WO2022210740A1 - Ink composition for forming surface-protecting layers - Google Patents

Ink composition for forming surface-protecting layers Download PDF

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Publication number
WO2022210740A1
WO2022210740A1 PCT/JP2022/015558 JP2022015558W WO2022210740A1 WO 2022210740 A1 WO2022210740 A1 WO 2022210740A1 JP 2022015558 W JP2022015558 W JP 2022015558W WO 2022210740 A1 WO2022210740 A1 WO 2022210740A1
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Prior art keywords
ink composition
acrylate
photopolymerizable compound
meth
cyclic structure
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PCT/JP2022/015558
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French (fr)
Japanese (ja)
Inventor
宗平 小谷
宏樹 林
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大日本塗料株式会社
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Publication of WO2022210740A1 publication Critical patent/WO2022210740A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • the present invention relates to an ink composition for forming a surface protective layer, and more particularly to an ink composition for forming a surface protective layer capable of forming a film having excellent weather resistance, blocking resistance, and stretchability.
  • Patent Document 1 discloses that a building board patterned with a yellow pigment, a magenta pigment, and a cyan pigment is provided with substantially the same color difference before and after discoloration, thereby reducing weather resistance. It describes an obfuscating invention. This is an effective method when inorganic pigments with excellent weather resistance are used, but the effect is insufficient for bright and easily faded designs such as organic pigments and dyes.
  • Patent Document 2 describes an invention relating to an active energy ray-curable inkjet ink composition having excellent weather resistance using a pigment ink containing a light stabilizer.
  • the coexistence of pigments has the problem of limiting the effect of light stabilizers.
  • Patent Document 3 describes an invention of a decorative sheet containing an ultraviolet absorber and a light stabilizer in a topcoat layer that covers a decorative portion.
  • the decorative sheet described in Patent Document 3 is produced by dry lamination, extrusion lamination, or the like.
  • there is a method to protect the decorative part by lamination or other method but it is necessary to separately protect the decorative layer with a laminating machine or the like.
  • the material selectivity was large, and there was a difficult problem.
  • Patent Document 4 proposes improving weather resistance by preparing clear ink separately. There was room.
  • a method for improving weather resistance for example, as described in Japanese Patent No. 6094771 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2011-148918 (Patent Document 6), an ultraviolet absorber or a radical scavenger is blended. method is known.
  • Patent Document 5 Japanese Patent No. 6094771
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2011-148918
  • an ultraviolet absorber or a radical scavenger is blended. method is known.
  • the sustainability of the effects of ultraviolet absorbers and radical scavengers has become a problem. has attempted to solve this problem.
  • Such a film with good weather resistance is suitable as a surface protective layer for protecting the decorative layer, but when applied as a surface protective layer, there are problems such as blocking resistance. Gender is also required.
  • an object of the present invention is to provide an ink composition for forming a surface protective layer capable of forming a film having excellent weather resistance, blocking resistance, and stretchability.
  • the present inventors have found that, in an ink composition containing a photopolymerizable compound, a photopolymerization initiator, and an ultraviolet absorber, a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure Combined use of a compound and a monofunctional photopolymerizable compound having a cyclic structure that does not contain a heteroatom, and by increasing the ratio of the monofunctional photopolymerizable compound in the photopolymerizable compound, provide excellent weather resistance and blocking resistance. It has been found that a film having excellent stretchability can be formed, and that such a film is suitable as a surface protective layer.
  • a first aspect of the present invention is an ink composition for forming a surface protective layer, comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) an ultraviolet absorber, wherein (A ) The photopolymerizable compound includes at least (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure and (A2) a monofunctional photopolymerizable compound having a heteroatom-free cyclic structure, and (A) light
  • the ink composition for forming a surface protective layer is characterized in that the ratio of the monofunctional photopolymerizable compound in the polymerizable compound is within the range of 75 to 95% by mass.
  • (A1) the monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure and (A2) the cyclic structure constituting the monofunctional photopolymerizable compound having a heteroatom-free cyclic structure is an aromatic ring. It is a cyclic structure that does not have.)
  • the photopolymerizable compound contains (A3) a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure.
  • the amount of (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure in the ink composition is 30 to 90% by mass. Within range.
  • the monofunctional photopolymerizable compound having a heteroatom-free cyclic structure does not contain isobornyl (meth)acrylate.
  • the ultraviolet absorber has a molar absorption coefficient of 1.5 ⁇ 10 3 (l ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ) at a wavelength of 385 nm. ) contains at least an ultraviolet absorber that is
  • Another preferred example of the ink composition for forming a surface protective layer of the present invention further contains (D) a radical scavenger other than methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT).
  • D a radical scavenger other than methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT).
  • the radical scavenger contains a hindered amine compound.
  • the ratio AM of the total number of moles of photopolymerizable functional groups AM of (A) the photopolymerizable compound and the number of moles of (D) the radical scavenger DM /DM is 10 or more.
  • Another preferred example of the ink composition for forming a surface protective layer of the present invention further contains a resin.
  • an ink composition for forming a surface protective layer capable of forming a film having excellent weather resistance, blocking resistance, and stretchability.
  • One aspect of the present invention is an ink composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) an ultraviolet absorber.
  • the ink composition of the present invention is preferably a photocurable ink composition.
  • the photocurable ink means an ink composition that can be cured by irradiation with active energy rays such as ultraviolet rays, visible rays, and electron beams.
  • the photopolymerizable compound has a functional group (for example, an acryloyl group, a methacryloyl group, a vinyl group or an allyl group constituting a carbon-carbon double bond that exhibits reactivity when irradiated with an active energy ray). It is a compound that undergoes a polymerization reaction via a group).
  • a photopolymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the amount of (A) the photopolymerizable compound in the ink composition of the present invention is preferably 70 to 95% by mass, more preferably 80 to 95% by mass, and more preferably 85 to 95% by mass. More preferred.
  • the photopolymerizable compound is classified into a monofunctional photopolymerizable compound or a polyfunctional photopolymerizable compound.
  • the monofunctional photopolymerizable compound includes a monofunctional photopolymerizable monomer having one functional group exhibiting reactivity when irradiated with an active energy ray (for example, a monofunctional photopolymerizable monomer having one photopolymerizable unsaturated group).
  • monomers monofunctional photopolymerizable oligomers having one functional group exhibiting reactivity upon irradiation with active energy rays (for example, monofunctional polymerizable oligomers having one photopolymerizable unsaturated group), and the like.
  • a polyfunctional photopolymerizable monomer having two or more functional groups exhibiting reactivity when irradiated with an active energy ray e.g., a polyfunctional photopolymerizable monomer having two or more photopolymerizable unsaturated groups.
  • monomers and polyfunctional photopolymerizable oligomers having two or more functional groups exhibiting reactivity upon irradiation with active energy rays e.g., polyfunctional photopolymerizable oligomers having two or more polymerizable unsaturated groups.
  • monofunctional photopolymerizable compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6 - hydroxyhexyl (meth)acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, stearyl (meth) acrylate, N-acryloylmorpholine, N-methacryloylmorpholine , ⁇ -butyrolactone (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, 4-t-butylcyclohexyl acrylate, dimethylacrylamide, hydroxyethylacrylamide, hydroxyethylmethacrylamide, diethylacrylamide, isopropylacrylamide, dimethylaminopropyl Ac
  • a monomer that does not leave an odor on the printed material when used in places where people can see it such as outdoor advertisements and plastic cardboard.
  • Morpholine, N-methacryloylmorpholine, 1-acryloylpyrrolidin-2-one, 1-methacryloylpyrrolidin-2-one, 1-acryloylpiperidin-2-one, 1-methacryloylpiperidin-2-one, 2-hydroxy-3-phenoxy Propyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, hydroxyethylmethacrylamide, dimethylaminopropyl Acrylamide, dimethylaminopropyl methacrylamide, 4-t-butylcyclohexyl acrylate and the like are preferred.
  • the ratio of the monofunctional photopolymerizable compound in (A) the photopolymerizable compound is preferably in the range of 75 to 95% by mass, and is in the range of 80 to 95% by mass. is more preferred.
  • polyfunctional photopolymerizable compounds a specific example of a polyfunctional photopolymerizable monomer (bifunctional photopolymerizable monomer) having two functional groups exhibiting reactivity upon irradiation with an active energy ray is 1,12-dodecanediol.
  • a monomer that does not leave an odor on the printed matter when used in places where people can see it such as outdoor advertisements and plastic cardboard.
  • Di(meth)acrylate, polypropylene glycol di(meth)acrylate and the like are preferred.
  • polyfunctional photopolymerizable monomers having three or more functional groups that exhibit reactivity upon irradiation with active energy rays include trimethylolpropane tri(meth)acrylate, ethoxy trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, EO modified Diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate and the like
  • (meth)acrylate means methacrylate or acrylate.
  • 2-hydroxyethyl (meth)acrylate is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
  • each (meth)acrylate may be the same or different. good.
  • the photopolymerizable compound preferably contains a monofunctional photopolymerizable compound having a cyclic structure.
  • Monofunctional photopolymerizable compounds having a cyclic structure can be classified into monofunctional photopolymerizable compounds having a heteroatom-containing cyclic structure and monofunctional photopolymerizable compounds having a heteroatom-free cyclic structure.
  • Heteroatoms refer to atoms other than carbon and hydrogen.
  • the photopolymerizable compound comprises (A1) a monofunctional photopolymerizable compound (preferably a monomer) having a heteroatom-containing cyclic structure and (A2) a heteroatom-free cyclic structure. It is preferable to include both monofunctional photopolymerizable compounds (preferably monomers) having However, the "cyclic structure containing a heteroatom" constituting "(A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure" is a cyclic structure having no aromatic ring, and "(A2 ) “a monofunctional photopolymerizable compound having a heteroatom-free cyclic structure” is a cyclic structure having no aromatic ring.
  • (A1) A monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure (heterocyclic structure) is preferable from the viewpoint of blocking resistance and stretchability of the resulting film.
  • the amount of (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure is preferably in the range of 30 to 90% by mass, more preferably in the range of 40 to 90% by mass. It is more preferably within the range of 40 to 80% by mass.
  • (A2) A monofunctional photopolymerizable compound having a heteroatom-free cyclic structure is preferable from the viewpoint of the balance between the adhesion and blocking resistance of the resulting film.
