JP2010229185A - Photo-curable ink composition, inkjet recording method, and recorded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-curable ink composition provided with sufficient curing sensitivity and excellent in a base material conforming property and rubbing-resistance. <P>SOLUTION: The photo-curable ink composition includes urethane (meth)acrylate, an alicyclic (meth)acrylate, a siloxane (meth)acrylate, a pigment, and a photo-polymerization initiator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photocurable ink, an ink jet recording method, and a recorded matter, and more specifically, a photocurable ink composition, an ink jet recording method having sufficient curing sensitivity and excellent substrate followability and abrasion resistance, and It relates to the recorded material.

  Conventionally, a photocurable ink composition capable of forming an excellent image cured by light irradiation has been proposed.

  In Patent Document 1, specified for the purpose of forming an image having high sensitivity to irradiation with actinic radiation and excellent curability, and that the image after curing has high adhesion to a recording medium. An ink composition for ink-jet recording containing the above compound and a radical polymerization initiator is disclosed.

  Patent Document 2 aims to form an image having high sensitivity to irradiation with actinic radiation and excellent curability, and that the image after curing has high adhesion to a recording medium. Ink jet recording ink compositions containing a heterocyclic compound containing two or more heteroatoms in the ring and substituted with a vinyl group and a radical polymerization initiator are disclosed.

JP 2008-189887 A JP 2008-195882 A

  However, in the conventionally proposed photo-curing type ink, the adhesiveness with the recording medium is reduced due to volume shrinkage at the time of curing. There were problems such as radicals generated from the agent being trapped and lowering the curing sensitivity.

An object of the present invention is to provide a photocurable ink composition having sufficient curing sensitivity and excellent in substrate followability and abrasion resistance.
Another object of the present invention is to provide an ink jet recording method capable of forming a recorded image excellent in substrate followability and abrasion resistance after curing, and a recorded matter containing the recorded image.

  In order to solve the above problems, the present inventors have conducted intensive studies, and at least, photocuring containing alicyclic (meth) acrylate, phenoxyethyl (meth) acrylate, and siloxane (meth) acrylate. We have found that the type of ink can achieve the above-mentioned purpose. This invention is made | formed based on this knowledge, and is shown below.

[1] A photocurable ink composition comprising urethane (meth) acrylate, alicyclic (meth) acrylate, siloxane (meth) acrylate, a pigment, and a photopolymerization initiator.

[2] The photocurable ink composition according to [1], containing 0.3 to 2.0% by mass of siloxane (meth) acrylate.

[3] The photocurable ink composition according to [1] or [2], further including phenoxyethyl (meth) acrylate.

[4] The photocurable ink composition according to any one of [1] to [3], further including an adhesion component that improves adhesion of the photocurable ink composition to a recording medium.

[5] The photocurable ink composition according to the above [4], wherein the adhesion component is N-hydroxyethyl (meth) acrylamide.

[6] An ink jet recording method comprising a step of discharging a droplet of the photocurable ink composition according to any one of the above [1] to [5] and attaching the droplet to a recording medium for recording.

[7] A recorded matter recorded by the inkjet recording method of [8] above.

  According to the present invention, it is possible to provide a photocurable ink composition having sufficient curing sensitivity and excellent in substrate followability and abrasion resistance. Moreover, according to the present invention, it is possible to provide an ink jet recording method capable of forming a recorded image having excellent substrate followability and abrasion resistance after curing, and a recorded matter including the recorded image.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. In the present specification, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto, and “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto.

The photocurable ink composition of this embodiment contains urethane (meth) acrylate, alicyclic (meth) acrylate, siloxane acrylate, a pigment, and a photopolymerization initiator. The photocurable ink composition of the present embodiment is provided with such a configuration, so that it has sufficient curing sensitivity and is excellent in substrate followability and abrasion resistance.
Here, sufficient curing sensitivity means complete curing with a predetermined light energy, and substrate follow-up property means that a coating film obtained by applying ink on a substrate and photocuring it was pulled together with the substrate. Sometimes, if the coating film cannot follow the substrate, cracks or peeling will occur, which is the difference in the state of occurrence. Abrasion resistance refers to the difficulty of scratching the coating film surface on the substrate.

