JP2009203310A - Photocurable coating composition, overprint, and its production method - Google Patents

Abstract

Provided are a photocurable coating composition excellent in surface smoothness, non-tackiness (surface tackiness suppression) and odor suppression, an overprint obtained using the photocurable coating composition, and a method for producing the same. thing.
A photocurable coating composition comprising (A) a fragrance, (B) a photopolymerization initiator, and (C) a polymerizable compound, and the photocurable coating composition. The overprint used and its manufacturing method.
[Selection figure] None

Description

  The present invention relates to a photocurable coating composition, an overprint, and a method for producing the same. More specifically, the present invention relates to a photocurable coating composition that can be cured by irradiation with active radiation such as an electron beam and ultraviolet rays. In particular, light for coating an image created by arranging ink and / or toner on a printing substrate (image receiving substrate) by a method such as planographic printing, relief printing, intaglio printing, screen printing, ink jetting, and electrophotography. The present invention relates to a curable coating composition. More particularly, it relates to photocurable overprint compositions that can be used particularly suitably for coating toner-based prints printed by electrophotography.

In recent years, a large number of actinic radiation curable compositions that can be used for UV-curable printing inks, paints, and coatings have been developed and are now being popularized. However, it is difficult to obtain a photocurable composition that satisfies all of the curability, surface smoothness, strength, storage stability, and the like.
In particular, toner-based images such as electrophotography are more difficult to obtain the desired performance when a feather oil layer is present on the image surface.
In a conventional method for generating a toner-based image, such as electrophotography, an electrostatic charge is formed on the surface of the latent image carrier by uniformly charging the surface of the latent image carrier, for example, a photoreceptor. Let Then, the uniformly charged area is selectively released by the activation irradiation pattern corresponding to the image of the original. The latent image charge pattern remaining on the surface corresponds to the areas not exposed to irradiation. The photoreceptor is then passed through one or more development housings containing toner, so that the toner adheres in a charge pattern due to electrostatic attraction, thereby visualizing the latent image charge pattern. The developed image is then fixed to the imaging surface or transferred to a printing substrate, such as paper, and fixed to it by a suitable fixing technique to obtain an electrophotographic print, i.e. a toner-based print. .

As a known method for protecting a printed matter, it has been proposed to apply an overprint coating to the printed matter. For example, Patent Documents 1 and 2 propose a method of covering the surface by performing fixing after transferring a transparent toner onto a toner-based image, such as electrophotography.
Patent Document 3 proposes a method of performing overprint coating by applying a liquid film coating that can be cured by ultraviolet rays or the like, and polymerizing (crosslinking) the coating components with light.
In addition, Patent Document 4 discloses a polyfunctional alkoxylated acrylic monomer or polycrystal comprising a radiation curable oligomer selected from the group consisting of trifunctional unsaturated acrylic resins and one or more di-acrylates or tri-acrylates. An overprint composition comprising a radiation curable monomer selected from the group consisting of alkoxylated acrylic monomers, at least one photopolymerization initiator, and at least one surfactant is disclosed.

However, toner-based images such as electrophotography, when there is a feather oil layer on the image surface, the printed surface is hydrophobic and the surface energy is low, so the curability, surface smoothness, It is difficult to obtain a photocurable composition satisfying all of strength, storage stability and the like.
In particular, when an overprint coating is applied on toner-based image information and handled as an alternative to silver salt photographic prints, the odor and safety of the product are important qualities that are generally used by ordinary consumers. Become one.
The cause of odor generation is the remaining of volatile compounds such as polymerizable monomers (uncured monomer) and polymerization that is not incorporated into the cured film because it does not copolymerize with the curable composition. Examples include decomposition products of initiators.
Regarding the reduction of odor caused by the polymerizable monomer, it is conceivable to use a solid monomer or a high molecular weight liquid monomer from the viewpoint of low volatility, but the surface smoothness decreases because the viscosity of the polymerizable composition increases. There is a problem that streaks occur on the surface of the printed material.
On the other hand, regarding the polymerization initiator, a polymer-type initiator in which a phenyl ketone derivative having a polymerization initiating ability is polymerized is disclosed in Patent Document 5, but the reactivity of phenyl ketone is improved in terms of odor. It is low and sufficient curability cannot be obtained with a practical irradiation dose.
Moreover, although the monoacrylate photoinitiator which can be copolymerized is also disclosed by patent document 6, the probability that monoacrylate will be copolymerized at the time of reaction is low, and an odor cannot be prevented.

JP-A-11-70647 JP 2003-241414 A JP-A-61-210365 JP-A-2005-321882 JP 7-33811 A European Patent No. 377191

  An object of the present invention is to provide a photocurable coating composition excellent in surface smoothness, non-tackiness (surface tackiness suppression) and odor suppression, an overprint obtained using the photocurable coating composition, and a method for producing the same Is to provide.

The above object has been achieved by the following <1> and <9> to <11>. It is described below together with <2> to <8> which are preferred embodiments.
<1> A photocurable coating composition comprising (A) a fragrance, (B) a photopolymerization initiator, and (C) a polymerizable compound,
<2> (A) The photocurable coating composition according to <1>, wherein the fragrance includes a natural fragrance,
<3> (A) The photocurable coating composition according to <1> or <2> above, wherein the fragrance comprises a synthetic fragrance,
<4> (A) The photocurable coating composition according to any one of <1> to <3> above, wherein the fragrance contains an ester compound,
<5> (A) The photocurable coating composition according to any one of <1> to <4> above, wherein the fragrance contains a terpene compound,
<6> The photocurable coating composition according to any one of <1> to <5>, which has substantially no absorption in a visible region,
<7> The photocurable coating composition according to any one of <1> to <6> above, which is for overprinting,
<8> The photocurable coating composition according to any one of <1> to <7> above, which is for overprinting of an electrophotographic printed material,
<9> An overprint having an overprint layer obtained by photocuring the photocurable coating composition according to any one of <1> to <8> above on a printed material,
<10> An overprint having an overprint layer obtained by photocuring the photocurable coating composition according to any one of <1> to <8> above on an electrophotographic printed material,
<11> A step of obtaining an electrophotographic printed material by electrophotographic printing on a printing substrate, and applying the photocurable coating composition according to any one of <1> to <8> above on the electrophotographic printed material. And a method of photocuring the photocurable coating composition.

  According to the present invention, a photocurable coating composition excellent in surface smoothness, non-tackiness (surface tackiness suppression), and odor suppression, an overprint obtained using the photocurable coating composition, and its A manufacturing method could be provided.

The photocurable coating composition of the present invention (hereinafter also simply referred to as “coating composition”) contains (A) a fragrance, (B) a photopolymerization initiator, and (C) a polymerizable compound. Features.
The overprint of the present invention has an overprint layer obtained by photocuring the photocurable coating composition on an electrophotographic printed material.
The overprint production method of the present invention includes a step of electrophotographic printing on a printing substrate to obtain an electrophotographic printed matter, a step of applying the above-mentioned photocurable coating composition on the electrophotographic printed matter, and the coating Photocuring the composition.
Hereinafter, the present invention will be described in detail.

(Photocurable coating composition)
The photocurable coating composition of the present invention contains (A) a fragrance, (B) a photopolymerization initiator, and (C) a polymerizable compound.
The photocurable coating composition of the present invention preferably has substantially no absorption in the visible range. “Substantially no absorption in the visible region” means that there is no absorption in the visible region of 400 to 700 nm, or there is absorption in the visible region only to the extent that there is no problem as a photocurable coating composition. It means not. Specifically, it means that the 5 μm optical path length transmittance of the coating composition is 70% or more, preferably 80% or more in the wavelength range of 400 to 700 nm.
The photocurable coating composition of the present invention can be suitably used for overprinting, and can be particularly suitably used for overprinting of electrophotographic prints.
The photocurable coating composition of the present invention is excellent in non-tackiness and surface smoothness, glossy and glossy even when an overprint layer is formed on an electrophotographic print having an image portion having a thickness equivalent to the toner. It gives a certain overprint and can visually give an impression close to that of a conventional silver halide photographic print.
In addition, the photocurable coating composition of the present invention is excellent in non-tackiness and surface smoothness, gloss, gloss, and flexibility with little warpage, even for a toner image having a feather oil layer on the image surface. Image prints rich in color, and an overprint visually close to a silver salt photographic print can be obtained.