  • the amount of (A2) a monofunctional photopolymerizable monomer having a heteroatom-free cyclic structure is preferably in the range of 1 to 60% by mass, and 5 to 50% by mass. It is more preferably within the range, and still more preferably within the range of 5 to 40% by mass.
  • the total amount of (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure and (A2) a monofunctional photopolymerizable compound having a heteroatom-free cyclic structure is It is preferably within the range of 50 to 92% by mass.
  • Examples of (A1) monofunctional photopolymerizable compounds having a heteroatom-containing cyclic structure include N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylcaprolactam, ⁇ -butyrolactone (meth)acrylate, and N-vinyl-2.
  • -pyrrolidone cyclic trimethylolpropane formal (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, N-methacryloyloxyethylhexahydrophthalimide, 1-acryloylpyrrolidin-2-one, 1-methacryloylpyrrolidin-2-one, 1-acryloylpiperidin-2-one, 1-methacryloylpiperidin-2-one, N-vinylimidazole, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl (meth)acrylate and the like can be mentioned.
  • Examples of monofunctional photopolymerizable compounds having a heteroatom-free cyclic structure include 4-t-butylcyclohexyl acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and benzyl (meth)acrylate.
  • the monofunctional photopolymerizable compound having a heteroatom-free cyclic structure preferably has a boiling point of 180° C. or higher. In particular, 4-t-butylcyclohexyl acrylate is preferred.
  • the photopolymerizable compound includes isobornyl (meth)acrylate, particularly isobornyl (meth)acrylate, as (A2) a monofunctional photopolymerizable monomer having a heteroatom-free cyclic structure, from the viewpoint of suppressing odor. is preferably free of isobornyl acrylate.
  • Isobornyl (meth)acrylate has a peculiar odor, and when isobornyl (meth)acrylate is used, blocking resistance may be reduced due to difficulty in curing, and adhesion to plastic substrates may be reduced.
  • the photopolymerizable compound preferably contains (A3) a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure.
  • A3 By using a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure, it is possible to obtain a printed material having high curability and excellent blocking resistance.
  • the ratio of (A3) a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure contained in the photopolymerizable compound is preferably 3 to 20% by mass, more preferably 5 to 20% by mass, and further It is preferably within the range of 5 to 15% by mass.
  • the bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure is preferably a polyester acrylate.
  • the number of functional groups of the polyester acrylate is preferably 2 to 12, more preferably 2 to 4, and the molecular weight is preferably 5,000 or less.
  • the molecular weight of the polyester acrylate is the polystyrene-equivalent number-average molecular weight.
  • polyester acrylate CN2285 ⁇ CN2203 NS ⁇ CN2254 NS ⁇ CN2271 ⁇ CN2273 ⁇ CN2279 ⁇ CN2281 ⁇ CN2283 NS,CN8201 NS ⁇ CN7001 NS ⁇ CN2259 ⁇ CN2261 ⁇ CN292 ⁇ CN294 ⁇ CN299 ⁇ CN2282 ⁇ CN2295 ⁇ CN293 ⁇ CN296 ⁇ CN2267 ( ⁇ ) ⁇ U-200PA, UA-122P (manufactured by Shin-Nakamura Chemical Co., Ltd.), EBECRYL 436 ⁇ EBECRYL 438 ⁇ EBECRYL 450 ⁇ EBECRYL 524 ⁇ EBECRYL 525 ⁇ EBECRYL 800 ⁇ EBECRYL 811 ⁇ EBECRYL 812 ⁇ EBECRYL 1830 ⁇ EBECRYL 846 ⁇ EBECRYL 851 ⁇ EBECRYL 852 ⁇ EBECRYL 853 ⁇ EBECRYL 870 ⁇ EBECRYL 884 ⁇ EBECRYL 1885 ⁇ EBECRYL
  • the photopolymerizable compound in the ink composition of the present invention preferably does not contain a compound having an aromatic ring. Since the use of a compound having an aromatic ring tends to cause yellowing in the obtained film, it is preferable not to use a compound having an aromatic ring from the viewpoint of improving yellowing resistance. Further, even when the (A) photopolymerizable compound contains a compound having an aromatic ring, the amount of the compound having an aromatic ring contained in the (A) photopolymerizable compound is in the range of 40% by mass or less. It is preferably within the range of 30% by mass or less, more preferably within the range of 25% by mass or less.
  • Compounds having an aromatic ring include N-vinyl-2-pyrrolidone, N-acryloyloxyethylhexahydrophthalimide, N-methacryloyloxyethylhexahydrophthalimide, N-vinylimidazole, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol ( meth)acrylate, benzyl (meth)acrylate, neopentyl glycol (meth)acrylic acid benzoate, and the like.
  • the photopolymerizable compound may contain a polyfunctional photopolymerizable compound having a cyclic structure.
  • polyfunctional photopolymerizable compounds having a cyclic structure include tricyclodecanedimethanol diacrylate and cyclohexanedimethanol diacrylate.
  • the photopolymerizable compound preferably contains a photopolymerizable monomer having a glass transition temperature of 0°C or lower and a photopolymerizable monomer having a glass transition temperature of 85°C or higher.
  • the amount of each of the photopolymerizable monomer having a glass transition temperature of 0° C. or lower and the photopolymerizable monomer having a glass transition temperature of 85° C. or higher in the ink composition of the present invention is 10% by mass or more. is preferred, and 15% by mass or more is more preferred.
  • the Tg of the coating film as a whole is lower than room temperature, a high-molecular-weight film can be obtained, but the hardness is insufficient, and blocking resistance and abrasion resistance are often difficult.
  • the Tg of the entire coating film is higher than room temperature, the film is hard and the movement of molecules is restricted, so that the polymerization does not proceed sufficiently, and problems such as stickiness tend to occur.
  • These Tg, polymerizability, and the properties of the resulting coating film are derived from the side chain structure. By blending, it is possible to ensure curability and toughness of the film. Further, by designing the total Tg at 15° C. to 50° C., especially around 20° C. to 45° C., a more balanced design becomes possible.
  • the glass transition temperature (Tg) of a photopolymerizable monomer is the glass transition temperature of a homopolymer composed of the photopolymerizable monomer.
  • the theoretical value of the glass transition temperature of the cured coating film of the photopolymerizable ink obtained by combining these monomers can be obtained using the Fox equation.
  • the theoretical value of the glass transition temperature of the cured coating film [Tg (K)] is the glass transition temperature of the homopolymer of each polymer component (monomer and oligomer having an ethylenically unsaturated group) that forms the cured coating film. and can be obtained using the following Fox equation [equation (1)].
  • photopolymerizable monomers having a glass transition temperature of 0° C. or lower examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • acrylates 6-hydroxyhexyl (meth)acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, isodecyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, EO (ethylene oxide)-modified 2-ethylhexyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate and the like.
  • photopolymerizable monomers having a glass transition temperature of 85° C. or higher examples include N-acryloylmorpholine, N-methacryloylmorpholine, dimethylacrylamide, hydroxyethylacrylamide, hydroxyethylmethacrylamide, isopropylacrylamide, dimethylaminopropylacrylamide, and dimethylaminopropylmethacrylamide. , diacetone acrylamide, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate and the like.
  • the photopolymerizable compound is preferably a photopolymerizable compound whose homopolymer glass transition point is room temperature (23°C) or lower and whose viscosity is low.
  • a photopolymerizable compound can keep the viscosity of the ink low, facilitates the design of an ink with excellent ejection stability, has excellent curability, and has the effect of improving the copolymerizability of the ink. .
  • Examples of such (A) photopolymerizable compound include phenoxyethyl (meth)acrylate, phenoxydiethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, and 2-ethylhexyl-diglycol acrylate. , methoxydipropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate and the like.
  • it preferably contains a cyclic structure from the viewpoint of further improving curability, and in the present invention, it most preferably contains tetrahydrofurfuryl acrylate that does not contain ethylene oxide as a structural unit from the viewpoint of protecting the coating film from yellowing. .
  • the ink composition of the invention preferably does not contain a compound containing ethylene oxide as a structural unit.
  • a compound containing ethylene oxide as a structural unit When a compound containing ethylene oxide as a structural unit is used, the obtained film tends to yellow. Therefore, from the viewpoint of improving yellowing resistance, it is preferable not to use a compound containing ethylene oxide as a structural unit. .
  • the amount of the compound containing ethylene oxide as a structural unit contained in the ink composition of the present invention is 10 mass. % or less, more preferably 5 mass % or less, and even more preferably 3 mass % or less.
  • Compounds containing ethylene oxide as structural units include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, ethoxyethyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, glycidyl (meth)acrylate, allyl glycidyl ether, and various ethylene oxide-modified acrylates. etc.
  • the photopolymerization initiator has the effect of initiating the polymerization of the photopolymerizable compound described above when irradiated with an active energy ray.
  • the amount of the photopolymerization initiator (B) in the ink composition is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, even more preferably 3 to 15% by mass.
  • the content of the photopolymerization initiator is less than 1% by mass, the film may be poorly cured. Sometimes.
  • an auxiliary agent such as a photosensitizer may be used in combination.
  • Photopolymerization initiators include benzophenone-based compounds, acetophenone-based compounds, thioxanthone-based compounds, phosphine oxide-based compounds, and the like. It is preferred that the absorption wavelengths of the agents overlap as much as possible.
  • the photopolymerization initiator preferably contains an acylphosphine oxide-based initiator from the viewpoint of LED curing and coloring during curing.
  • a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.
  • photopolymerization initiator examples include: 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl ⁇ -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, bis
  • the ultraviolet absorber has the effect of absorbing ultraviolet rays and preventing deterioration due to ultraviolet rays.
  • UV absorbers include cyanoacrylate compounds, benzophenone compounds, benzoate compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, benzylidene camphor compounds, inorganic fine particles, and the like.
  • the (C) UV absorber preferably has a triazine skeleton, and among them, a hydroxyphenyltriazine-based compound that absorbs UV light at a shorter wavelength is preferable from the viewpoint of ink curability.
  • hydroxyphenyltriazine-based compounds solid ones are particularly preferable, and they tend to have lower fluidity than liquid ones and are less likely to bleed out.
  • the wavelength of the irradiated active energy ray and the absorption wavelength of (C) the ultraviolet absorber do not overlap as much as possible.