The siloxane (meth) acrylate contained in the photocurable ink composition of the present embodiment has a function as a slip agent (leveling agent) having an action of reducing the coefficient of friction of the image after curing. Examples of the siloxane (meth) acrylate include polyether-modified (meth) acrylate and polyester-modified (meth) acrylate. Examples of the polyether group include a polyoxyethyl group and a polyoxypropylene group. Furthermore, examples of the alkyl group in the polymonoalkylsiloxane and polydialkylsiloxane include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Of these, polydialkylsiloxanes are preferred, polyether groups are preferred, polyether groups are preferably polyoxyethylene groups, and alkyl groups are preferably methyl groups.
Moreover, as a commercial item of siloxane (meth) acrylate, BYK-UV3500, BYK-UV3570 (above, BYK company make, brand name), EBECRYL350, 1360 (above, Daicel Cytec company make, brand name) are mentioned, for example. .

  A siloxane (meth) acrylate is used individually by 1 type or in combination of 2 or more types. Moreover, it is preferable that the photocurable ink composition of this embodiment contains siloxane acrylate from the viewpoint of increasing the curing speed during photocuring.

  The photocurable ink composition of the present embodiment preferably contains 0.3 to 2.0% by mass of siloxane (meth) acrylate, more preferably 0.35 to 1.5% by mass, based on the total amount. , 0.4 to 1.0% by mass is more preferable. When the content of siloxane (meth) acrylate is 0.3% by mass or more, the rub resistance effect can be exhibited more effectively and reliably, and when the content is 2.0% by mass or less, the adhesion to the substrate is further increased. Can be secured at a high level.

  The urethane (meth) acrylate contained in the photocurable ink composition of the present embodiment is a reactive oligomer having a urethane bond and a (meth) acryloyl group in its structure. Urethane acrylate is synthesized by forming a urethane compound having a urethane bond by addition reaction of diisocyanate and polyol, and further adding (meth) acrylate having an active hydrogen group such as a hydroxyl group to the remaining isocyanate group.

  Examples of the diisocyanate compound include methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid. Chain aliphatic diisocyanates such as dimerisocyanate, in which the carboxyl group of the compound is replaced by an isocyanate group; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-di (isocyanate methyl) Cycloaliphatic diisocyanates such as cyclohexane and methylcyclohexane diisocyanate; 4,4'-diphenyldimethylmethane Dialkyldiphenylmethane diisocyanate such as diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4′-diphenyltetramethylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, Aromatic diisocyanates such as 4,4′-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate; amino acid diisocyanates such as lysine diisocyanate Is mentioned. These diisocyanate compounds and other polyisocyanate compounds are used alone or in admixture of two or more.

  Examples of the polyol include polyester polyols such as pivalic acid neopentyl glycol ester and polycaprolactone polyol; polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol; polycarbonate polyols such as polyhexamethylene carbonate glycol; Ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, methylpentanediol, neopentylglycol, 3,3-dimethylolheptane, Alkanediol having 7 to 22 carbon atoms, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedi Tanol, alkane-1,2-diol having 17 to 20 carbon atoms, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A Glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) ) Propane, 2,2-bis (hydroxymethyl) -3-butanol, other aliphatic triols having 8 to 24 carbon atoms, tetramethylolmethane, D-sorbitol, xylitol, D-mannitol, D-mannitol It is done. Of these, polyester polyols and polyether polyols are preferred.