(A) Fragrance The photocurable coating composition of the present invention contains a fragrance as an essential component. The perfume is effective in reducing the odor of the photocurable coating composition.
The fragrance is preferably one that neutralizes or masks the odor derived from the polymerizable compound. As a fragrance | flavor, a well-known fragrance | flavor can be selected suitably and can be used, a fragrance | flavor can also be used individually by 1 type, and a several fragrance | flavor can also be selected and used.
The fragrance is preferably selected as appropriate depending on the polymerizable compound or solvent used in the photocurable coating composition, and is preferably optimized by combining known fragrances. Moreover, as a fragrance | flavor, both a natural fragrance | flavor and a synthetic | combination fragrance | flavor can be used.

  Natural flavors can be broadly classified into animal flavors and vegetable flavors. Examples of animal flavors include castrium (sea scented incense), musk (scented scented incense), ambergris (dragon scented incense), and civet (spirit scented incense). Examples of vegetable flavors include lemon oil, orange oil, lime oil, bergamot oil, eucalyptus oil, mandarin oil, winter green oil, camphor oil, pepper oil, oak moss oil, oppoponax oil, copaiba oil, sandals Oil, cedarwood oil, trubalsum oil, perubalsum oil, benzoin oil, vanilla oil, abies fa oil, almond oil, columnus oil, camomil oil, cardamom oil, galvanum oil, caraway oil, cumin oil, coriander oil, juniper Berry oil, spearmint oil, sage oil, celery oil, thyme oil, tarragon oil, nutmeg oil, basil oil, hyssop oil, pettigren oil, butchu oil, penny royal oil, peppermint oil, mace oil, lavender oil, rosemary oil, Lobe oil, laurel oil, amylis oil Elemi oil, Cassia oil, Guayac oil, Clove oil, Stylax oil, Geranium oil, Tangerine oil, Patchouli oil, Vetiver oil, Labdanum oil, Lemongrass oil, Angelica oil, Hinoki oil, Hiba oil, Citronella oil, Anise seed oil, Ylang Ylang Oil, Clarisage Oil, Cinnamon Oil, Star Anise Oil, Cananga Oil, Black Currant Oil, Amblet Seed Oil, Bay Oil, Boad Rose Oil, Kayapte Oil, Cassie Oil, Coriander Oil, Costas Oil, Davana Oil, Dill Oil , Fennel oil, Fenigree oil, Gene oil, Grapefruit oil, Ginger oil, Hop oil, Hyacinth oil, Inmortel oil, Jasmine oil, Jonquil oil, Labandin oil, Linaroe oil, Lycea cubeba oil, Marjoram oil, Mimosa oil, Mill oil, Myrtle oil, Narushi Oil, Olivenham Oil, Oris Oil, Parsley Oil, Palmarosa Oil, Pepper Oil, Perilla Oil, Neroli Oil, Orange Flower Oil, Pimenta Oil, Pine Oil, Rose Oil, Spike Lavender Oil, Tadget Oil, Tonka Beans Oil, Tuberose Oil , Turpentine oil, valerian oil, violet oil, wormwood oil, yuzu oil and the like.

The natural fragrance component may be any shape such as essential oil, absolute, concrete, resinoid and the like.
In addition, depending on the purpose of use, the main component, special component, or necessary component contained can be fractionated from the natural fragrance and used as a fractionated fragrance. Separation and purification can be achieved by distillation, recrystallization, chromatography, chemical treatment, and the like.

  Synthetic fragrances are classified into fractionated fragrances and chemically synthesized fragrances obtained by separating and purifying active ingredients contained in plant essential oils. The latter is produced by petrochemical products and natural terpene compounds as raw materials, based on organic synthesis processes, by total synthesis, semi-synthesis, and biosynthesis methods. Chemically synthesized fragrances may be those obtained by chemically synthesizing the same active ingredients as natural fragrances, and newly discovered compounds that are not found in natural fragrances but are excellent in fragrance. .

  Focusing on the molecular structure of fragrances, the fragrances include aliphatic hydrocarbons, terpene hydrocarbons, hydrocarbons such as aromatic hydrocarbons, aliphatic alcohols, terpene alcohols, alcohols such as aromatic alcohols, and aliphatic ethers. , Ethers such as aromatic ethers, aliphatic oxides, oxides such as terpene oxides, aliphatic aldehydes, terpene aldehydes, alicyclic aldehydes, aldehydes such as thioaldehydes, aromatic aldehydes, aliphatic ketones , Terpene ketone, alicyclic ketone, aliphatic cyclic ketone, non-benzene aromatic ketone, aromatic ketone and other ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, fats Acids such as cyclic carboxylic acid and aromatic carboxylic acid, acid amides, aliphatic lactate , Macrocyclic lactones, terpene lactones, alicyclic lactones, aromatic lactones and other lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acids Examples include esters such as acid esters and aromatic carboxylic acid esters, nitrogen-containing compounds such as nitromusks, nitriles, amines, pyridines, quinolines, pyrrole and indole.

Specifically, the hydrocarbons include α-pinene, β-pinene, camphene, myrcene, limonene, terpyrene, osmene, γ-terpinene, α-ferrandylene, p-cymene, β-cariolefin, β-farnesene. 1,3,5-undecatriene, diphenylmethane and the like.
Examples of alcohols include trans-2-hexenol, cis-3-hexenol, 3-octanol, 1-octen-3-ol, 2,6-dimethyl-2-heptanol, 9-decenol, and 4-methyl-3-decene. -5-ol, 10-undecenol, trans-2-cis-6-nonadienol, linalool, geraniol, nerol, citronellol, rosinol, myrsenol, lavandulol, tetrahydrogeraniol, tetrahydrolinalol, hydroxycitronellol, dihydromyrcenol, allo Osimenol, α-terpineol, tarpinen-4-ol, 1-menthol, borneol, isopulegol, nopol, farnesol, nerolidol, bisabolol, cedrol, patchoulialcohol, vetivero 2,4-dimethyl-3-cyclohexene-1-methanol, 4-isopropylcyclohexanol, 4-isopropylcyclohexanemethanol, 1- (4-isopropylcyclohexyl) ethanol, 2,2-dimethyl-3- (3-methylphenyl) ) Propanol, pt-butylcyclohexanol, ot-butylcyclohexanol, ambrinol, 1- (2-tert-butylcyclohexyloxy) -2-butanol, pentamethylcyclohexylpropanol, 1- (2,2, 6-trimethylcyclohexyl) -3-hexanol, benzyl alcohol, phenethyl alcohol, phenoxyethyl alcohol, styryl alcohol, anise alcohol, cinnamic alcohol, phenylpropyl alcohol, dimethylbenz Aliphatic alcohols such as lucarbinol, dimethylphenyl ethyl carbinol, phenethyl methyl ethyl carbinol, 3-methyl-5-phenylpentanol, thymol, carvacrol, orcinol monomethyl ether, eugenol, isoeugenol, propenyl guaetol, aromatic Group alcohols and terpene alcohol compounds.

  Examples of ethers include nerol oxide, miloxide, 1,8-cineol, rose oxide, limethol, mentfuran, linalool oxide, butyldimethyldihydropyran, acetoxyamyltetrahydropyran, cedolmethyl ether, methoxycyclodecane, 1-methyl -1-methoxycyclodecane, ethoxymethylcyclododecyl ether, tricyclodecenyl methyl ether, rubofix, cedroxide, ambroxan, glycalva, voiris, anisole, dimethylhydroquinone, paracresylmethylether, acetanisole, anethole, dihydro Anethole, Estragol, Diphenyl ether, Methyl eugenol, Methyl isoeugenol, Benzyl isoeugenol, Phenylmethy Isoamyl ether, beta-naphthyl methyl ether, beta-naphthyl ethyl ether, beta-naphthyl isobutyl ether, aliphatic ethers such as hexamethyl hydro cyclopentane benzopyran, aromatic ethers, terpene oxide compounds.