  • the (C) UV absorber may contain at least a UV absorber having a molar extinction coefficient of 1.5 ⁇ 10 3 (l ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ) or less at a wavelength of 385 nm. It preferably contains at least an ultraviolet absorber with a concentration of 2.0 ⁇ 10 2 (l ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ) or less.
  • the molar extinction coefficient of an ultraviolet absorber is calculated using Beer-Lambert's law based on the absorbance obtained by ultraviolet-visible absorption spectrum measurement.
  • Acetonitrile or tetrahydrofuran is used as a solvent for the measurement of the UV-visible absorption spectrum, and the UV-visible absorption spectrum is measured using a 1 cm cell at a concentration of 50 to 100 ⁇ M.
  • (C) As a specific example of the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone-2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole 2-[2'-hydroxy-3',5'-bis( ⁇ , ⁇ -(dimethylbenzyl)phenyl]benzotriazole, 2-(2'
  • the amount of (C) the ultraviolet absorber is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 5% by mass. preferably within If the amount of UV absorber is too high, the film may not cure sufficiently.
  • (C) UV absorbers may be used singly or in combination of two or more, but (C) UV absorbers preferably contain at least two UV absorbers. By using a plurality of types of ultraviolet absorbers having different structures, the effects of the ultraviolet absorbers can be maintained longer.
  • the UV absorber (C) preferably has a value B determined by the following formula (1) of 100 or more, more preferably 120 or more, in relation to the photopolymerizable compound. Yes, more preferably 200 or more. Also, the upper limit of the value B is, for example, 20000 or less.
  • B Formula (1)
  • the above formula (1) is derived from the compatibility (SP value) between the ultraviolet absorber (UVA) and the film and the molecular weight of UVA. When the value B is 100 or more, the effect of suppressing UVA bleed out is high.
  • the value B is less than 100, the difference (absolute value) between the SP values of the UVA and the photopolymerizable compound is large and/or the UVA has a low molecular weight, so the effect of suppressing the bleeding out of the ultraviolet absorber is low. Sometimes.
  • the SP values of UV absorbers and photopolymerizable compounds are Hansen solubility parameter values and are calculated using the Y-MB method.
  • the SP values of each photopolymerizable compound are SP 1 , SP 2 , . W 1 , W 2 , . . . , W n ( W 1 +W 2 + .
  • Average SP value SP 1 ⁇ W 1 +SP 2 ⁇ W 2 + . . . +SP n ⁇ W n
  • the ink composition of the present invention preferably contains (D) a radical scavenger.
  • the radical scavenger can scavenge free radicals and the like to improve photostability.
  • the (D) radical scavenger also includes a substance that reacts with free radicals and has a function of preventing polymerization reaction from occurring (so-called polymerization inhibitor).
  • polymerization inhibitor a function of preventing polymerization reaction from occurring.
  • Using a radical scavenger is also preferable from the viewpoint of preventing cracks from occurring.
  • Radical scavengers include hindered amine-based compounds, hydroquinone-based compounds, phenol-based compounds, phenothiazine-based compounds, nitroso-based compounds, N-oxyl-based compounds, and particularly hindered amine-based light stabilizers (HALS). preferable.
  • HALS hindered amine-based light stabilizers
  • the radical scavenger is preferably a radical scavenger other than methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT). Methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT) are less effective in preventing cracks than other radical scavengers.
  • radical scavengers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- ⁇ 2-(3-(3,5-di-t-butyl -4-hydroxyphenyl)propionyloxy)ethyl ⁇ -2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro ⁇ 4.5 ⁇ Hindered amine compounds such as decane-2,4-dione, phenol, o-, m- or p-cresol, 2-t-butyl-4-methylphenol, 6-t-butyl-2,4 -dimethylphenol, 2,6-di-t-butyl-4-methylphenol, 2-t-butylphenol, 4-t-butylphenol, 2,4-di-t-butylphenol, 2-methyl-4-t-butylphenol , phenolic compounds such as 4-
  • the amount of (D) the radical scavenger is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less. Too much radical scavenger may cause poor curing.
  • the lower limit of the content of the radical scavenger is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.
  • Radical scavengers may be used singly or in combination of two or more.
  • the ratio AM/DM of the total number of moles of photopolymerizable functional groups AM of (A) the photopolymerizable compound and the number of effective moles DM of (D) the radical scavenger is preferably 10 or more.
  • a radical scavenger has an effect of inhibiting polymerization because it captures radicals necessary for polymerization. Therefore, if a large amount of radical scavenger is blended, the curing rate will decrease.
  • AM/DM represents the ratio of the polymerizable component and the radical scavenger around the generated radicals, and if AM/DM is ⁇ 10, it is judged that the influence of the radical scavenger on the polymerization is sufficiently small. be.
  • the effective number of moles in the radical scavenger represents the number of functional groups capable of capturing radicals. For example, in the case of a molecule having five sites capable of scavenging radicals in one molecule, if the number of moles of the radical scavenger is 1 mole, the number of effective moles is 5 moles.
  • the ink composition of the present invention may contain a resin. By blending a resin into the ink composition, it is possible to improve the flying property and stability of the ink.
  • the resin used in the ink composition of the present invention is preferably a resin that does not have a functional group that exhibits reactivity when irradiated with active energy rays.
  • the resin may be used singly or in combination of two or more.
  • the amount of resin is preferably 5% by mass or less.
  • the number average molecular weight of the resin is preferably 500,000 or less, more preferably 20,000 or less.
  • the number average molecular weight is a value measured by gel permeation chromatography, and polystyrene is used as a standard substance.
  • resins include polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, chlorinated rubber, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate resin, acrylic resin, and polystyrene resin.
  • the ink composition of the present invention preferably contains at least one of a cellulose derivative and a polyvinyl alcohol derivative as a resin, and more preferably contains a cellulose derivative.
  • resins are highly effective in improving the flight properties and stability of the ink, and cellulose derivatives are particularly suitable.
  • cellulose derivatives include cellulose ether, cellulose ester, nitrocellulose, cellulose sulfate, cellulose phosphate, and cellulose acetate nitrate.
  • Cellulose ethers include, for example, methyl cellulose, ethyl cellulose, benzyl cellulose, trityl cellulose, cyanoethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, aminoethyl cellulose, oxyethyl cellulose (also referred to as hydroxyethyl cellulose) and the like.
  • Cellulose esters include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate and the like.
  • cellulose derivatives include acrylic-modified cellulose derivatives, polyester-modified cellulose derivatives, and polyurethane-modified cellulose derivatives.
  • Acryl-modified cellulose derivatives are compounds obtained by graft-polymerizing acrylic components such as (meth)acrylates onto cellulose derivatives such as cellulose ethers and cellulose esters.
  • Polyester-modified cellulose derivatives are cellulose derivatives such as cellulose ethers and cellulose esters, and polyester components such as polytrimethylene terephthalate, polyethylene terephthalate and polybutylene terephthalate (that is, components having a plurality of ester bonds in the main chain). It is a compound obtained by binding.
  • a polyurethane-modified cellulose derivative is a compound obtained by reacting, for example, an isocyanate prepolymer with a hydroxyl group of a cellulose derivative such as a cellulose ether or a cellulose ester.
  • cellulose acetate alkylate is preferred, cellulose acetate alkylate substituted with an acyl group having about 1 to 6 carbon atoms is more preferred, and cellulose acetate propionate and cellulose acetate butyrate are even more preferred.
  • the ink composition of the present invention may contain coloring agents such as dyes and pigments, but in that case, it is preferable to contain pigments from the viewpoint of weather resistance.
  • coloring agents such as dyes and pigments
  • the content of the coloring agent is, for example, 0.1 to 15% by mass in the ink composition.
  • a coloring agent may be used individually by 1 type, and may be used in combination of 2 or more types.
  • colorants include: C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 32, 34, 35, 36, 37, 41, 42, 43, 49, 53, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 128, 129, 130, 133, 138, 139, 150, 151, 152, 153, 154, 155, 165, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 191, 193, 194, 199, 205, 206, 209, 212, 21
  • I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28, Examples include aluminum flakes, glass flakes, pearl pigments and hollow particles.
  • the ink composition of the present invention may contain various compounds for the purpose of imparting functionality.
  • Indium-tin composite oxide, antimony-tin composite oxide, etc. may be contained in order to impart a heat-absorbing function to the film obtained, and fine-particle titanium oxide, fine-particle zirconium oxide, etc. may be added to increase the refractive index of the resulting film. may contain.
  • the pigment particles dispersed in the ink composition preferably have a volume average particle diameter of 0.05 to 0.4 ⁇ m and a maximum volume particle diameter of 0.2 to 1 ⁇ m. .
  • the volume average particle size is larger than 0.4 ⁇ m and the volume maximum particle size is larger than 1 ⁇ m, it tends to be difficult to stably eject the ink composition.
  • the volume average particle size and the volume maximum particle size can be measured with a measuring instrument using a dynamic light scattering method.
  • the ink composition of the present invention may further contain a pigment dispersant in order to disperse the pigment.
  • the content of the pigment dispersant is, for example, 0.1 to 5% by mass in the ink composition.
  • Pigment dispersants may be used singly or in combination of two or more.
  • pigment dispersants include: ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-
  • the ink composition of the present invention may further contain a surface modifier from the viewpoint of improving wettability.
  • a surface modifier means a substance that has a hydrophilic site and a hydrophobic site in its molecular structure and that can be added to adjust the surface tension of the ink composition.
  • anionic surface modifiers such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts
  • polyoxyethylene alkyl ethers polyoxyethylene nonionic surface conditioners such as alkylallyl ethers, acetylene glycols, and polyoxyethylene/polyoxypropylene
  • silicon-based surface conditioners and acrylic-based surface conditioners are preferred, and commercially available products such as BYK-Chemie, Evonik, and Dow Corning Toray can be used.
  • a silicone-based surface conditioner it is preferably a polyether-modified silicone oil and has an HLB of 7.6 to 12.
  • the amount of the surface modifier can be appropriately selected depending on the purpose of use, but is preferably 0.01 to 1% by mass in the ink composition, for example.
  • the surface conditioners may be used singly or in combination of two or more.
  • surface conditioners include: BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-325, BYK-326, BYK- 330, BYK-331, BYK-333, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-370, BYK-375, BYK-377, BYK-378, BYK-381, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYK- 3455, BYK-3550, BYK-3560, BYK
  • the ink composition of the present invention contains, as other components, an antioxidant, a plasticizer, a rust inhibitor, a solvent, a filler, an antifoaming agent, a charge control agent, a stress relaxation agent, a penetrating agent, a light guide material, and a glitter material.