  Furthermore, examples of the (meth) acrylate having an active hydrogen group such as a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

The urethane (meth) acrylate is preferably bifunctional or more from the viewpoint of reactivity with other monomers and the flexibility and strength of the polymer, and in particular, bifunctional is preferred because of a good balance between flexibility and strength. . Moreover, it is preferable that molecular weight is 100-5,000, and it is more preferable that it is 400-2,000.
As urethane (meth) acrylate, commercially available products are EBECRYL8402 (viscosity: 12,500 mPa · s, bifunctional, molecular weight: 1000), and 9270 (viscosity: 7,500 mPa · s, bifunctional, molecular weight: 1,000). 4858 (viscosity: 7,000 mPa · s, bifunctional, molecular weight: 450) (manufactured by Daicel Cytec Co., Ltd.) and the like can be suitably used.

  Urethane (meth) acrylates are used singly or in combination of two or more. Moreover, it is preferable that the photocurable ink composition of this embodiment contains urethane acrylate from the viewpoint of increasing the curing speed during photocuring.

  The photocurable ink composition of the present embodiment preferably contains 0.1 to 30% by mass of urethane (meth) acrylate, more preferably 1 to 20% by mass, based on the total amount.

Examples of the alicyclic (meth) acrylate contained in the photocurable ink composition of the present embodiment include dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth). Examples include acrylate and isobornyl (meth) acrylate. These can particularly improve the strength of the image after curing. In particular, acrylates are preferable in terms of UV curability.
Moreover, as the commercial item, for example, FANCLIL FA-512A (S), FA-511A (S), FA-513A (S) (above, manufactured by Hitachi Chemical Co., Ltd., trade name) can be mentioned.

  More specifically, Shinzo Yamashita, “Crosslinker Handbook”, (1981 Taiseisha); Kato Kiyosumi, “UV / EB Curing Handbook (Materials)” (1985, Polymer Publications); Radtech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products or alicyclic (meth) acrylates known in the industry can be used.

An alicyclic (meth) acrylate is used individually by 1 type or in combination of 2 or more types. Moreover, it is preferable that the photocurable ink composition of this embodiment contains an alicyclic acrylate from the viewpoint of increasing the curing speed during photocuring.
The photocurable ink composition of this embodiment preferably contains 1 to 50% by mass of alicyclic (meth) acrylate, more preferably 10 to 45% by mass, based on the total amount.

  The photocurable ink composition of this embodiment contains a pigment as a colorant. Such a pigment is not particularly limited, and an inorganic pigment or an organic pigment can be used.

  As the inorganic pigment, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method is used in addition to titanium oxide and iron oxide. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelate, acidic dye chelate), nitro pigment, nitroso pigment, aniline black, and the like.

  More specifically, as carbon black, for example, C.I. I. Pigment Black 7, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. Raven5750, 5250, 5000, 3500, 1255, 700 (above product names) manufactured by Columbia, Regal 400R, 330R, 660R, Mogu L, 700 manufactured by Cabot , Monarch 800, 880, 900, 1000, 1100, 1300, 1300, 1400 (above product names), Color Black FW1, FW2, FW2V, FW18, FW18, FW200, S150, manufactured by Degussa S160, S170, Printex 35, U, V, 140U, Special Black 6, 5, 4A, and 4 (above product names).

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 180, 185, 213.

  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, 168, 184, 202, 209, C.I. I. And CI Pigment Violet 19.

  Examples of pigments used for cyan ink include C.I. I. And CI Pigment Blue 1, 2, 3, 15: 3, 15: 4, 60, 16, and 22.

  The average particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably about 50 to 150 nm. The photocurable ink composition of the present embodiment preferably contains about 0.1 to 25% by mass, more preferably about 0.5 to 15% by mass of a pigment as a colorant, based on the total amount.

  The photocurable ink composition of this embodiment preferably contains these pigments as a pigment dispersion obtained by dispersing them in an aqueous medium with a dispersant or a surfactant. As a preferable dispersant, a dispersant commonly used for preparing a pigment dispersion, for example, a polymer dispersant can be used.