  Aldehydes include hexyl aldehyde, heptyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, tridecyl aldehyde, trimethyl hexyl aldehyde, methyl octyl acetaldehyde, methyl nonyl acetaldehyde, trans-2-hexenal, cis -4-heptenal, 2,6-nonadienal, cis-4-decenal, undecylene aldehyde, trans-2-dodecenal, trimethylundecenal, 2,6,10-trimethyl-5,9-undecadienal, citral, Citronellal, hydroxycitronellal, perilaldehyde, methoxydihydrocitronellal, citronellyloxyacetaldehyde, 2,4-dimethyl-3- Chlohexenyl aldehyde, isocyclocitral, centenal, mylacaldehyde, rilal, Bernaldehyde, dupical, macear, boronal, setneral, benzaldehyde, phenylacetaldehyde, phenylpropional, cinnamic aldehyde, α-amylcinnamic aldehyde, α-hexylcin Namic aldehyde, hydrotropic aldehyde, anisaldehyde, p-methylphenylacetaldehyde, cuminaldehyde, cyclamenaldehyde, 3- (pt-butylphenyl) propanal, p-ethyl-2,2-dimethylhydrocinnamic aldehyde, 2 -Methyl-3- (p-methoxyphenyl) propanal, pt-butyl-α-methylhydrocinnamic aldehyde, salicyl Aldehyde, heliotropin, ocean propanal, vanillin, ethyl vanillin, aliphatic aldehydes such as methyl vanillin, aromatic aldehydes include terpene aldehyde compounds.

  As acetals, octanal glycol acetal, acetaldehyde ethyl cis-3-hexenyl acetal, citral dimethyl acetal, citral diethyl acetal, acetaldehyde ethyl linalyl acetal, hydroxycitronellal dimethyl acetal, phenylacetaldehyde dimethyl acetal, hydrotropic aldehyde dimethyl acetal , Phenylacetaldehyde glyceryl acetal, acetaldehyde phenylethylethyl acetal, acetaldehyde phenylethylpropyl acetal, phenylpropanal propylene glycol acetal, 4,4,6-trimethyl-2-benzyl-1,3-dioxane, 2,4,6-trimethyl -2-phenyl-1,3-dioxane, 4,4 6-trimethyl-2-butyl-1,3-dioxane, tetrahydropyran indeno -m- dioxin, dimethyl tetrahydroindenyl indeno -m- dioxin include acetal compounds such Karanaru.

  As ketones, acetoin, diacetyl, methyl amyl ketone, ethyl amyl ketone, methyl hexyl ketone, methyl nonyl ketone, methyl heptenone, coabon, camphor, carvone, menthone, d-pulegone, pepitone, fension, geranylacetone, cedryl methyl Ketone, Nootkaton, Ionone, Methylionone, Allylionone, Iron, Damascon, Damasenone, Dynascon, Maltol, Ethylmaltol, 2,5-Dimethyl-4-hydroxyfuranone, pt-butylcyclohexanone, amylcyclopentanone, heptylcyclopentanone , Dihydrojasmon, cis-jasmon, Florex, pricatone, muscone, cybeton, cyclopentadecanone, cyclohexadecenone, 4-cyclohexyl 4-methyl-2-pentanone, p-mentel-6-yl-propanone, 2,2,5-trimethyl-5-menthylcyclopentanone, ethoxyvinyltetramethylcyclohexanone, dihydropentamethylindanone, iso-Esuper (product) Name), Trimofix (trade name), acetophenone, p-methylacetophenone, benzylacetophenone, calone, raspberry ketone, anisylacetone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, methylnaphthyl ketone, 4 Aliphatic such as phenyl-4-methyl-2-pentanone, benzophenone, 6-acetylhexamethylindane, 4-acetyldimethyl-t-butylindane, 5-acetyltetramethylisopropylindane, 6-acetylhexatetralin Tons, aromatic ketones, terpene ketone compounds.

  Esters include ethyl formate, cis-3-hexenyl formate, linalyl formate, citronellyl formate, geranyl formate, benzyl formate, phenyl ethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, methyl cyclopentylidene acetate, hexyl acetate, acetic acid Cis-3-hexenyl, trans-3-hexenyl acetate, isononyl acetate, citronellyl acetate, lavandulyl acetate, geranyl acetate, linalyl acetate, mircenyl acetate, tervinyl acetate, menthyl acetate, menthanyl acetate, nopyru acetate, boronyl acetate, isobornyl acetate, acetic acid p-t-butylcyclohexyl, o-t-butylcyclohexyl acetate, tricyclodecenyl acetate, 2,4-dimethyl-3-cyclohexene-1-methanyl acetate, benzyl acetate, phenylethyl acetate, styrylyl acetate, vinegar Cinnamyl, anisyl acetate, p-cresyl acetate, heliotropyl acetate, guayl acetate, cedryl acetate, vetiberyl acetate, decahydro-β-naphthyl acetate, acetyl eugenol, acetyl isoeugenol, ethyl propionate, isoamyl propionate, citronellyl propionate, propionic acid Geranyl, linalyl propionate, terpinyl propionate, benzyl prolionate, cinnamyl propionate, allyl cyclohexylpropionate, tricyclodecenyl propionate, ethyl butyrate, ethyl 2-methylbutyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, butyric acid Linalyl, geranyl butyrate, citronellyl butyrate, benzyl butyrate, cis-3-hexenyl isobutyrate, citronellyl isobutyrate, geranyl isobutyrate, linalyl isobutyrate, isobutyrate Benzyl acid, phenylethyl isobutyrate, phenoxyethyl isobutyrate, tricyclodecenyl isobutyrate, ethyl isovalerate, propyl valerate, citronellyl isovalerate, geranyl isovalerate, benzyl isovalerate, cinnamyl isovalerate, Phenyl ethyl isovalerate, ethyl caproate, allyl caproate, ethyl enanthate, allyl enanthate, ethyl caprate, citronellyl tiglate, methyl octynecarboxylate, allyl 2-pentyloxyglycolate, cis-3-hexenylmethyl carbonate , Ethyl pyruvate, isoamyl pyruvate, ethyl acetoacetate, ethyl levulinate, methyl benzoate, ethyl benzoate, isobutyl benzoate, isoamyl benzoate, benzyl benzoate, geranyl benzoate, linalyl benzoate, feline benzoate Ruethyl, methyl dihydroxydimethylbenzoate, methyl phenylacetate, ethyl phenylacetate, isobutyl phenylacetate, isoamyl phenylacetate, geranyl phenylacetate, benzyl phenylacetate, phenylethyl phenylacetate, p-cresyl phenylacetate, methyl cinnamate, ethyl cinnamate , Benzyl cinnamate, cinnamyl cinnamate, phenylethyl cinnamate, methyl salicylate, ethyl salicylate, isobutyl salicylate, isoamyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, ethyl anislate, anthranil Methyl acid, ethyl anthranilate, methyl methyl anthranilate, methyl jasmonate, methyl dihydrojasmonate, methyl phenyl glycy Ethyl, phenylglycidic acid ethyl Gurikomeru, fractons, Fureisuton, Furuteto, Jibesukon, aliphatic esters such as Karikisoru (trade name), an aromatic ester, carbonate compounds.

  Examples of the carboxylic acids include carboxylic acid compounds such as geranilic acid, citronellic acid, benzoic acid, phenylacetic acid, phenylpropionic acid, cinnamic acid, and 2-methyl-2-pentenonic acid.

  Examples of lactones include γ-octalactone, γ-nonalactone, γ-decalactone, γ-undecalactone, δ-decalactone, coumarin, dihydrocoumarin, jasmolactone, jasmine lactone, sugar lactone, cyclopentadecanolide, cyclohexanone. Sadecanolide, 12-cyclopentadecanolide, cyclohexadecenolide, 12-oxa-16-hexadecanolide, 11-oxa-16-hexadecanolide, 10-oxa-16-hexadecanolide, ethylene brush note, ethylenedodecanedioate And aliphatic lactones and aromatic lactone compounds.