  • an antioxidant e.g., an antioxidant, a plasticizer, a rust inhibitor, a solvent, a filler, an antifoaming agent, a charge control agent, a stress relaxation agent, a penetrating agent, a light guide material, and a glitter material.
  • a magnetic material e.g., a fluorescent substance, an antibacterial agent, an antiviral agent, an anti-algae agent, and the like may be used as necessary.
  • the ink composition of the present invention is obtained by mixing various components appropriately selected as necessary, and optionally using a filter having a pore size of about 1/10 or less of the nozzle diameter of the ink jet print head to be used. can be prepared by filtering the resulting mixture.
  • the ink composition of the present invention preferably has a viscosity at 40°C of 5 to 25 mPa ⁇ s, more preferably 5 to 15 mPa ⁇ s. If the ink viscosity at 40° C. is within the specified range, good ejection stability can be obtained. Ink viscosity can be measured using a cone-plate viscometer.
  • the ink composition of the present invention preferably has a surface tension of 20 to 35 mN/m at 25°C, more preferably 23 to 28 mN/m. If the surface tension of the ink at 25° C. is within the specified range, good ejection stability can be obtained. Ink surface tension can be measured by the plate method.
  • the ink composition of the present invention is preferably clear ink.
  • clear ink refers to a clear ink having a light transmittance of 80% or more in a wavelength range of 380 to 800 nm when a film having a thickness of 30 ⁇ m is formed, and the light transmittance is preferably 90% or more. , more preferably 95% or more, and still more preferably 97% or more.
  • the light transmittance is measured according to JIS K7361-1:1997 "Plastics-Testing method for total light transmittance of transparent materials-Part 1: Single beam method".
  • the ink composition of the present invention is preferably used for surface protection, and is suitable as an ink composition for forming surface protection.
  • the ink composition of the present invention is preferably a clear ink for protecting the surface of a decorative layer, particularly a decorative layer containing a dye or an organic pigment.
  • the decorative layer is, for example, a decorative layer formed of at least one of paint, ink (eg, printing ink, inkjet ink), and powder toner.
  • the glass transition temperature of the film formed from the ink composition of the present invention is preferably 15 to 50°C.
  • the glass transition point for heating the ink for printing and curing is 60° C. or lower.
  • the glass transition temperature (Tg) of the film formed from the ink composition is calculated using the FOX formula.
  • Another aspect of the present invention is a printing method using the ink composition of the present invention.
  • the printing method of the present invention is characterized by performing printing (preferably inkjet printing) on the surface of the decorative layer with the ink composition of the present invention described above.
  • the contents described in the description of the ink composition of the present invention also apply to the printing method of the present invention.
  • the decorative layer is a colored layer containing coloring agents such as dyes and pigments, and is used for decoration.
  • the decorative layer is, for example, a decorative layer formed of at least one of paint, ink (eg, printing ink, inkjet ink), and powder toner.
  • the decorative layer contains resins, ultraviolet absorbers, radical scavengers, antioxidants, plasticizers, antirust agents, anti-algae agents, antibacterial agents, antiviral agents, fillers, charge control agents, conductors.
  • Luminescent materials, luster materials, magnetic materials, phosphors, waxes, and the like can be included as necessary.
  • the decorative layer is formed on at least part of the surface of the base material and the undercoat layer formed on the base material.
  • the shape of the substrate includes, for example, a film shape, a sheet shape, a plate shape, and the like.
  • materials for the substrate include plastics such as epoxy resin, ABS resin, polycarbonate, polyvinyl chloride, polystyrene, acrylic resin, particularly polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP), etc.
  • plastics such as epoxy resin, ABS resin, polycarbonate, polyvinyl chloride, polystyrene, acrylic resin, particularly polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP), etc.
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • PP polypropylene
  • metals such as iron, stainless steel and aluminum, wood, cement, concrete, gypsum, calcium silicate, calcium carbonate, and glass.
  • base materials include PVC sheet, tarpaulin, plastic cardboard (cardboard made of plastic), acrylic board, flexible board, calcium silicate board, gypsum slag barite board, calcium carbonate board, wood chip cement board, precast concrete board, lightweight Examples include foamed concrete (ALC) boards, gypsum boards, tiles, and glass boards.
  • ALC foamed concrete
  • the base material may be surface-treated.
  • the substrate may have a primer layer on its surface.
  • printing is preferably carried out by an inkjet printing method, but is not limited thereto, and gravure printing, offset printing, flexographic printing, screen printing, coater method, spray printing, etc. It is also possible to carry out by various printing methods such as a system.
  • inkjet printing it can be used for various inkjet printers.
  • inkjet printers include inkjet printers that eject an ink composition by a charge control method or a piezo method.
  • a large-sized inkjet printer as a specific example, an inkjet printer for the purpose of printing on articles produced on an industrial line can also be suitably used.
  • a layer covering the decorative layer is formed by printing using the ink composition of the present invention.
  • This layer is preferably a clear layer.
  • the clear layer has a light transmittance of 80% or more, preferably 90% or more, more preferably 95% or more, and still more preferably 97% or more in the wavelength range of 380 to 800 nm when the thickness is 30 ⁇ m. and can be formed from the clear ink described above.
  • the ink composition of the present invention when there is a portion where the decorative layer does not exist on a part of the surface of the base material or the undercoat layer formed on the base material, the ink composition of the present invention can be used.
  • the layer to be formed may be formed on the surface of a base material or an undercoat layer formed on the base material.
  • a layer formed by printing using the ink composition of the present invention is cured by irradiation with active energy rays such as ultraviolet rays.
  • active energy rays such as ultraviolet rays.
  • a high-pressure mercury lamp, a metal halide lamp, an LED lamp, or the like can be used as a light source for active energy rays.
  • the wavelength of the active energy ray irradiated to cure this layer preferably overlaps with the absorption wavelength of the photopolymerization initiator, and the dominant wavelength of the active energy ray is preferably 350 to 400 nm. It is preferable that the integrated amount of active energy rays is in the range of 100 to 2000 mJ/cm 2 .
  • the ink composition of the present invention can be subjected to surface finishing such as gloss tone and matte tone by appropriately selecting ejection conditions for inkjet printing and subsequent curing conditions. For example, if the ink composition spreads and then cures after a period of time, it will have a gloss finish, and if the ink droplets remain in the form of a lens and harden, it will have a matte finish.
  • the printed matter of the present invention comprises a decorative layer and a layer positioned on the decorative layer, wherein the layer positioned on the decorative layer is a layer formed from the ink composition of the present invention described above. and preferably a clear layer.
  • the contents described in the description of the ink composition of the present invention and the printing method of the present invention also apply to the printed matter of the present invention.
  • the decorative layer is arranged on at least part of the surface of the base material or the undercoat layer positioned on the base material.
  • the printed matter of the present invention can be a printed matter comprising a base material, a decorative layer positioned on the base material, and a layer positioned on the decorative layer and formed from the ink composition of the present invention. and comprises a substrate, an undercoat layer positioned on the substrate, a decorative layer positioned on the undercoat layer, and a layer positioned on the decorative layer and formed from the ink composition of the present invention. It can also be printed.
  • the layer formed by the ink composition of the present invention is a layer covering at least a part of the decorative layer, and the layer formed by the ink composition of the present invention It is preferably a layer that covers the entire surface of the decorative layer.
  • the layer formed from the ink composition of the present invention is or an undercoat layer.
  • Photopolymerizable compound Compound name/product name (manufacturer), molecular weight (g/mol), Tg (K) 1) Acryloylmorpholine (KJ Chemicals Co., Ltd.), 141, 418 2) N-vinylcaprolactam (BASF), 139, 363 3) (3-ethyloxetan-3-yl)methyl acrylate (Osaka Organic Chemical Industry Co., Ltd.), 170, 275 4) (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (Osaka Organic Chemical Industry Co., Ltd.), 200, 266 5) Cyclic trimethylolpropane formal acrylate (Osaka Organic Chemical Industry Co., Ltd.), 200, 300 6) Tetrahydrofurfuryl acrylate (Kyoeisha Chemical Co., Ltd.), 156, 261 7) Isobornyl acrylate (K) 1) Acryloylmorpholine (KJ Chemical
  • ⁇ Weather resistance test 2 Crack resistance> Accelerated weather resistance (based on JIS K 5600-7-7:2008) ⁇ Weather resistance test 1.
  • a cured film was prepared in the same manner as in Yellowing resistance>, and an accelerated weather resistance test was performed. After conducting the test up to 1500 hours, the appearance of the coating film was visually evaluated based on the following criteria. The results are shown in Tables 1-5. [Evaluation criteria] ⁇ : No cracks at all even after 1500 hours of test time. ⁇ : Cracks occurred at the test time of 1200 to 1500 hours. ⁇ : Cracks occurred after 1000 to 1200 hours of test time. x: Cracks occurred 1000 hours before the test time.
  • ⁇ Adhesion> A printed matter obtained in the same manner as in weather resistance test 1 was subjected to a cross cut of 100 squares with a width of 1 mm on the printed layer. Thereafter, the cross-cut surface was bent at 90°, the cellophane tape was sufficiently adhered, the cellophane tape was peeled off, and the adhesion was evaluated according to the following criteria. The results are shown in Tables 1-5. [Evaluation criteria] A: Peeling is not observed at the cut portion. ⁇ : Less than 5% peeling was observed at the cut portion. ⁇ : Peeling of 5% or more and less than 20% was confirmed at the cut portion. x: Peeling of 20% or more was confirmed at the cut portion.
  • the ink was applied using a bar coater #10 on a polyvinyl chloride sheet with release paper on the back, and then exposed to an active energy ray (dominant wavelength 385 nm ) was irradiated and sufficiently cured to produce a printed matter. After that, it was cut into a size of 50 mm long and 10 mm wide, and the release paper on the back was peeled off to obtain a sample for measurement. The sample for measurement was subjected to a tensile test at 23° C.
  • (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure/ink composition is (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure in the ink composition. Shows the ratio (mass%) of.
  • (A2) monofunctional photopolymerizable/ink composition having a heteroatom-free cyclic structure in the table refers to (A2) monofunctional photopolymerizable having a heteroatom-free cyclic structure in the ink composition. The ratio (% by mass) of the compound is shown.