  Moreover, the ink composition containing a colorant may have a plurality of colorants for each color. For example, in addition to the basic four colors of yellow, magenta, cyan, and black, when adding the same series of dark and light colors for each color, in addition to magenta, light light magenta, dark red, and cyan In addition to light light cyan, dark blue, and black, light gray, light black, and dark matte black can be listed.

  The photocurable ink composition of this embodiment contains a photopolymerization initiator. The photopolymerization initiator is an actinic ray to be irradiated, for example, 400 to 200 nm ultraviolet ray, far ultraviolet ray, g ray, h ray, i ray, KrF excimer laser beam, ArF excimer laser beam, electron beam, X ray, molecular beam. Or what has a sensitivity to an ion beam etc. can be selected suitably, and can be used.

  As a specific photopolymerization initiator, those known to those skilled in the art can be used without limitation, and specifically, for example, Bruce M. et al. Monroe et al., Chemical Review, 93, 435 (1993). R. S. By Davidson, Journal of Photochemistry and biologic A: Chemistry, 73.81 (1993). J. P. Faussier “Photoinitiated Polymerization—Theory and Applications”: Rapra Review vol. 9, Report, Rapra Technology (1998). M. Tsunooka et al. , Prog. Polym. Sci. , 21, 1 (1996). Those described in (1) are used. In addition, chemical amplification type photoresists described in “Organic Materials for Imaging” edited by Organic Electronics Materials Study Group, Bunshin Publishing (1993), pages 187 to 192, and compounds used for photocation polymerization are also used. Further, F.I. D. Saeva, Topics in Current Chemistry, 156, 59 (1990). G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993). H., et al. B. Shuster et al, JACS, 112, 6329 (1990). I. D. F. Eaton et al, JACS, 102, 3298 (1980). A group of compounds that undergo bond oxidative or reductive cleavage through interaction with an electronically excited state of a sensitizing dye as described in the above.

  Preferred photopolymerization initiators include aromatic ketones, aromatic onium salt compounds, organic peroxides, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples include compounds having a bond. Among these, the photopolymerization initiator is preferably at least one selected from the group consisting of α-aminoketone, α-hydroxyketone, and acylphosphine oxide.

  Examples of the photopolymerization initiator include Vicure 10, 30 (manufactured by Stauffer Chemical), IRGACURE 127, 184, 500, 651, 2959, 907, 369, 379, 754, 1700, 1800, 1850, 1870, 819, OXE01, Available under the trade names Darocur 1173, TPO, ITX (Ciba Specialty Chemicals), Quanture CTX (Aceto Chemical), Kayacure DETX-S (Nippon Kayaku), ESACURE KIP150 (Lamberti) Any radical photopolymerization initiator can be used.

  The photocurable ink composition of the present embodiment preferably contains 1 to 20% by mass of the photopolymerization initiator, more preferably 2 to 10% by mass, based on the total amount.

  The photocurable ink composition of this embodiment preferably contains phenoxyethyl (meth) acrylate from the viewpoint of imparting spreadability to the cured image.

Specific examples of phenoxyethyl (meth) acrylate include, for example, Biscote # 192 (above, trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), EBECRYL 114 (trade name, manufactured by Daicel Cytec Co., Ltd.), POA (Kyoeisha Chemical). Product name).
Phenoxyethyl (meth) acrylate is used singly or in combination of two or more. In addition, the photocurable ink composition of the present embodiment preferably contains phenoxyethyl acrylate from the viewpoint of increasing the curing speed during photocuring.

  The photocurable ink composition of the present embodiment preferably contains 1 to 50% by mass, more preferably 5 to 30% by mass of phenoxyethyl (meth) acrylate, based on the total amount.