  Examples of nitrogen-containing compounds include acetylpyrrole, indole, skatole, indolene, 2-acetylpyridine, maritima, 6-methylquinoline, 6-isopropylquinoline, 6-isobutylquinoline, 2-acetylpyrazine, 2,3-dimethylpyrazine, 2-Isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, 2-sec-butyl-3-methoxypyrazine, trimethylpyrazine, geranylnitrile, citronellylnitrile, 5-phenyl-3-methyl-2-pentene Nitrogen-containing compounds such as nitrile, 3,7-dimethyl-2,6-nonadiene nitrile, cinnamon nitrile, cumin nitrile, dodecane nitrile, tridecene-2-nitrile, 5-methyl-3-heptanone oxime and the like can be mentioned.

  Among these, representative examples include acetyl cedrene, IsoEsuper (trade name), ethyl isovalerate, benzyl isovalerate, ethyl vanillin, ethylene brushate, 1-octen-3-ol, galaxolide (trademark) Name), camphor, methyl cinnamate, geraniol, geranyl acetate, benzyl acetate, linalyl acetate, sandalol (trade name), cyclamenaldehyde, cyclopentadecanolide, citral, citronellal, citronellol, methyl dihydrojasmonate, cisjasmine, Damascon, Turpiol, Tonalid (trade name), Vacdanol, Vanillin, Hydroxycitronellal, Phenylacetaldehyde, 2-Phenylethanol, Hexylcinnamic aldehyde, Cis-3-hexenol, Heliotro Emissions, methyl ATRA preparative rates, methyl ionone, menthol, ionone, linalool, lyral (trade name), Kobanoru (trade name), Lilial (brand name), rose oxide can be exemplified.

  Among these, as perfumes, terpene hydrocarbons, terpene alcohols, terpene oxides, terpene aldehydes, terpene ketones, terpene carboxylic acids, terpene lactones, terpene carboxylic esters and the like terpene compounds and / or aliphatic esters It is preferable to use ester compounds such as furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, and aromatic carboxylic acid esters.

Hereinafter, the fragrance | flavor with respect to an acrylic odor is explained in full detail.
Acrylic acid ester monomers and methacrylic acid ester monomers are important raw materials in photocurable coating compositions and have an odor as an acrylic odor. These raw materials give an odor when a trace amount (100 ppb) remains even after the photocurable coating composition is cured by light irradiation.

Especially for photocurable coating compositions and overprints having such an acrylic odor,
Group A fragrance: At least one fragrance selected from the group of fragrances having an orange note.
Group B fragrance: At least one fragrance selected from the group of fragrances having a green note.
By adding, it is possible to reduce the acrylic odor.

  As the fragrance selected from the fragrance (group A) having an orange note, for example, orange oil Valencia, bergamot oil, neroli oil, pettigren oil, d-limonene, linalool, orange flower absolute, linalyl acetate, methylanthranilate, Examples include uranium thiol, methyl beta naphthyl ketone, and Yarayara, and these can be used alone or in admixture of two or more. Particularly preferred are orange oil Valencia and bergamot oil. The blending amount of these fragrances is preferably 0.001 to 2.0% by weight (hereinafter simply referred to as “%”), more preferably 0.005 to 1.5%, based on the total amount of the photocurable coating composition. 0%.

  Examples of the fragrance selected from the fragrance (group B) group having a green note include, for example, cis-3-hexenol, cis-3-hexenyl acetate, phenylacetaldehyde, dimethyltetrahydrobenzaldehyde, methylphenylcarbinyl acetate, and methyloctyne. Examples include carbonate, allyl butyrate, cumin aldehyde, allyl cyclohexyl oxyacetate, butyl orthobutyl glycolate, pyrazine, ethyl benzoate and the like, and these can be used alone or in combination of two or more, and particularly preferred Cis-3-hexenol, cis-3-hexenyl acetate, phenylacetaldehyde, dimethyltetrahydrobenzaldehyde, methylphenylcarbinyl acetate, methyloctyne carbonate It is. These green notes are fragrance components that are also present in natural fragrances such as rose, geranium, and violet leaf, but their origins are not particularly limited. The blending amount of these fragrances in the photocurable coating composition is preferably 0.001 to 2.0%, more preferably the same as the fragrance group having an orange note with respect to the total amount of the photocurable coating composition. Is 0.005 to 1.0%.

  If the blending amount of these Group A or Group B fragrances is less than 0.001%, the masking effect is not sufficiently obtained. On the other hand, if the amount exceeds 2.0%, the masking effect is sufficiently obtained. The aromaticity of the fragrance is too strong, which is not preferable for practical use. Moreover, the preferable weight ratio (A group fragrance | flavor: B group fragrance | flavor) of A group fragrance | flavor and B group fragrance | flavor becomes like this. Preferably it is 150: 1 to 1: 1, More preferably, it is 100: 1 to 1: 1. If the weight ratio is less than 150: 1, the masking effect is not sufficient, and if it exceeds 1: 1, the fragrance balance becomes poor.

  In the present invention, the role of the fragrance in the actual photocurable coating composition should be good in addition to masking, that is, neutralizing the acrylic odor. Therefore, for example, in addition to the fragrance having the orange note of the group A fragrance and the green note of the group B fragrance, conventionally known fragrance components described above can be used freely.

(B) Photopolymerization initiator The coating composition of the present invention contains a photopolymerization initiator.
A known photopolymerization initiator can be used as the photopolymerization initiator. In the present invention, when a radical polymerizable compound is used as the polymerizable compound, it is preferable to use a radical photopolymerization initiator. When a cationic polymerizable compound is used, a cationic photopolymerization initiator is used. It is preferable.
The photopolymerization initiator used in the coating composition of the present invention is a compound that generates a polymerization initiating species by absorbing external energy due to actinic radiation. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays. Although the wavelength to be used is not specifically limited, Preferably it is a 200-500 nm wavelength range, More preferably, it is a 200-450 nm wavelength range.

<Radical photopolymerization initiator>
Examples of radical photopolymerization initiators that can be preferably used in the present invention include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thios. Compound, (f) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, (l) carbon halogen bond And (m) alkylamine compounds and the like.
A preferable photopolymerization initiator from the viewpoint of transparency is preferably a compound having an absorbance at a wavelength of 400 nm of 0.3 or less when the photopolymerization initiator is formed to a thickness of 3 g / cm ^2. More preferably, the compound is 2 or less, and further preferably 0.1 or less.
Among these, preferable photopolymerization initiators include (a) aromatic ketones, (b) acylphosphine compounds, and (c) aromatic onium salt compounds.
The photopolymerization initiator in the present invention may be used alone or in combination.

<Cationic photopolymerization initiator>
In the present invention, as the cationic photopolymerization initiator (photoacid generator) used in combination with the cationic polymerizable compound, for example, a chemically amplified photoresist or a compound used for photocationic polymerization is used (for example, an organic electronics material). (Refer to Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187 to 192).
Examples of the cationic photopolymerization initiator suitable for the present invention are listed below.
That is, first, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salt of an aromatic onium compound such as diazonium, ammonium, iodonium, sulfonium or phosphonium. Can be mentioned. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide by light can also be used. Fourthly, iron arene complexes can be mentioned.
The cationic photopolymerization initiator as described above may be used alone or in combination of two or more.

The content of the photopolymerization initiator in the present invention is preferably 0.01 to 35% by weight, more preferably 0.1 to 30% by weight, based on the total amount of the polymerizable compound (C). More preferably, it is 0.5 to 30% by weight.
Moreover, when using a sensitizer described later, the photopolymerization initiator is preferably 200: 1 to 1: 200 in a weight ratio of photopolymerization initiator: sensitizer with respect to the sensitizer. It is more preferably 50: 1 to 1:50, and further preferably 20: 1 to 1: 5.