  • (A3) polyfunctional photopolymerizable compound having a polyester structure/ink composition indicates the proportion (mass %).
  • “Monofunctional polymerizable compound/photopolymerizable compound” in the table indicates the proportion (% by mass) of the monofunctional photopolymerizable compound in the photopolymerizable compound.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract

The present invention pertains to an ink composition for forming surface-protecting layers which is capable of forming a film having excellent weather resistance, blocking resistance and stretching properties, and more specifically, an ink composition for forming surface-protecting layers which contains (A) a photopolymerizable compound, (B) a photopolymerization initiator and (C) an ultraviolet absorber, said composition being characterized in that: (A) the photopolymerizable compound at least contains (A1) a monofunctional photopolymerizable compound which has a cyclic structure containing a heteroatom and (A2) a monofunctional photopolymerizable compound which has a cyclic structure which does not contain a heteroatom; and the monofunctional photopolymerizable compounds constitute a proportion in the range of 75-100 mass% of (A) the photopolymerizable compound (the cyclic structures which constitute (A1) the monofunctional photopolymerizable compound which has a cyclic structure containing a heteroatom and (A2) the monofunctional photopolymerizable compound which has a cyclic structure which does not contain a heteroatom are cyclic structures which do not have an aromatic ring).

Description

表面保護層形成用インク組成物Ink composition for forming surface protective layer
　本発明は、表面保護層形成用インク組成物に関し、耐候性に優れるとともに耐ブロッキング性、延伸性にも優れる膜を形成可能な表面保護層形成用インク組成物に関するものである。 The present invention relates to an ink composition for forming a surface protective layer, and more particularly to an ink composition for forming a surface protective layer capable of forming a film having excellent weather resistance, blocking resistance, and stretchability.
　近年、インクジェットプリンタ等による印刷技術の向上によって、様々な意匠を有する印刷物が広く普及している。特に、活性エネルギー線等によって硬化する光硬化型インクは、プラスチックや塩ビシート等のインクを吸収しにくい非吸収性あるいは難吸収性メディアに対する加飾において、速乾性があり、滲みの少ない画像を提供できることから、利用の幅が広がってきている。しかしながら、これら印刷物を屋外に設置したとき、インク加飾部が光によって劣化しやすくなり、印刷物が退色して、経時で見た目が悪くなる課題があった。 In recent years, printed materials with various designs have become widespread due to improvements in printing technology such as inkjet printers. In particular, photo-curable inks that are cured by active energy rays, etc., can be used to decorate non-absorbent or non-absorbent media such as plastics and vinyl chloride sheets that do not easily absorb ink. Since it can be used, the range of use is expanding. However, when these printed materials are installed outdoors, the ink-decorated portion is likely to deteriorate due to light, and the printed materials fade, resulting in a problem that the appearance deteriorates over time.
　特開２０１１－４７１５２号公報（特許文献１）は、イエロー顔料、マゼンタ顔料、シアン顔料で模様付けされている建築板について、変退色前後の色差を略同一とすることで、耐候性の低下を分かりにくくする発明を記載している。これは、耐候性に優れる無機顔料を用いた際には効果的な手法であるが、有機顔料や染料等の鮮やかで退色し易い意匠面においては効果が不十分であった。 Japanese Patent Application Laid-Open No. 2011-47152 (Patent Document 1) discloses that a building board patterned with a yellow pigment, a magenta pigment, and a cyan pigment is provided with substantially the same color difference before and after discoloration, thereby reducing weather resistance. It describes an obfuscating invention. This is an effective method when inorganic pigments with excellent weather resistance are used, but the effect is insufficient for bright and easily faded designs such as organic pigments and dyes.
　特開２０１２－２１４６０３号公報（特許文献２）は、光安定剤を含む顔料インクを用いた、耐候性に優れる活性エネルギー線硬化型インクジェットインク組成物に関する発明を記載しているが、インク中に顔料が共存することで、光安定剤の効果が限定的になる課題があった。 Japanese Patent Application Laid-Open No. 2012-214603 (Patent Document 2) describes an invention relating to an active energy ray-curable inkjet ink composition having excellent weather resistance using a pigment ink containing a light stabilizer. The coexistence of pigments has the problem of limiting the effect of light stabilizers.
　特開２０１９－３０９９８号公報（特許文献３）は、加飾部を覆うトップコート層に紫外線吸収剤と光安定剤を含む化粧シートの発明を記載している。特許文献３に記載の化粧シートは、ドライラミネート又は押出ラミネートなどで製造される。このように、ラミネート等の手法で加飾部を保護する方法があるが、加飾層をラミネート機等で別途保護処理する必要があり、また、透明なラミネート材に、紫外線吸収剤と光安定剤を溶かし込んで加工し、さらに耐候性を持続させる効果を発現するためには、材料選択性が大きく、難しい課題があった。 Japanese Patent Application Laid-Open No. 2019-30998 (Patent Document 3) describes an invention of a decorative sheet containing an ultraviolet absorber and a light stabilizer in a topcoat layer that covers a decorative portion. The decorative sheet described in Patent Document 3 is produced by dry lamination, extrusion lamination, or the like. As described above, there is a method to protect the decorative part by lamination or other method, but it is necessary to separately protect the decorative layer with a laminating machine or the like. In order to achieve the effect of dissolving and processing the agent and maintaining the weather resistance, the material selectivity was large, and there was a difficult problem.
　これら課題に対して、特開２０１９－８１８６７号公報（特許文献４）ではクリアインクを別途用意することで耐候性を向上させることを提案しているが、クリアインクの耐候性向上には改善の余地があった。耐候性を向上させる手法としては、例えば特許第６０９４７７１号公報（特許文献５）や特開２０１１－１４８９１８号公報（特許文献６）に記載されるように、紫外線吸収剤やラジカル捕捉剤を配合する方法が知られている。しかしながら、これらは経時で印刷膜からブリードしやすいため、紫外線吸収剤やラジカル捕捉剤の効果の持続性が課題となっており、特許文献６では、紫外線吸収剤の選択やラジカル捕捉剤の分子量調整によって、この課題の解決が図られている。 To address these issues, Japanese Patent Laid-Open No. 2019-81867 (Patent Document 4) proposes improving weather resistance by preparing clear ink separately. There was room. As a method for improving weather resistance, for example, as described in Japanese Patent No. 6094771 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2011-148918 (Patent Document 6), an ultraviolet absorber or a radical scavenger is blended. method is known. However, since these tend to bleed from the printed film over time, the sustainability of the effects of ultraviolet absorbers and radical scavengers has become a problem. has attempted to solve this problem.
特開２０１１－４７１５２号公報JP 2011-47152 A 特開２０１２－２１４６０３号公報JP 2012-214603 A 特開２０１９－３０９９８号公報JP 2019-30998 A 特開２０１９－８１８６７号公報JP 2019-81867 A 特許第６０９４７７１号公報Japanese Patent No. 6094771 特開２０１１－１４８９１８号公報JP 2011-148918 A
　上記のように、光硬化型インクにより得られる膜の耐候性を改善する手法について種々提案されている。そして、このような耐候性が良好な膜は、加飾層を保護する表面保護層として好適であるものの、表面保護層として適用する場合には、耐ブロッキング性などの課題があり、また、延伸性なども求められる。 As described above, various methods have been proposed for improving the weather resistance of films obtained with photocurable inks. Such a film with good weather resistance is suitable as a surface protective layer for protecting the decorative layer, but when applied as a surface protective layer, there are problems such as blocking resistance. Gender is also required.
　そこで、本発明の目的は、耐候性に優れるとともに耐ブロッキング性、延伸性にも優れる膜を形成可能な表面保護層形成用インク組成物を提供することにある。 Accordingly, an object of the present invention is to provide an ink composition for forming a surface protective layer capable of forming a film having excellent weather resistance, blocking resistance, and stretchability.
　本発明者は、上記目的を達成するために鋭意検討した結果、光重合性化合物、光重合開始剤、紫外線吸収剤を含むインク組成物において、ヘテロ原子を含む環状構造を有する単官能光重合性化合物とヘテロ原子を含まない環状構造を有する単官能光重合性化合物とを併用するとともに、光重合性化合物中の単官能光重合性化合物の割合を高めることで、耐候性に優れるとともに耐ブロッキング性、延伸性にも優れる膜を形成することができ、かかる膜は表面保護層として好適であることを見出した。 As a result of intensive studies to achieve the above object, the present inventors have found that, in an ink composition containing a photopolymerizable compound, a photopolymerization initiator, and an ultraviolet absorber, a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure Combined use of a compound and a monofunctional photopolymerizable compound having a cyclic structure that does not contain a heteroatom, and by increasing the ratio of the monofunctional photopolymerizable compound in the photopolymerizable compound, provide excellent weather resistance and blocking resistance. It has been found that a film having excellent stretchability can be formed, and that such a film is suitable as a surface protective layer.
　したがって、本発明の第１の態様は、（Ａ）光重合性化合物、（Ｂ）光重合開始剤、（Ｃ）紫外線吸収剤を含む、表面保護層形成用インク組成物であって、（Ａ）光重合性化合物が（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物と（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物を少なくとも含み、（Ａ）光重合性化合物中の単官能光重合性化合物の割合が７５～９５質量％の範囲内であることを特徴とする、表面保護層形成用インク組成物である。（ただし、（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物および（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物を構成する前記環状構造は、芳香環を有しない環状構造である。） Accordingly, a first aspect of the present invention is an ink composition for forming a surface protective layer, comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) an ultraviolet absorber, wherein (A ) The photopolymerizable compound includes at least (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure and (A2) a monofunctional photopolymerizable compound having a heteroatom-free cyclic structure, and (A) light The ink composition for forming a surface protective layer is characterized in that the ratio of the monofunctional photopolymerizable compound in the polymerizable compound is within the range of 75 to 95% by mass. (However, (A1) the monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure and (A2) the cyclic structure constituting the monofunctional photopolymerizable compound having a heteroatom-free cyclic structure is an aromatic ring. It is a cyclic structure that does not have.)
　本発明の表面保護層形成用インク組成物の好適例においては、（Ａ）光重合性化合物が（Ａ３）ポリエステル構造を有する２官能以上の多官能光重合性化合物を含む。 In a preferred example of the ink composition for forming a surface protective layer of the present invention, (A) the photopolymerizable compound contains (A3) a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure.