  The photocurable ink composition of the present embodiment has a fixing property (adhesion) to a recording medium (media; for example, polyethylene terephthalate film, polyvinyl chloride, polypropylene, polyethylene film, container, etc.) of the ink composition. It is preferable to further include an adhesion component that improves the property. Examples of the adhesion component include N-hydroxyalkyl (meth) acrylamide compounds, and more specifically, N-hydroxyethyl (meth) acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-acryloylmorpholine, and the like. It is done. Among these, N-hydroxyethyl (meth) acrylamide is preferable in terms of high fixability and ultraviolet curability, and N-hydroxyethylacrylamide is more preferable from the same viewpoint.

As N-hydroxyethyl (meth) acrylamide, for example, photoreactivity for ultraviolet rays and electron beam curable resins, which is mainly composed of hydroxyethyl (meth) acrylamide described in JP-A-2001-270973. A diluent etc. are mentioned, Specifically, N-hydroxyethyl acrylamide ("HEAA", the Kojin Co., Ltd. product) is used as a commercial item.
An adhesion component is used individually by 1 type or in combination of 2 or more types.

  The photocurable ink composition of the present embodiment preferably contains 1 to 10% by mass of the adhesion component, and more preferably 3 to 7% by mass, based on the total amount.

The photocurable ink composition of this embodiment preferably contains benzyl (meth) acrylate as a diluent.
Specific examples of benzyl (meth) acrylate include FZ-BZA (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and light ester BZ (manufactured by Kyoeisha Chemical Co., Ltd.).
A benzyl (meth) acrylate is used individually by 1 type or in combination of 2 or more types. Moreover, it is preferable that the photocurable ink composition of this embodiment contains benzyl acrylate from the viewpoint of increasing the curing rate during photocuring.

  The photocurable ink composition of the present embodiment preferably contains 5 to 40% by mass of benzyl (meth) acrylate, more preferably 10 to 30% by mass, based on the total amount.

  The photocurable ink composition of the present embodiment may contain a sensitizing dye in order to promote decomposition of the photopolymerization initiator (radical polymerization initiator) by irradiation with actinic rays. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state is brought into contact with the polymerization initiator to cause actions such as electron transfer, energy transfer, and heat generation, thereby causing a chemical change of the polymerization initiator, that is, decomposition, radical, acid or base. It promotes the generation of.

  As the sensitizing dye, a compound corresponding to the wavelength of actinic radiation that generates an initiation species in the radical polymerization initiator used in the ink composition may be used. Considering that it is used for a curing reaction of a general ink composition, examples of preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region. Can be mentioned.

As sensitizing dyes, polynuclear aromatics (eg, anthracene, pyrene, perylene, triphenylene), thioxanthones (eg, isopropylthioxanthone), xanthenes (eg, fluorescein, eosin, erythrosin, rhodamine B, rose bengal) , Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, Acriflavine), anthraquinones (for example, anthraquinone), squariums (for example, squalium), coumarins (for example, 7-diethylamino-4-methylcoumarin), and the like. Nuclear aromatics and thioxanthones as preferred class. Furthermore, what was mentioned as an example of the more preferable sensitizing dye as described in Unexamined-Japanese-Patent No. 2008-195882 may be used.
A sensitizing dye is used individually by 1 type or in combination of 2 or more types.

  The photocurable ink of this embodiment may contain a vinylamide compound from the viewpoint of improving the sensitivity to irradiation with actinic radiation and image formation with excellent curability, and improving the adhesion between the cured image and the recording medium. Examples of such a vinylamide compound include a compound represented by the general formula (1) described in JP-A-2008-189887 (hereinafter also referred to as “specific vinylamide compound”).

Specific vinylamide compounds include, for example, Journal of the American Chemical Society 69, 911-915 (1947), Tetrahedron Letters 26, 2732-3238 (1985), Journal of Organic Chemi42, 1983, Vol. For example). Some are also available as those sold as test and research reagents by Sigma-Aldrich Japan, Tokyo Kasei Kogyo, etc.
A vinylamide compound is used individually by 1 type or in combination of 2 or more types.

