energy ray curable offset ink.
A printed matter comprising a cured product of the active energy ray-curable offset ink according to claim 1 on a substrate.