(C) Polymerizable compound The coating composition of this invention contains (C) polymeric compound.
As the polymerizable compound, a radical polymerizable compound can be used, and a cationic polymerizable compound can also be used.
<Radically polymerizable compound>
In the present invention, the radical polymerizable compound is preferably a compound having an ethylenically unsaturated bond.
The radical polymerizable compound in the present invention may be any compound as long as it has at least one ethylenically unsaturated bond, and includes compounds having chemical forms such as monomers, oligomers and polymers.
Only one type of radically polymerizable compound may be used, or two or more types thereof may be used in combination at an arbitrary ratio in order to improve target properties. From the viewpoint of controlling performance such as reactivity and physical properties, it is preferable to use two or more kinds of radically polymerizable compounds in combination.

  Examples of radically polymerizable compounds include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and other unsaturated carboxylic acids and salts thereof, anhydrides having ethylenically unsaturated bonds, acrylonitrile, styrene Furthermore, radically polymerizable compounds such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated urethanes can be mentioned.

  Specifically, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4- (Acryloxypolyethoxyphenyl) propane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene Glycol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate and other acrylic acid derivatives, methyl methacrylate, ethyl Methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene Glycol derivatives such as glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, N-vinylpyrrolidone, N-vinylcaprolactam Derivatives of allyl compounds such as N-vinyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc., more specifically, Shinzo Yamashita, “Handbook of cross-linking agents” (1981, Taiseisha); edited by Kiyomi Kato, “UV / EB Curing Handbook (raw material)” (1985, Polymer Publishing Society); edited by Radtech Research Group, “Application and Market of UV / EB Curing Technology”, page 79, (1989, CMC) Commercially available products described in Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun Co., Ltd.) or the like, or radically polymerizable or crosslinkable monomers, oligomers, and polymers known in the industry can be used.

  Examples of the radical polymerizable compound include those disclosed in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, and the like. Photocurable polymeric compound materials used for the described photopolymerizable compositions are known and can also be applied to the coating compositions of the present invention.

Furthermore, it is also preferable to use a vinyl ether compound as the radical polymerizable compound. Suitable vinyl ether compounds include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, and cyclohexanedimethanol. Di- or trivinyl ether compounds such as divinyl ether and trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl Monovinyl ether compounds such as ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl vinyl ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, etc. Is mentioned.
Among these vinyl ether compounds, a divinyl ether compound or a trivinyl ether compound is preferable from the viewpoint of curability, adhesion, and surface hardness, and a divinyl ether compound is particularly preferable. A vinyl ether compound may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.

  Examples of other polymerizable compounds that can be used in the present invention include (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, or (meth) acrylic acid esters such as urethane monomers or prepolymers (hereinafter referred to as “polymeric esters”). As appropriate, it is also referred to as “acrylate compound”). More preferably, they are the following compounds.

  That is, 2-ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalate neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxypolyethylene glycol acrylate, tetramethylol Methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol ethylene oxide (EO) adduct acrylate, Modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate , Phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, propylene oxide (PO) adduct diacrylate of bisphenol A, EO adduct diacrylate of bisphenol A, dipentaerythritol hexaacrylate, pentaerythritol triacrylate Tolylene diisocyanate urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydi Propylene glycol acrylate, ditrimethylolpropane tetraacrylate, Data triacrylate hexamethylene diisocyanate urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate, lactone-modified acrylate.

  The acrylate compounds listed here have high reactivity, low viscosity, and excellent adhesion to a printing substrate.

In the present invention, in order to further improve non-tackiness (surface tackiness) and transparency, among the above-mentioned radical polymerizable compounds, it is preferable to use a polyfunctional acrylate compound in combination.
As the polyfunctional acrylate, bisphenol A epoxy diacrylate and tripropylene glycol diacrylate can be particularly preferably exemplified.
Moreover, when using a polyfunctional ethylenically unsaturated compound, it is preferable that it is 5 to 80 weight% with respect to the total weight of a coating composition as content of a polyfunctional ethylenically unsaturated compound, 40-70 More preferably, it is% by weight. Within the above range, non-tackiness is excellent.

  In the present invention, depending on various purposes, a combination of a radical polymerizable compound and a radical photopolymerization initiator, a combination of a cationic polymerizable compound and a cationic photopolymerization initiator, or a combination of these radicals. -It is good also as a hybrid type coating composition of a cation.

<Cationically polymerizable compound>
The cationically polymerizable compound in the present invention is not particularly limited as long as it is a compound that generates and cures a cationic polymerization reaction by applying some energy, and can be used regardless of the type of monomer, oligomer, or polymer. Various known cationically polymerizable monomers known as photocationically polymerizable monomers that cause a polymerization reaction with an initiation species generated from the aforementioned cationic polymerization initiator can be used. The cationic polymerizable compound may be a monofunctional compound or a polyfunctional compound.

As the cationically polymerizable compound in the present invention, an oxetane ring-containing compound and an oxirane ring-containing compound are preferable from the viewpoint of curability and scratch resistance, and an embodiment containing both the oxetane ring-containing compound and the oxirane ring-containing compound is preferable. More preferred.
Here, in this specification, an oxirane ring-containing compound (hereinafter sometimes referred to as “oxirane compound” as appropriate) is a compound containing at least one oxirane ring (oxiranyl group, epoxy group) in the molecule. Specifically, it can be appropriately selected from those usually used as an epoxy resin, and examples thereof include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Any of a monomer, an oligomer, and a polymer may be sufficient. An oxetane ring-containing compound (hereinafter sometimes referred to as “oxetane compound” as appropriate) is a compound containing at least one oxetane ring (oxetanyl group) in the molecule.

Hereinafter, the cationically polymerizable compound applicable to the present invention will be described in detail.
Examples of the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-4006, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and 2001. Epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

  Examples of monofunctional epoxy compounds that can be used in the present invention include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide etc. are mentioned.

Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl) -7,8-epoxy-1,3-dioxaspiro [5.5] undecane, bis (3,4-epoxycyclohexyl) Rumethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate) , Epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Reserin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,13-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane 1,2,5,6-diepoxycyclooctane and the like.
Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of monofunctional vinyl ethers that can be used in the present invention include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Cyclohexylmethyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether Methoxypolyethylene Coal vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, Examples include chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxypolyethylene glycol vinyl ether, and the like.

Examples of the polyfunctional vinyl ether include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

  As the oxetane compound in the present invention, known oxetane compounds as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217 can be arbitrarily selected and used.

  The oxetane compound that can be used in the present invention is preferably a compound having 1 to 4 oxetane rings in its structure. By using such a compound, it becomes easy to maintain the viscosity of the liquid for ink-jet recording in a good handling range, and it is possible to obtain high adhesion of the cured ink to the recording medium. it can.

  Examples of monofunctional oxetane compounds used in the present invention include, for example, 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) Methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl [benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3 -Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl) -3-oxetanylmethyl) ether, 2-ethylhexyl (3- Til-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3- Oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxe) Nylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Examples include pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Examples of polyfunctional oxetane compounds include, for example, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene) ) Bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether , Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3 Ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3 -Ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl- 3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3- Til-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentane Kiss (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, Propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) Examples thereof include polyfunctional oxetanes such as ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

Such oxetane compounds are described in detail in JP-A No. 2003-341217, paragraphs 0021 to 0084, and the compounds described herein can be suitably used in the present invention.
Among the oxetane compounds used in the present invention, it is preferable to use a compound having 1 to 2 oxetane rings.
In the present invention, these cationically polymerizable compounds may be used alone or in combination of two or more.

The content of the polymerizable compound (C) in the photocurable coating composition of the present invention is in the range of 10 to 97% by weight with respect to the total weight of the coating composition from the viewpoint of curability and surface smoothness. The range of 30 to 95% by weight is more preferable, and the range of 50 to 90% by weight is particularly preferable.
Moreover, (C) polymeric compound may be used by 1 type, and may use 2 or more types together.

<Sensitizer>
A sensitizer can be added to the coating composition of the present invention in order to promote decomposition of the photopolymerization initiator by irradiation with active radiation.
The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photopolymerization initiator to cause actions such as electron transfer, energy transfer, and heat generation, thereby causing a chemical change of the photopolymerization initiator, that is, decomposition, radical, acid. Or it promotes the production of bases.
In addition, the sensitizer that can be used in the present invention is preferably a compound or an amount having a small influence of coloring or the like when the coating composition of the present invention is used for overprinting.
The content of the sensitizer in the present invention is preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight, based on the total weight of the coating composition. With this addition amount, curability is improved and the influence of coloring is small.