  The photocurable ink composition of this embodiment is preferably prepared by adjusting the types and composition ratios of the above components so that the Tg (glass transition temperature) of the coating film is 20 to 30 ° C. . Thereby, it is possible to maintain the mechanical strength of the coating film at a high level and to improve the spreadability.

  The ink jet recording method of the present embodiment includes a step of discharging a droplet of the above-described photocurable ink composition and attaching the droplet to a recording medium for recording. The ink jet recording method may be the same as a conventionally known recording method except that it includes the above-described steps. According to the ink jet recording method of the present embodiment, a recorded image having excellent substrate followability and abrasion resistance can be formed after curing.

  The recorded matter of the present embodiment is a recorded matter recorded by the ink jet recording method described above. The recorded matter is not particularly limited as long as it is a recorded matter recorded by the inkjet recording method. The recorded matter of this embodiment is provided with a recorded image having excellent substrate followability and abrasion resistance.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the embodiments in these examples.

Example 1
The following components were mixed and stirred to obtain a photocurable ink composition.
Pigment (CI Pigment Red 122) 2.0 mass%
Urethane acrylate (trade name “EBECRYL8402”, manufactured by Daicel Cytec Co., Ltd.) 13.1% by mass
Benzyl methacrylate (trade name “FZ-BZA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 21.0% by mass
Dicyclopentenyloxyethyl acrylate (trade name “Fancryl FA-512A”, manufactured by Hitachi Chemical Co., Ltd.) 42.2% by mass
Phenoxyethyl acrylate (trade name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 7.0% by mass
N-hydroxyethylacrylamide (trade name “HEAA”, manufactured by Kojin Co., Ltd.) 4.4% by mass
Siloxane acrylate (trade name “BYK-UV3500”, manufactured by BYK) 0.70% by mass
Photopolymerization initiator (trade name “IRGACURE 1173”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 4.4% by mass
Photopolymerization initiator (trade name “IRGACURE907”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%
Photopolymerization initiator (trade name “IRGACURE819”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%

(Example 2)
The following components were mixed and stirred to obtain a photocurable ink composition.
Pigment (CI Pigment Red 122) 2.0 mass%
Urethane acrylate (trade name “EBECRYL8402”, manufactured by Daicel Cytec Co., Ltd.) 13.2% by mass
Benzyl methacrylate (trade name “FZ-BZA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 21.1% by mass
Dicyclopentenyloxyethyl acrylate (trade name “Fancryl FA-512A”, manufactured by Hitachi Chemical Co., Ltd.) 42.3 mass%
Phenoxyethyl acrylate (trade name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 7.0% by mass
N-hydroxyethylacrylamide (trade name “HEAA”, manufactured by Kojin Co., Ltd.) 4.4% by mass
Siloxane acrylate (trade name “BYK-UV3500”, manufactured by BYK) 0.4% by mass
Photopolymerization initiator (trade name “IRGACURE 1173”, Ciba Specialty Chemicals Co., Ltd., 4.4% by mass)
Photopolymerization initiator (trade name “IRGACURE907”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%
Photopolymerization initiator (trade name “IRGACURE819”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%

Example 3
The following components were mixed and stirred to obtain a photocurable ink composition.
Pigment (CI Pigment Red 122) 2.0 mass%
Urethane acrylate (trade name “EBECRYL8402”, manufactured by Daicel Cytec Co., Ltd.) 13.0% by mass
Benzyl methacrylate (trade name “FZ-BZA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 20.8% by mass
Dicyclopentenyloxyethyl acrylate (trade name “Fancryl FA-512A”, manufactured by Hitachi Chemical Co., Ltd.) 41.7% by mass
Phenoxyethyl acrylate (trade name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 7.0% by mass
N-hydroxyethylacrylamide (trade name “HEAA”, manufactured by Kojin Co., Ltd.) 4.4% by mass
Siloxane acrylate (trade name “BYK-UV3500”, manufactured by BYK) 2.0% by mass
Photopolymerization initiator (trade name “IRGACURE 1173”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 4.3 mass%
Photopolymerization initiator (trade name “IRGACURE907”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%
Photopolymerization initiator (trade name “IRGACURE819”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%