　本発明の表面保護層形成用インク組成物の他の好適例においては、インク組成物中の（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物の量が３０～９０質量％の範囲内である。 In another preferred embodiment of the ink composition for forming a surface protective layer of the present invention, the amount of (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure in the ink composition is 30 to 90% by mass. Within range.
　本発明の表面保護層形成用インク組成物の他の好適例においては、（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物が、イソボルニル（メタ）アクリレートを含まない。 In another preferred embodiment of the ink composition for forming a surface protective layer of the present invention, (A2) the monofunctional photopolymerizable compound having a heteroatom-free cyclic structure does not contain isobornyl (meth)acrylate.
　本発明の表面保護層形成用インク組成物の他の好適例においては、（Ｃ）紫外線吸収剤が、波長３８５ｎｍにおけるモル吸光係数が１．５×１０３（ｌ・ｍｏｌ－１・ｃｍ－１）以下である紫外線吸収剤を少なくとも含む。 In another preferred embodiment of the ink composition for forming a surface protective layer of the present invention, (C) the ultraviolet absorber has a molar absorption coefficient of 1.5×10 3 (l·mol −1 ·cm −1 ) at a wavelength of 385 nm. ) contains at least an ultraviolet absorber that is
　本発明の表面保護層形成用インク組成物の他の好適例においては、さらにメチルハイドロキノン（ＭＥＨＱ）及びブチルヒドロキシトルエン（ＢＨＴ）以外の（Ｄ）ラジカル捕捉剤を含有する。 Another preferred example of the ink composition for forming a surface protective layer of the present invention further contains (D) a radical scavenger other than methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT).
　本発明の表面保護層形成用インク組成物の他の好適例においては、（Ｄ）ラジカル捕捉剤が、ヒンダードアミン系化合物を含む。 In another preferred embodiment of the ink composition for forming a surface protective layer of the present invention, (D) the radical scavenger contains a hindered amine compound.
　本発明の表面保護層形成用インク組成物の他の好適例においては、（Ａ）光重合性化合物の合計光重合性官能基モル数ＡＭと（Ｄ）ラジカル捕捉剤のモル数ＤＭの比ＡＭ／ＤＭが１０以上である。 In another preferred embodiment of the ink composition for forming a surface protective layer of the present invention, the ratio AM of the total number of moles of photopolymerizable functional groups AM of (A) the photopolymerizable compound and the number of moles of (D) the radical scavenger DM /DM is 10 or more.
　本発明の表面保護層形成用インク組成物の他の好適例においては、さらに樹脂を含有する。 Another preferred example of the ink composition for forming a surface protective layer of the present invention further contains a resin.
　本発明によれば、耐候性に優れるとともに耐ブロッキング性、延伸性にも優れる膜を形成可能な表面保護層形成用インク組成物を提供することができる。 According to the present invention, it is possible to provide an ink composition for forming a surface protective layer capable of forming a film having excellent weather resistance, blocking resistance, and stretchability.
　以下に、本発明を詳細に説明する。 The present invention will be described in detail below.
　本発明の１つの態様は、（Ａ）光重合性化合物、（Ｂ）光重合開始剤、（Ｃ）紫外線吸収剤を含む、インク組成物である。本発明のインク組成物は、光硬化型のインク組成物であることが好ましい。本明細書において、光硬化型のインクとは、紫外線、可視光線、電子線等の活性エネルギー線の照射により硬化させることができるインク組成物を意味する。 One aspect of the present invention is an ink composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) an ultraviolet absorber. The ink composition of the present invention is preferably a photocurable ink composition. As used herein, the photocurable ink means an ink composition that can be cured by irradiation with active energy rays such as ultraviolet rays, visible rays, and electron beams.
　（Ａ）光重合性化合物は、活性エネルギー線照射時に反応性を示す官能基（例えば、アクリロイル基、メタクリロイル基、ビニル基またはアリル基を構成する炭素－炭素二重結合等の光重合性不飽和基）を介して重合反応を起こす化合物である。（Ａ）光重合性化合物は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。本発明のインク組成物中において（Ａ）光重合性化合物の量は７０～９５質量％であることが好ましく、８０～９５質量％であることがより好ましく、８５～９５質量％であることが更に好ましい。 (A) The photopolymerizable compound has a functional group (for example, an acryloyl group, a methacryloyl group, a vinyl group or an allyl group constituting a carbon-carbon double bond that exhibits reactivity when irradiated with an active energy ray). It is a compound that undergoes a polymerization reaction via a group). (A) A photopolymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types. The amount of (A) the photopolymerizable compound in the ink composition of the present invention is preferably 70 to 95% by mass, more preferably 80 to 95% by mass, and more preferably 85 to 95% by mass. More preferred.
　（Ａ）光重合性化合物は、単官能光重合性化合物または多官能光重合性化合物に分類される。ここで、単官能光重合性化合物としては、活性エネルギー線照射時に反応性を示す官能基を１つ有する単官能光重合性モノマー（例えば１つの光重合性不飽和基を有する単官能光重合性モノマー）や活性エネルギー線照射時に反応性を示す官能基を１つ有する単官能光重合性オリゴマー（例えば、１つの光重合性不飽和基を有する単官能重合性オリゴマー）等が挙げられる。多官能光重合性化合物としては、活性エネルギー線照射時に反応性を示す官能基を２つ以上有する多官能光重合性モノマー（例えば２つ以上の光重合性不飽和基を有する多官能光重合性モノマー）や活性エネルギー線照射時に反応性を示す官能基を２つ以上有する多官能光重合性オリゴマー（例えば、２つ以上の重合性不飽和基を有する多官能光重合性オリゴマー）等が挙げられる。 (A) The photopolymerizable compound is classified into a monofunctional photopolymerizable compound or a polyfunctional photopolymerizable compound. Here, the monofunctional photopolymerizable compound includes a monofunctional photopolymerizable monomer having one functional group exhibiting reactivity when irradiated with an active energy ray (for example, a monofunctional photopolymerizable monomer having one photopolymerizable unsaturated group). monomers), monofunctional photopolymerizable oligomers having one functional group exhibiting reactivity upon irradiation with active energy rays (for example, monofunctional polymerizable oligomers having one photopolymerizable unsaturated group), and the like. As the polyfunctional photopolymerizable compound, a polyfunctional photopolymerizable monomer having two or more functional groups exhibiting reactivity when irradiated with an active energy ray (e.g., a polyfunctional photopolymerizable monomer having two or more photopolymerizable unsaturated groups). monomers) and polyfunctional photopolymerizable oligomers having two or more functional groups exhibiting reactivity upon irradiation with active energy rays (e.g., polyfunctional photopolymerizable oligomers having two or more polymerizable unsaturated groups). .
　単官能光重合性化合物の具体例としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシキプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、ポリオキシエチレンモノ（メタ）アクリレート、ポリオキシプロピレンモノ（メタ）アクリレート、ポリオキシブチレンモノ（メタ）アクリレート、ステアリル（メタ）アクリレート、Ｎ－アクリロイルモルホリン、Ｎ－メタクリロイルモルホリン、γ－ブチロラクトン（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、４－t－ブチルシクロヘキシルアクリレート、ジメチルアクリルアミド、ヒドロキシエチルアクリルアミド、ヒドロキシエチルメタアクリルアミド、ジエチルアクリルアミド、イソプロピルアクリルアミド、ジメチルアミノプロピルアクリルアミド、ジメチルアミノプロピルメタアクリルアミド、ダイアセトンアクリルアミド、Ｎ－ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－ビニルカプロラクタム、デシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、オクチル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、イソアミル（メタ）アクリレート、２－エチルヘキシル－ジグリコール（メタ）アクリレート、ＥＯ（エチレンオキシド）変性２－エチルヘキシル（メタ）アクリレート、ネオペンチルグリコール（メタ）アクリル酸安息香酸エステル、Ｎ－アクリロイルオキシエチルヘキサヒドロフタルイミド、Ｎ－メタクリロイルオキシエチルヘキサヒドロフタルイミド、１－アクリロイルピロリジン－２－オン、１－メタクリロイルピロリジン－２－オン、１－アクリロイルピペリジン－２－オン、１－メタクリロイルピペリジン－２－オン、Ｎ－ビニル－２－ピロリドン、Ｎ－ビニルイミダゾール、テトラヒドロフルフリル（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート、環状トリメチロールプロパンフォルマル（メタ）アクリレート、エトキシ－ジエチレングリコール（メタ）アクリレート等が挙げられる。 Specific examples of monofunctional photopolymerizable compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6 - hydroxyhexyl (meth)acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, stearyl (meth) acrylate, N-acryloylmorpholine, N-methacryloylmorpholine , γ-butyrolactone (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, 4-t-butylcyclohexyl acrylate, dimethylacrylamide, hydroxyethylacrylamide, hydroxyethylmethacrylamide, diethylacrylamide, isopropylacrylamide, dimethylaminopropyl Acrylamide, dimethylaminopropyl methacrylamide, diacetone acrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methylolacrylamide, N-vinylcaprolactam, decyl (meth)acrylate, phenoxy ethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, octyl ( meth)acrylate, isooctyl (meth)acrylate, octyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl -diglycol (meth)acrylate, EO (ethylene oxide)-modified 2-ethylhexyl (meth)acrylate, neopentyl glycol (meth)acrylic acid benzoate, N-acryloyloxyethylhexahydrophthalimide, N-methacryloyloxyethylhexahydrophthalimide , 1-acryloylpyrrolidin-2-one, 1-methacryloylpyrrolidin-2-one, 1-acryloylpiperidin-2-one , 1-methacryloylpiperidin-2-one, N-vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydrofurfuryl (meth)acrylate, methoxydipropylene glycol (meth)acrylate, (2-methyl-2-ethyl-1 ,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate and the like.