The sensitizer may be a compound corresponding to the wavelength of actinic radiation that generates an initiating species in the photopolymerization initiator to be used, but considering that it is used for a curing reaction of a general coating composition. Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, 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 (eg, anthraquinone), squalium (eg, Squalium), coumarins (for example, 7-diethylamino-4-methylcoumarin), benzophenones (for example, benzophenone) and the like.

  More preferable examples of the sensitizer include compounds represented by the following formulas (II) to (VI).

In the formula (II), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a non-nuclear group that forms a basic nucleus together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metal atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus. W represents an oxygen atom or a sulfur atom.

In formula (III), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in Formula (II).

In the formula (IV), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (V), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus together with adjacent A ³ , A ^4, and adjacent carbon atoms, R ⁶⁰ , R Each ⁶¹ is independently a hydrogen atom or a monovalent nonmetallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.

In the formula (VI), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or NR ⁶⁷ . R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ are each an aliphatic or aromatic ring. Can be combined to form

  Preferable specific examples of the compounds represented by formulas (II) to (VI) include those shown below. In the specific examples below, Ph represents a phenyl group, and Me represents a methyl group.

<Co-sensitizer>
The coating composition of the present invention can also contain a co-sensitizer.
In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizer to actinic radiation or suppressing polymerization inhibition of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. And JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like.
Specific examples include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-A-55-500806, and JP-A-5-142277, The disulfide compound of 56-75643 gazette etc. are mentioned.
Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like.

  Other examples include amino acid compounds (for example, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (for example, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (for example, trithiane), phosphorus compounds described in JP-A-6-250387 (for example, diethyl phosphite), Si described in JP-A-8-54735 -H, Ge-H compounds and the like.

<Surfactant>
The coating composition of the present invention may contain a surfactant.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. Further, an organic fluoro compound or a polysiloxane compound may be used as the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826. Among these, as the surfactant, polydimethylsiloxane can be preferably exemplified.
These surfactants may be used alone or in combination of two or more.

<Other ingredients>
If necessary, other components can be added to the coating composition of the present invention. Examples of other components include a polymerization inhibitor, a solvent, inorganic particles, and organic particles.
A polymerization inhibitor may be added from the viewpoint of enhancing the storage stability. The polymerization inhibitor is preferably added in an amount of 200 to 20,000 ppm based on the total amount of the coating composition of the present invention.
Examples of the polymerization inhibitor include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cuperon Al.
Inorganic particles such as Aerosil (Degussa silicon dioxide particles) and organic particles such as crosslinked polymethylmethacrylate (PMMA) are added to the coating composition of the present invention to intentionally reduce the surface gloss. A print layer or overprint can be formed.

In view of the fact that the coating composition of the present invention is a radiation curable coating composition, it is preferable that the coating composition of the present invention does not contain a solvent so that it can react quickly and be cured after application. However, a predetermined solvent can be included as long as the curing rate of the coating composition is not affected.
In the present invention, an organic solvent can be used as the solvent, and it is preferable that water is not substantially added from the viewpoint of curing speed. An organic solvent can be added to improve adhesion to a printing substrate (image receiving substrate such as paper).
When using an organic solvent, the amount is preferably as small as possible, preferably 0.1 to 5% by weight, and preferably 0.1 to 3% by weight, based on the total weight of the coating composition of the present invention. Is more preferable.

In addition, known compounds can be added to the coating composition of the present invention as necessary.
For example, surfactants, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes and the like are appropriately selected and added. be able to.

  Moreover, in order to improve the adhesiveness to printing base materials, such as polyolefin and a polyethylene terephthalate (PET), it is also preferable to contain the tackifier (tackifier) which does not inhibit superposition | polymerization. Specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, pages 5 to 6 (for example, (meth) acrylic acid and an alcohol having an alkyl group having 1 to 20 carbon atoms). Esters, copolymers of (meth) acrylic acid and C3-14 alicyclic alcohols, copolymers of (meth) acrylic acid and C6-14 aromatic alcohols), ethylenic Examples thereof include a low molecular weight tackifying resin having an unsaturated bond.

<Properties of photocurable coating composition>
The preferred physical properties of the photocurable coating composition of the present invention will be described.
When used as a photocurable coating composition, the viscosity at 25 to 30 ° C. is preferably 5 to 100 mPa · s, more preferably 7 to 75 mPa · s in consideration of applicability.
It is preferable that the composition ratio of the photocurable coating composition of the present invention is appropriately adjusted so that the viscosity is in the above range.
By setting the viscosity at 25 ° C. to 30 ° C. to the above value, an overprint having an overprint layer excellent in non-tackiness (no surface stickiness) and excellent in surface smoothness can be obtained.
The surface tension of the photocurable coating composition of the present invention is preferably 16 to 40 mN / m, and more preferably 18 to 35 mN / m.

(Overprint and manufacturing method thereof)
The overprint of the present invention has an overprint layer obtained by photocuring the coating composition of the present invention on a printed material.
The overprint forms at least one overprint layer on the surface of a printed material obtained by a printing method such as electrophotographic printing, inkjet printing, screen printing, flexographic printing, planographic printing, intaglio printing, or relief printing. It is what.
The overprint layer in the overprint of the present invention may be formed on a part of the printed matter or on the entire surface of the printed matter. In the case of a double-sided printed matter, it is formed on the entire surface of both sides of the printing substrate. It is preferable. Needless to say, the overprint layer may be formed in a non-printed portion of the printed material.
The printed material used for the overprint of the present invention is preferably an electrophotographic printed material. By forming an overprint layer, which is a cured layer of the coating composition of the present invention, on an electrophotographic printed matter, it is excellent in non-tackiness, surface smoothness and gloss, and visually similar to a silver salt photographic print. Can be obtained.
Further, since the overprint of the present invention is excellent in non-tackiness, even if a plurality of overprints of the present invention are stacked and stored for a long period of time, the overprints do not stick to each other and are excellent in storability.
The thickness of the overprint layer in the overprint of the present invention is preferably 1 to 10 μm, and more preferably 3 to 6 μm.

The overprint production method of the present invention includes a step of printing on a printing substrate to obtain a printed material, a step of applying the photocurable coating composition of the present invention on the printed material, and the photocurable coating composition. It is preferable to include a step of photocuring.
The overprint manufacturing method of the present invention includes a step of generating an electrostatic latent image on a latent image carrier, a step of developing the electrostatic latent image with toner, and printing the developed electrostatic image. A step of transferring to a substrate to obtain an electrophotographic printed material, a step of applying the photocurable coating composition of the present invention on the electrophotographic printed material, and a step of photocuring the photocurable coating composition. It is more preferable.
The printing substrate is not particularly limited, and known materials can be used. However, image receiving paper is preferable, plain paper or coated paper is more preferable, and coated paper is further used. preferable. As the coated paper, a double-sided coated paper is preferable because a full color image can be printed on both sides beautifully. When the printing substrate is paper or double-side coated paper, the preferred basis weight is 20 to 200 g / m ² , and the more preferred basis weight is 40 to 160 g / m ² .

The method for developing an image in electrophotography is not particularly limited, and can be arbitrarily selected from methods known to those skilled in the art. For example, a cascade method, a touchdown method, a powder cloud method, a magnetic brush method, and the like can be given.
Examples of a method for transferring the developed image to the printing substrate include a method using a corotron or a bias roll.
A fixing step for fixing an image in the electrophotographic method can be performed by various appropriate methods. Examples thereof include flash fixing, heat fixing, pressure fixing, and vapor fixing.
The image forming method, apparatus, and system by electrophotography are not particularly limited, and known ones can be used. Specifically, as described in the following US patents.
US Pat. No. 4,585,884, US Pat. No. 4,584,253, US Pat. No. 4,563,408, US Pat. No. 4,265,990, US Pat. US Pat. No. 6,180,308, US Pat. No. 6,212,347, US Pat. No. 6,187,499, US Pat. No. 5,966,570, US Pat. No. 5,627,002, US Pat. No. 5,366,840; US Pat. No. 5,346,795, US Pat. No. 5,223,368, and US Pat. 826, 147 specification.