(Comparative Example 1)
The following components were mixed and stirred to obtain a photocurable ink composition.
Pigment (CI Pigment Red 122) 2.0 mass%
Urethane acrylate (trade name “EBECRYL8402”, manufactured by Daicel Cytec Co., Ltd.) 13.2% by mass
Benzyl methacrylate (trade name “FZ-BZA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 21.2% by mass
Dicyclopentenyloxyethyl acrylate (trade name “Fancryl FA-512A”, manufactured by Hitachi Chemical Co., Ltd.) 42.5% by mass
Phenoxyethyl acrylate (trade name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 7.1 mass%
N-hydroxyethylacrylamide (trade name “HEAA”, manufactured by Kojin Co., Ltd.) 4.4% by mass
Photopolymerization initiator (trade name “IRGACURE 1173”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 4.4% by mass
Photopolymerization initiator (trade name “IRGACURE907”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%
Photopolymerization initiator (trade name “IRGACURE819”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%

(Comparative Example 2)
The following components were mixed and stirred to obtain a photocurable ink composition.
Pigment (CI Pigment Red 122) 2.0 mass%
Urethane acrylate (trade name “EBECRYL8402”, manufactured by Daicel Cytec Co., Ltd.) 13.2% by mass
Benzyl methacrylate (trade name “FZ-BZA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 21.2% by mass
Dicyclopentenyloxyethyl acrylate (trade name “Fancryl FA-512A”, manufactured by Hitachi Chemical Co., Ltd.) 42.4% by mass
Phenoxyethyl acrylate (trade name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 7.1 mass%
N-hydroxyethylacrylamide (trade name “HEAA”, manufactured by Kojin Co., Ltd.) 4.4% by mass
Siloxane acrylate (trade name “BYK-UV3500”, manufactured by BYK) 0.1% by mass
Photopolymerization initiator (trade name “IRGACURE 1173”, Ciba Specialty Chemicals Co., Ltd., 4.4% by mass)
Photopolymerization initiator (trade name “IRGACURE907”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%
Photopolymerization initiator (trade name “IRGACURE819”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%

(Comparative Example 3)
The following components were mixed and stirred to obtain a photocurable ink composition.
Pigment (CI Pigment Red 122) 2.0% by mass
Urethane acrylate (trade name “EBECRYL8402”, manufactured by Daicel Cytec Co., Ltd.) 12.8% by mass
Benzyl methacrylate (trade name “FZ-BZA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 20.5% by mass
Dicyclopentenyloxyethyl acrylate (trade name “Fancryl FA-512A”, manufactured by Hitachi Chemical Co., Ltd.) 41.0% by mass
Phenoxyethyl acrylate (trade name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 6.8% by mass
N-hydroxyethylacrylamide (trade name “HEAA”, manufactured by Kojin Co., Ltd.) 4.3 mass%
Siloxane acrylate (trade name “BYK-UV3500”, manufactured by BYK) 3.0% by mass
Photopolymerization initiator (trade name “IRGACURE 1173”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 4.4% by mass
Photopolymerization initiator (trade name “IRGACURE907”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%
Photopolymerization initiator (trade name “IRGACURE819”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.6 mass%

(Evaluation of ink composition)
(Curable)
The obtained photocurable ink composition was applied to Lumirror 125E20 (trade name, manufactured by Panac Co., Ltd.), PETWH50, PVC 80M (trade name, manufactured by Lintec Co., Ltd.) using a bar coater and a film thickness of 10 μm. Next, with an ultraviolet irradiation device ECS-151U-TOKU (product name, manufactured by Eye Graphics Co., Ltd.), irradiation is performed under conditions of an integrated irradiation amount of 500 mJ / cm ² and an illuminance of 360 mW / cm ² , and tack-free. The accumulated irradiation dose until the time was evaluated according to the following criteria.
A: 500~1000mJ / cm becomes tack-free within ² ranges B: a tack-free when it exceeds 1000 mJ / cm ²