　また、屋外広告やプラダン等の、人の目に触れる箇所で使用される際には印刷物に臭気を残さないモノマーを用いることが好ましく、トリデシルアクリレート、エトキシジエチレングリコールアクリレート、ヒドロキシエチルアクリルアミド、Ｎ－アクリロイルモルホリン、Ｎ－メタクリロイルモルホリン、１－アクリロイルピロリジン－２－オン、１－メタクリロイルピロリジン－２－オン、１－アクリロイルピペリジン－２－オン、１－メタクリロイルピペリジン－２－オン、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、環状トリメチロールプロパンフォルマル（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート、ヒドロキシエチルメタアクリルアミド、ジメチルアミノプロピルアクリルアミド、ジメチルアミノプロピルメタアクリルアミド、４－t－ブチルシクロヘキシルアクリレート等が好ましい。 In addition, it is preferable to use a monomer that does not leave an odor on the printed material when used in places where people can see it, such as outdoor advertisements and plastic cardboard. Morpholine, N-methacryloylmorpholine, 1-acryloylpyrrolidin-2-one, 1-methacryloylpyrrolidin-2-one, 1-acryloylpiperidin-2-one, 1-methacryloylpiperidin-2-one, 2-hydroxy-3-phenoxy Propyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, hydroxyethylmethacrylamide, dimethylaminopropyl Acrylamide, dimethylaminopropyl methacrylamide, 4-t-butylcyclohexyl acrylate and the like are preferred.
　本発明のインク組成物において、（Ａ）光重合性化合物中の単官能光重合性化合物の割合が７５～９５質量％の範囲内であることが好ましく、８０～９５質量％の範囲内であることが更に好ましい。（Ａ）光重合性化合物中の単官能光重合性化合物の割合を高くすることで、柔軟性に優れる膜を得ることができ、また、これによりクラックの発生を抑えることも可能である。 In the ink composition of the present invention, the ratio of the monofunctional photopolymerizable compound in (A) the photopolymerizable compound is preferably in the range of 75 to 95% by mass, and is in the range of 80 to 95% by mass. is more preferred. (A) By increasing the ratio of the monofunctional photopolymerizable compound in the photopolymerizable compound, it is possible to obtain a film having excellent flexibility and thereby suppress the occurrence of cracks.
　多官能光重合性化合物のうち、活性エネルギー線照射時に反応性を示す官能基を２つ有する多官能光重合性モノマー（２官能光重合性モノマー）の具体例としては、１，１２－ドデカンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、２－メチル－１，８－オクタンジオールジ（メタ）アクリレート、２－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，８－オクタンジオールジ（メタ）アクリレート、１，７－ヘプタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、３－メチル－１，５－ペンタンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジアクリレート、シクロヘキサンジメタノールジアクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ＰＯ（プロピレンオキシド）変性ネオペンチルグリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート等が挙げられる。 Among polyfunctional photopolymerizable compounds, a specific example of a polyfunctional photopolymerizable monomer (bifunctional photopolymerizable monomer) having two functional groups exhibiting reactivity upon irradiation with an active energy ray is 1,12-dodecanediol. Di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di( meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Acrylates, 1,4-butanediol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, tricyclodecanedimethanol diacrylate, cyclohexanedimethanol diacrylate, neopentyl glycol di(meth)acrylate, PO (propylene oxide)-modified neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate and the like.
　また、屋外広告やプラダン等の、人の目に触れる箇所で使用される際には印刷物に臭気を残さないモノマーを用いることが好ましく、３－メチル－１，５－ペンタンジオールジアクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等が好ましい。 In addition, it is preferable to use a monomer that does not leave an odor on the printed matter when used in places where people can see it, such as outdoor advertisements and plastic cardboard. Di(meth)acrylate, polypropylene glycol di(meth)acrylate and the like are preferred.
　活性エネルギー線照射時に反応性を示す官能基を３つ以上有する多官能光重合性モノマー（３官能以上の多官能光重合性モノマー）の具体例としては、トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、エトキシ化グリセリントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、ＥＯ変性ジグリセリンテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ＥＯ変性ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 Specific examples of polyfunctional photopolymerizable monomers having three or more functional groups that exhibit reactivity upon irradiation with active energy rays (trifunctional or higher polyfunctional photopolymerizable monomers) include trimethylolpropane tri(meth)acrylate, ethoxy trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, EO modified Diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate and the like.
　本明細書において、（メタ）アクリレートの用語は、メタクリレートまたはアクリレートを意味する。例えば、２－ヒドロキシエチル（メタ）アクリレートは、２－ヒドロキシエチルアクリレートまたは２－ヒドロキシエチルメタクリレートである。また、ジ（メタ）アクリレート、トリ（メタ）アクリレート等のように、複数であることを示す接頭語が（メタ）アクリレートに付されている場合、各（メタ）アクリレートは同一でも異なっていてもよい。 In this specification, the term (meth)acrylate means methacrylate or acrylate. For example, 2-hydroxyethyl (meth)acrylate is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. In addition, when a prefix indicating a plurality of (meth)acrylates such as di(meth)acrylate and tri(meth)acrylate is attached to each (meth)acrylate, each (meth)acrylate may be the same or different. good.
　本発明のインク組成物において、（Ａ）光重合性化合物は、環状構造を有する単官能光重合性化合物を含むことが好ましい。環状構造を有する単官能光重合性化合物は、ヘテロ原子を含む環状構造を有する単官能光重合性化合物とヘテロ原子を含まない環状構造を有する単官能光重合性化合物に分類することができる。ヘテロ原子とは、炭素、水素以外の原子を指す。 In the ink composition of the present invention, (A) the photopolymerizable compound preferably contains a monofunctional photopolymerizable compound having a cyclic structure. Monofunctional photopolymerizable compounds having a cyclic structure can be classified into monofunctional photopolymerizable compounds having a heteroatom-containing cyclic structure and monofunctional photopolymerizable compounds having a heteroatom-free cyclic structure. Heteroatoms refer to atoms other than carbon and hydrogen.
　本発明のインク組成物において（Ａ）光重合性化合物は、（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物（好ましくはモノマー）と（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物（好ましくはモノマー）の両方を含むことが好ましい。ただし、ここでいう「（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物」を構成する「ヘテロ原子を含む環状構造」は、芳香環を有しない環状構造であり、「（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物」を構成する「ヘテロ原子を含まない環状構造」は、芳香環を有しない環状構造である。 In the ink composition of the present invention, (A) the photopolymerizable compound comprises (A1) a monofunctional photopolymerizable compound (preferably a monomer) having a heteroatom-containing cyclic structure and (A2) a heteroatom-free cyclic structure. It is preferable to include both monofunctional photopolymerizable compounds (preferably monomers) having However, the "cyclic structure containing a heteroatom" constituting "(A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure" is a cyclic structure having no aromatic ring, and "(A2 ) “a monofunctional photopolymerizable compound having a heteroatom-free cyclic structure” is a cyclic structure having no aromatic ring.
　（Ａ１）ヘテロ原子を含む環状構造（ヘテロ環構造）を有する単官能光重合性化合物は、得られる膜の耐ブロッキング性および延伸性の観点から、好ましい。本発明のインク組成物中において、（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物の量は３０～９０質量％の範囲内であることが好ましく、４０～９０質量％の範囲内であることがより好ましく、４０～８０質量％の範囲内であることが更に好ましい。 (A1) A monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure (heterocyclic structure) is preferable from the viewpoint of blocking resistance and stretchability of the resulting film. In the ink composition of the present invention, the amount of (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure is preferably in the range of 30 to 90% by mass, more preferably in the range of 40 to 90% by mass. It is more preferably within the range of 40 to 80% by mass.
　（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物は、得られる膜の付着性と耐ブロッキング性のバランスの観点から、好ましい。本発明のインク組成物中において、（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性モノマーの量は１～６０質量％の範囲内であることが好ましく、５～５０質量％の範囲内であることがより好ましく、５～４０質量％の範囲内であることが更に好ましい。 (A2) A monofunctional photopolymerizable compound having a heteroatom-free cyclic structure is preferable from the viewpoint of the balance between the adhesion and blocking resistance of the resulting film. In the ink composition of the present invention, the amount of (A2) a monofunctional photopolymerizable monomer having a heteroatom-free cyclic structure is preferably in the range of 1 to 60% by mass, and 5 to 50% by mass. It is more preferably within the range, and still more preferably within the range of 5 to 40% by mass.
　本発明のインク組成物中において、（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物と（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物の合計量は、５０～９２質量％の範囲内であることが好ましい。 In the ink composition of the present invention, the total amount of (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure and (A2) a monofunctional photopolymerizable compound having a heteroatom-free cyclic structure is It is preferably within the range of 50 to 92% by mass.
　（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物としては、例えば、Ｎ－アクリロイルモルホリン、Ｎ－メタクリロイルモルホリン、Ｎ－ビニルカプロラクタム、γ－ブチロラクトン（メタ）アクリレート、Ｎ－ビニル－２－ピロリドン、環状トリメチロールプロパンフォルマル（メタ）アクリレート、Ｎ－アクリロイルオキシエチルヘキサヒドロフタルイミド、Ｎ－メタクリロイルオキシエチルヘキサヒドロフタルイミド、１－アクリロイルピロリジン－２－オン、１－メタクリロイルピロリジン－２－オン、１－アクリロイルピペリジン－２－オン、１－メタクリロイルピペリジン－２－オン、Ｎ－ビニルイミダゾール、テトラヒドロフルフリル（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート等が挙げられる。 Examples of (A1) monofunctional photopolymerizable compounds having a heteroatom-containing cyclic structure include N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylcaprolactam, γ-butyrolactone (meth)acrylate, and N-vinyl-2. -pyrrolidone, cyclic trimethylolpropane formal (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, N-methacryloyloxyethylhexahydrophthalimide, 1-acryloylpyrrolidin-2-one, 1-methacryloylpyrrolidin-2-one, 1-acryloylpiperidin-2-one, 1-methacryloylpiperidin-2-one, N-vinylimidazole, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl (meth)acrylate and the like can be mentioned.
　（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物としては、例えば、４－t－ブチルシクロヘキシルアクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、ネオペンチルグリコール（メタ）アクリル酸安息香酸エステル等が挙げられる。（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物は、沸点が１８０℃以上であることが好ましい。特に、４－t－ブチルシクロヘキシルアクリレートが好ましい。 (A2) Examples of monofunctional photopolymerizable compounds having a heteroatom-free cyclic structure include 4-t-butylcyclohexyl acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and benzyl (meth)acrylate. , isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, neo Pentyl glycol (meth)acrylic acid benzoate and the like can be mentioned. (A2) The monofunctional photopolymerizable compound having a heteroatom-free cyclic structure preferably has a boiling point of 180° C. or higher. In particular, 4-t-butylcyclohexyl acrylate is preferred.