In order to apply the photocurable coating composition, a commonly used liquid film coating device can be used. Specifically, roll coaters, rod coaters, blades, wire bars, dipping, air knives, curtain coaters, slide coaters, doctor knives, screen coaters, gravure coaters, offset gravure coaters, slot coaters, extrusion coaters, etc. It can be illustrated. These devices can be used in the same way as usual, but for example, direct and reverse roll coating, blanket coating, dampner coating, There are curtain coating, lithographic coating, screen coating, and gravure coating. In a preferred embodiment, the coating composition of the present invention is applied and cured using two or three roll coaters and a UV curing station.
Moreover, you may heat as needed at the time of application | coating and hardening of the coating composition of this invention.
Typical levels of coating weight of the coating composition of the present invention, a weight per unit area is preferably in the range of ^{1g / m 2 ~10g / m 2} , 3g / m 2 ~6g / m ² is more preferable.
The formation amount of the overprint layer in the overprint of the present invention, per unit area, it is preferably in the range of ^{1g / m 2 ~10g / m 2} , is 3g / m ² ~6g / m ² More preferred.

The energy source used to initiate the polymerization of the polymerizable compound contained in the coating composition of the present invention may be actinic, for example, radiation having a spectral ultraviolet or visible wavelength. ) (Active radiation). Polymerization by irradiation with actinic radiation is excellent in initiating polymerization and adjusting the polymerization rate.
Suitable actinic radiation irradiation sources include, for example, mercury lamps, xenon lamps, carbon arc lamps, tungsten filament lamps, lasers, sunlight, and the like.

  Under ultraviolet irradiation (UV light irradiation), irradiation with a medium pressure mercury lamp using a high-speed conveyor (preferably 20 to 70 m / min) is preferable, in which case UV light irradiation has a wavelength of 200 to 500 nm. And preferably for less than 1 second. More preferably, the speed of the high-speed conveyor is 15 to 35 m / min, and UV light having a wavelength of 200 to 450 nm is irradiated for 10 to 50 milliseconds (ms). The emission spectrum of the UV light source usually overlaps with the absorption spectrum of the UV polymerization initiator. Curing equipment used in some cases includes a reflector that collects and diffuses UV light, and a cooling system for removing heat generated by the UV light source. It is not limited.

<Properties of cured photocurable coating>
The cured product obtained by curing the photocurable coating composition of the present invention by ultraviolet irradiation (UV light irradiation) preferably has substantially no absorption in the visible region. “Substantially no absorption in the visible range” means that there is no absorption in the visible range of 400 to 700 nm, or that there is no absorption in the visible range to the extent that there is no problem as a photocurable coating. Means. Specifically, it means that the 5 μm optical path length transmittance of the coating composition is 70% or more, preferably 80% or more in the wavelength range of 400 to 700 nm.

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

[Example 1]
The following components were stirred with a stirrer to obtain a photocurable coating composition 1.
FA-513A (manufactured by Hitachi Chemical Co., Ltd.) 29% by weight
2-phenoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
N-vinylcaprolactam (Aldrich) 20% by weight
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
Fragrance A (Orange Oil Valencia) 0.7% by weight
Fragrance B (cis-3-cyclohexyl acetate) 0.3% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

[Examples 2 to 5]
Examples 2-5 obtained the photocurable coating composition like Example 1 except having changed the fragrance | flavor A of Example 1 and the fragrance | flavor B into the compound of Table 1. FIG.

Example 6
The following components were stirred with a stirrer to obtain a photocurable coating composition 6.
Tripropylene glycol diacrylate (Aldrich) 29% by weight
Lauryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 15% by weight
OTA-480 (Daicel Cytec Co., Ltd.) 25% by weight
(Glycerin propoxytriacrylate)
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
Fragrance A (Orange Oil Valencia) 0.7% by weight
Fragrance B (cis-3-cyclohexyl acetate) 0.3% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight
(Polyether-modified polymethylsiloxane)

[Examples 7 to 10]
Examples 7-10 obtained the photocurable coating composition like Example 6 except having changed the fragrance | flavor A of Example 6 and the fragrance | flavor B into the compound of Table 1. FIG.

Example 11
The following components were stirred with a stirrer to obtain a photocurable coating composition 11.
FA-513A (manufactured by Hitachi Chemical Co., Ltd.) 29% by weight
2-phenoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
N-vinylcaprolactam (Aldrich) 20% by weight
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
Fragrance A (Orange Oil Valencia) 1.0% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

Example 12
Example 12 obtained the photocurable coating composition like Example 11 except having changed the fragrance | flavor A of Example 11 into the compound of Table 1. FIG.

Example 13
The following components were stirred with a stirrer to obtain a photocurable coating composition 13.
FA-513A (manufactured by Hitachi Chemical Co., Ltd.) 29% by weight
2-phenoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
N-vinylcaprolactam (Aldrich) 20% by weight
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
Fragrance B (cis-3-cyclohexyl acetate) 1.0% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

Example 14
Example 14 obtained the photocurable coating composition like Example 13 except having changed the fragrance | flavor B of Example 13 into the compound of Table 1. FIG.

Example 15
The following components were stirred with a stirrer to obtain a photocurable coating composition 15.
Tripropylene glycol diacrylate (Aldrich) 29% by weight
Lauryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 15% by weight
OTA-480 (Daicel Cytec Co., Ltd.) 25% by weight
(Glycerin propoxytriacrylate)
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
Fragrance A (Orange Oil Valencia) 1.0% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

Example 16
Example 16 obtained the photocurable coating composition like Example 15 except having changed the fragrance | flavor A of Example 15 into the compound of Table 1. FIG.

Example 17
The following components were stirred with a stirrer to obtain a photocurable coating composition 17.
Tripropylene glycol diacrylate (Aldrich) 29% by weight
Lauryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 15% by weight
OTA-480 (Daicel Cytec Co., Ltd.) 25% by weight
(Glycerin propoxytriacrylate)
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
Fragrance B (cis-3-cyclohexyl acetate) 1.0% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

Example 18
Example 18 obtained the photocurable coating composition like Example 17 except having changed the fragrance | flavor B of Example 17 into the compound of Table 1. FIG.

Example 19
The following components were stirred with a stirrer to obtain a photocurable coating composition 19.
30% by weight of tripropylene glycol diacrylate (manufactured by Aldrich)
NK Ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 10% by weight
(Trimethylolpropane triacrylate)
DPCA-60 (Nippon Kayaku Co., Ltd.) 10% by weight
(Caprolactone-modified dipentaerythritol hexaacrylate)
Lauryl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
Fragrance A (Orange Oil Valencia) 0.7% by weight
Fragrance B (cis-3-cyclohexyl acetate) 0.3% by weight
1% by weight of polydimethylsiloxane (Aldrich)

Example 20
The following components were stirred with a stirrer to obtain a photocurable coating composition 20.
Celoxide 2021A (Daicel UCB) 20% by weight
(3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate)
OXT-221 (Toagosei Co., Ltd.) 45% by weight
(3,7-bis (3-oxetanyl) -5-oxanonane)
OXT-211 (Toagosei Co., Ltd.) 20% by weight
(3-ethyl-3-phenoxymethyloxetane)
TPS-TF (Ph ₃ —S ⁺ CF ₃ SO ₃ ⁻ : manufactured by Toyo Gosei Co., Ltd.) 12% by weight
9,10-dibutoxyanthracene 2% by weight
Fragrance A (Orange Oil Valencia) 0.7% by weight
Fragrance B (cis-3-cyclohexyl acetate) 0.3% by weight

[Comparative Example 1]
The following components were stirred with a stirrer to obtain a comparative photocurable coating composition 1.
FA-513A (manufactured by Hitachi Chemical Co., Ltd.) 30% by weight
2-phenoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
N-vinylcaprolactam (Aldrich) 20% by weight
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