(Substrate followability)
Using a TENSILON RTC1250A (trade name, manufactured by ORIENTEC Co., Ltd.), a medium on which a coating film obtained by curing the ink composition is formed, and a tensile speed of 10 mm / min and a chuck distance of 30 mm The tensile strength was confirmed. The results were evaluated according to the following criteria.
A: Even if the elongation exceeds 100%, cracks and film peeling do not occur in the coating film. B: Within the range of 50 to 100% elongation, cracks and film peeling occur in the coating film. C: When the elongation is less than 50%. , Cracks and film peeling occur in the coating film

(Abrasion resistance)
For the media (PETWH50, PVC80M) on which a coating film obtained by curing the ink composition is formed, using a Sousaland Love Desta (trade name, manufactured by Toyo Seiki Co., Ltd.) The state of the friction paper or media when the pasted friction paper was rubbed 100 times was confirmed. The results were evaluated according to the following evaluation criteria.

Evaluation criteria 1 No ink peeling scratches on media, no color on friction paper.
2 There is a small ink peeling scratch on the media, and there is a small coloration on the friction paper 1-2 places.
3 There is a little ink peeling scratches on the media, and there is a little coloring on the friction paper.
4 Medium ink peeling scratches on the media, and friction paper is slightly colored.
5 There are many peeling scratches on the media, and the entire surface of the friction paper is colored.
(Adhesion)
The media (the PETWH50 and PVC80M) on which the coating film obtained by curing the ink composition was formed were evaluated according to the method of JIS K-5600-5-6 (cross cut). The results were evaluated according to the following evaluation criteria.
Evaluation criteria 0 The edge of the cut is completely smooth, and there is no peeling in the eyes of any lattice.
1 Small peeling of the coating film at the crossing part (crosscut part) of the cut is partially observed. The area where peeling is recognized among the plurality of areas of the coating film surrounded by the cut is clearly 5% or less.
2 The coating film is partially peeled along the edge of the cut and / or at the intersection. The area where peeling is observed among the plurality of areas of the coating film surrounded by the cut is clearly more than 5% and 15% or less.
3 The coating film has been partially or wholly peeled along the edge of the cut, and some of the plurality of regions of the coating film surrounded by the cut have been partially or wholly dropped. Of the plurality of regions of the coating film surrounded by the cut, the region where peeling is observed is clearly more than 15% and 35% or less.
4 The coating film has been partially or wholly peeled along the edge of the cut, and among the multiple areas of the coating film surrounded by the cut, there are several places (however, clearly more than the standard 3 above). It is missing partially or completely. The area where peeling is observed among the plurality of areas of the coating film surrounded by the cut is clearly more than 35% and 65% or less.
5 Exfoliation and dropping to a degree exceeding the above standard 4 are observed.

The results are shown in Table 1.

Claims (7)

  A photocurable ink composition comprising urethane (meth) acrylate, alicyclic (meth) acrylate, siloxane (meth) acrylate, a pigment, and a photopolymerization initiator.   The photocurable ink composition according to claim 1, comprising 0.3 to 2.0 mass% of the siloxane (meth) acrylate.   The photocurable ink composition according to claim 1, further comprising phenoxyethyl (meth) acrylate.   The photocurable ink composition according to claim 1, further comprising an adhesion component that improves adhesion of the photocurable ink composition to a recording medium.   The photocurable ink composition according to claim 4, wherein the adhesion component is N-hydroxyethyl (meth) acrylamide.   An ink jet recording method comprising a step of discharging a droplet of the photocurable ink composition according to any one of claims 1 to 5 and attaching the droplet to a recording medium for recording.   A recorded matter recorded by the ink jet recording method according to claim 6.