[Comparative Example 2]
The following components were stirred with a stirrer to obtain a comparative photocurable coating composition 2.
FA-513A (manufactured by Hitachi Chemical Co., Ltd.) 29% by weight
2-phenoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
N-vinylcaprolactam (Aldrich) 20% by weight
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 4% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

[Comparative Example 3]
The following components were stirred with a stirrer to obtain a photocurable coating composition 3 for comparison.
FA-513A (manufactured by Hitachi Chemical Co., Ltd.) 30% by weight
2-phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 25% by weight
N-vinylcaprolactam (Aldrich) 20% by weight
Hexyl acrylate 18% by weight
Irgacure 907 (Ciba Specialty Chemicals) 5% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

[Comparative Example 4]
The following components were stirred with a stirrer to obtain a photocurable coating composition 4 for comparison.
30% by weight of tripropylene glycol diacrylate (manufactured by Aldrich)
Lauryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 15% by weight
OTA-480 (Daicel Cytec Co., Ltd.) 25% by weight
(Glycerin propoxytriacrylate)
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

[Comparative Example 5]
The following components were stirred with a stirrer to obtain a photocurable coating composition 5 for comparison.
Tripropylene glycol diacrylate (Aldrich) 29% by weight
Lauryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 15% by weight
OTA-480 (Daicel Cytec Co., Ltd.) 25% by weight
(Glycerin propoxytriacrylate)
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 4% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

[Comparative Example 6]
The following components were stirred with a stirrer to obtain a comparative photocurable coating composition 6.
30% by weight of tripropylene glycol diacrylate (manufactured by Aldrich)
Lauryl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
OTA-480 (Daicel Cytec Co., Ltd.) 25% by weight
(Glycerin propoxytriacrylate)
Hexyl acrylate 18% by weight
Irgacure 907 (Ciba Specialty Chemicals) 5% by weight
BYK-3510 (manufactured by BYK Chemie) 2% by weight

[Comparative Example 7]
The following components were stirred with a stirrer to obtain a comparative photocurable coating composition 7.
Tripropylene glycol diacrylate (Aldrich) 31% by weight
NK Ester A-TMPT (Shin Nakamura Chemical Co., Ltd.) 10% by weight
(Trimethylolpropane triacrylate)
DPCA-60 (Nippon Kayaku Co., Ltd.) 10% by weight
(Caprolactone-modified dipentaerythritol hexaacrylate)
Lauryl acrylate (Tokyo Chemical Industry Co., Ltd.) 20% by weight
Hexyl acrylate 15% by weight
Irgacure 907 (Ciba Specialty Chemicals) 10% by weight
Benzophenone (Tokyo Chemical Industry Co., Ltd.) 3% by weight
1% by weight of polydimethylsiloxane (Aldrich)

[Comparative Example 8]
The following components were stirred with a stirrer to obtain a comparative photocurable coating composition 8.
Celoxide 2021A (Daicel UCB) 20% by weight
(3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate)
OXT-221 (manufactured by Toagosei Co., Ltd.) 46% by weight
(3,7-bis (3-oxetanyl) -5-oxanonane)
OXT-211 (Toagosei Co., Ltd.) 20% by weight
(3-ethyl-3-phenoxymethyloxetane)
TPS-TF (Ph ₃ —S ⁺ CF ₃ SO ₃ ⁻ : Toyo Gosei Co., Ltd.) 12% by weight
9,10-dibutoxyanthracene 2% by weight

(Performance evaluation)
The performance of the photocurable coating compositions obtained in Examples and Comparative Examples was evaluated by the following method.
<Evaluation of surface smoothness (leveling property)>
For electrophotographic prints output to double-sided coated paper with a digital printer (DC8000) manufactured by Fuji Xerox Co., Ltd., coated on one side with a film thickness of 5 g / m ² using a UV varnish coater (SG610V) manufactured by Shinano Kenshi Co., Ltd. This was visually evaluated for the occurrence of vertical stripes on the surface of the coated printed material. The evaluation criteria are shown below.
◎: No vertical stripes ○: A little vertical stripes remain ×: Remarkably vertical stripes are observed

<Non-tackiness (surface stickiness suppression) evaluation>
It is obtained by applying a bar coating on one side of the electrophotographic printed matter outputted on a double-side coated paper with a digital printer (DC8000) manufactured by Fuji Xerox Co., Ltd. so that the coating composition has a film thickness of 5 g / m ^2. The coated film was exposed to 120 mJ / cm ² at an illuminance of 1.0 W / cm ² using a UV lamp (LC8) manufactured by Hamamatsu Photonics Co., Ltd., to prepare an overprint sample. The non-tackiness after exposure was evaluated by touch. The evaluation criteria are shown below.
◎: No stickiness ○: Almost no stickiness ×: With stickiness

  As a result of evaluation by the above-described method, the photocurable coating composition of Example 1 had a surface smoothness of ◎ and a non-tackiness of 性.

<Odor evaluation>
A varnish coater manufactured by Shinano Kenshi Co., Ltd. (SG610V) on one side of the electrophotographic printed material outputted on a double-side coated paper with a digital printer (DC8000) manufactured by Fuji Xerox Co., Ltd. so that the coating composition has a film thickness of 5 g / m ^2. ), The sensory evaluation was performed by smelling the odor and the odor level was evaluated according to the following criteria.
Evaluated by the following evaluation criteria (evaluation points) with 8 expert panelists.
Evaluation criteria (evaluation points):
5 (points): Eight out of eight people recognized the masking effect.
4 (points): 6 to 7 out of 8 people recognized the masking effect.
3 (points): 4 to 5 out of 8 people recognized the masking effect.
2 (points): 1 to 3 out of 8 people recognized the masking effect.
1 (point): No masking effect was observed.
In addition, when said evaluation score is 4 points or more, it is thought that there is no problem in practical use.

  The evaluation results are shown in Table 1 below.

Example 21
Twenty printed materials were produced by electrophotographic printing full color images of several frames each on both sides of A4 size double-side coated paper (basis weight 100 g / m ² ). Each of the photocurable coating compositions prepared in 10 was applied in the same manner as in Example 1 so that the coating amount was 5 g / m ² , and then irradiated with ultraviolet rays to prepare an overprint. When these were bound and used as a photo album together with the cover, a photo album with the same visibility as a silver halide photo print was obtained.

[Example 22]
A full color image including a menu photo and text were electrophotographic printed on both sides of 10 sheets of A3 size double coated paper (basis weight 100 g / m ² ). The photocurable coating compositions prepared in Examples 1 to 10 were applied to both sides of these printed materials in the same manner as in Example 1 so that the coating amount was 5 g / m ^{2 on} one side. Thereafter, ultraviolet light was irradiated to prepare a double-sided overprint. When these were bound into a restaurant menu, a restaurant menu was obtained that had the same visibility as a silver halide photographic print.

Claims (11)

(A) perfume,
(B) a photopolymerization initiator, and
(C) A photocurable coating composition comprising a polymerizable compound.   (A) The photocurable coating composition of Claim 1 in which a fragrance | flavor contains a natural fragrance | flavor.   (A) The photocurable coating composition of Claim 1 or 2 in which a fragrance | flavor contains a synthetic | combination fragrance | flavor.   (A) The photocurable coating composition of any one of Claims 1-3 in which a fragrance | flavor contains an ester compound.   (A) The photocurable coating composition of any one of Claims 1-4 in which a fragrance | flavor contains a terpene compound.   The photocurable coating composition according to any one of claims 1 to 5, which has substantially no absorption in the visible region.   The photocurable coating composition according to any one of claims 1 to 6, which is used for overprinting.   The photocurable coating composition according to any one of claims 1 to 7, which is used for overprinting an electrophotographic printed material.   The overprint which has the overprint layer which photocured the photocurable coating composition as described in any one of Claims 1-8 on printed matter.   The overprint which has the overprint layer which photocured the photocurable coating composition as described in any one of Claims 1-8 on an electrophotographic printed material. A step of obtaining an electrophotographic print by electrophotographic printing on a printing substrate;
Applying the photocurable coating composition according to any one of claims 1 to 8 on the electrophotographic printed material; and
A step of photocuring the photocurable coating composition.