　本発明のインク組成物において、（Ａ）光重合性化合物は、臭気を抑える観点から、（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性モノマーとして、イソボルニル（メタ）アクリレート、特にはイソボルニルアクリレートを含まないことが好ましい。イソボルニル（メタ）アクリレートは、特異的な臭気を有し、さらに、イソボルニル（メタ）アクリレートを用いると、硬化難によって耐ブロッキング性が低下したり、プラスチック基材への密着性が低下したりする場合がある。 In the ink composition of the present invention, (A) the photopolymerizable compound includes isobornyl (meth)acrylate, particularly isobornyl (meth)acrylate, as (A2) a monofunctional photopolymerizable monomer having a heteroatom-free cyclic structure, from the viewpoint of suppressing odor. is preferably free of isobornyl acrylate. Isobornyl (meth)acrylate has a peculiar odor, and when isobornyl (meth)acrylate is used, blocking resistance may be reduced due to difficulty in curing, and adhesion to plastic substrates may be reduced. There is
　本発明のインク組成物において、（Ａ）光重合性化合物は、（Ａ３）ポリエステル構造を有する２官能以上の多官能光重合性化合物を含むことが好ましい。（Ａ３）ポリエステル構造を有する２官能以上の多官能光重合性化合物を用いることで、硬化性が高く、耐ブロッキング性に優れる印刷物を得ることが出来る。（Ａ）光重合性化合物中に含まれる（Ａ３）ポリエステル構造を有する２官能以上の多官能光重合性化合物の割合は、好ましくは３～２０質量％、より好ましくは５～２０質量％、さらに好ましくは５～１５質量％の範囲内である。 In the ink composition of the present invention, (A) the photopolymerizable compound preferably contains (A3) a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure. (A3) By using a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure, it is possible to obtain a printed material having high curability and excellent blocking resistance. (A) The ratio of (A3) a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure contained in the photopolymerizable compound is preferably 3 to 20% by mass, more preferably 5 to 20% by mass, and further It is preferably within the range of 5 to 15% by mass.
　（Ａ３）ポリエステル構造を有する２官能以上の多官能光重合性化合物は、好ましくはポリエステルアクリレートである。ポリエステルアクリレートの官能基数は２～１２であることが好ましく、２～４であることがより好ましく、分子量は５０００以下であることが好ましい。ここで、ポリエステルアクリレートの分子量は、ポリスチレン換算の数平均分子量である。 (A3) The bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure is preferably a polyester acrylate. The number of functional groups of the polyester acrylate is preferably 2 to 12, more preferably 2 to 4, and the molecular weight is preferably 5,000 or less. Here, the molecular weight of the polyester acrylate is the polystyrene-equivalent number-average molecular weight.
　また、ポリエステルアクリレートとして、以下のものが知られている。
　ＣＮ２２８５、ＣＮ２２０３　ＮＳ、ＣＮ２２５４　ＮＳ、ＣＮ２２７１、ＣＮ２２７３、ＣＮ２２７９、ＣＮ２２８１、ＣＮ２２８３　ＮＳ，ＣＮ８２０１　ＮＳ、ＣＮ７００１　ＮＳ、ＣＮ２２５９、ＣＮ２２６１、ＣＮ２９２、ＣＮ２９４、ＣＮ２９９、ＣＮ２２８２、ＣＮ２２９５、ＣＮ２９３、ＣＮ２９６、ＣＮ２２６７　（サートマー社製）、
　Ｕ－２００ＰＡ、ＵＡ－１２２Ｐ（新中村化学工業社製）、
　ＥＢＥＣＲＹＬ　４３６、　ＥＢＥＣＲＹＬ　４３８、　ＥＢＥＣＲＹＬ　４５０、ＥＢＥＣＲＹＬ　５２４、ＥＢＥＣＲＹＬ　５２５、ＥＢＥＣＲＹＬ　８００、ＥＢＥＣＲＹＬ　８１１、ＥＢＥＣＲＹＬ　８１２、ＥＢＥＣＲＹＬ　１８３０、ＥＢＥＣＲＹＬ　８４６、ＥＢＥＣＲＹＬ　８５１、ＥＢＥＣＲＹＬ　８５２、ＥＢＥＣＲＹＬ　８５３、ＥＢＥＣＲＹＬ　８７０、ＥＢＥＣＲＹＬ　８８４、ＥＢＥＣＲＹＬ　１８８５、ＥＢＥＣＲＹＬ　８８８、ＥＢＥＣＲＹＬ　８９３、ＥＢＥＣＲＹＬ　５７１、ＥＢＥＣＲＹＬ　８０９（ダイセル・オルネクス社製）、
アロニックスＭ－６１００、Ｍ－６２５０、Ｍ－６５００、Ｍ－７１００、Ｍ－７３００Ｋ、Ｍ－８０３０、Ｍ－８０６０、Ｍ－８１００、Ｍ－８５３０、Ｍ－８５６０、Ｍ－９０５０（東亜合成社製） Moreover, the following are known as polyester acrylate.
ＣＮ２２８５、ＣＮ２２０３ ＮＳ、ＣＮ２２５４ ＮＳ、ＣＮ２２７１、ＣＮ２２７３、ＣＮ２２７９、ＣＮ２２８１、ＣＮ２２８３ ＮＳ，ＣＮ８２０１ ＮＳ、ＣＮ７００１ ＮＳ、ＣＮ２２５９、ＣＮ２２６１、ＣＮ２９２、ＣＮ２９４、ＣＮ２９９、ＣＮ２２８２、ＣＮ２２９５、ＣＮ２９３、ＣＮ２９６、ＣＮ２２６７ （サートマー社製）、
U-200PA, UA-122P (manufactured by Shin-Nakamura Chemical Co., Ltd.),
ＥＢＥＣＲＹＬ ４３６、 ＥＢＥＣＲＹＬ ４３８、 ＥＢＥＣＲＹＬ ４５０、ＥＢＥＣＲＹＬ ５２４、ＥＢＥＣＲＹＬ ５２５、ＥＢＥＣＲＹＬ ８００、ＥＢＥＣＲＹＬ ８１１、ＥＢＥＣＲＹＬ ８１２、ＥＢＥＣＲＹＬ １８３０、ＥＢＥＣＲＹＬ ８４６、ＥＢＥＣＲＹＬ ８５１、ＥＢＥＣＲＹＬ ８５２、ＥＢＥＣＲＹＬ ８５３、ＥＢＥＣＲＹＬ ８７０、ＥＢＥＣＲＹＬ ８８４、ＥＢＥＣＲＹＬ １８８５、ＥＢＥＣＲＹＬ ８８８ , EBECRYL 893, EBECRYL 571, EBECRYL 809 (manufactured by Daicel Allnex),
Aronix M-6100, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.)
　本発明のインク組成物において（Ａ）光重合性化合物は、芳香族環を有する化合物を含まないことが好ましい。芳香族環を有する化合物を用いると、得られる膜に黄変が生じる傾向があるため、耐黄変性を向上させる観点から、芳香族環を有する化合物を使用しないことが好ましい。また、（Ａ）光重合性化合物が芳香族環を有する化合物を含む場合であっても、（Ａ）光重合性化合物中に含まれる芳香族環を有する化合物の量は４０質量％以下の範囲内であることが好ましく、３０質量％以下の範囲内であることがより好ましく、２５質量％以下の範囲内であることが更に好ましい。 (A) the photopolymerizable compound in the ink composition of the present invention preferably does not contain a compound having an aromatic ring. Since the use of a compound having an aromatic ring tends to cause yellowing in the obtained film, it is preferable not to use a compound having an aromatic ring from the viewpoint of improving yellowing resistance. Further, even when the (A) photopolymerizable compound contains a compound having an aromatic ring, the amount of the compound having an aromatic ring contained in the (A) photopolymerizable compound is in the range of 40% by mass or less. It is preferably within the range of 30% by mass or less, more preferably within the range of 25% by mass or less.
　芳香族環を有する化合物としては、Ｎ－ビニル－２－ピロリドン、Ｎ－アクリロイルオキシエチルヘキサヒドロフタルイミド、Ｎ－メタクリロイルオキシエチルヘキサヒドロフタルイミド、Ｎ－ビニルイミダゾール、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、ネオペンチルグリコール（メタ）アクリル酸安息香酸エステル等が挙げられる。 Compounds having an aromatic ring include N-vinyl-2-pyrrolidone, N-acryloyloxyethylhexahydrophthalimide, N-methacryloyloxyethylhexahydrophthalimide, N-vinylimidazole, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol ( meth)acrylate, benzyl (meth)acrylate, neopentyl glycol (meth)acrylic acid benzoate, and the like.
　本発明のインク組成物において、（Ａ）光重合性化合物は、環状構造を有する多官能光重合性化合物を含んでもよい。環状構造を有する多官能光重合性化合物としては、例えば、トリシクロデカンジメタノールジアクリレート、シクロヘキサンジメタノールジアクリレート等が挙げられる。 In the ink composition of the present invention, (A) the photopolymerizable compound may contain a polyfunctional photopolymerizable compound having a cyclic structure. Examples of polyfunctional photopolymerizable compounds having a cyclic structure include tricyclodecanedimethanol diacrylate and cyclohexanedimethanol diacrylate.
　本発明のインク組成物において、（Ａ）光重合性化合物は、ガラス転移温度が０℃以下の光重合性モノマーと、ガラス転移温度が８５℃以上の光重合性モノマーとを含むことが好ましい。ここで、本発明のインク組成物中における、ガラス転移温度が０℃以下の光重合性モノマー、およびガラス転移温度が８５℃以上の光重合性モノマーのそれぞれの量が、１０質量％以上であることが好ましく、１５質量％以上であることが更に好ましい。塗膜全体のＴｇが室温付近である場合、高硬度、高分子量の強靭な膜が得られる。一方、塗膜全体のＴｇが室温より低い場合、高分子量の膜は得られるが硬度が足らず、耐ブロッキング性や擦過性に難があることが多い。また、塗膜全体のＴｇが室温より高い場合、膜が硬いため分子の運動が制限され、重合が十分に進行せずに粘着感等の不具合が生じやすくなる。これらＴｇや重合性、得られる塗膜の性質は側鎖構造に由来することから、Ｔｇの高いモノマーを一定量配合することで耐ブロッキング性や擦過性が確保でき、Ｔｇの低いモノマーを一定量配合することで硬化性と膜の強靭性を確保することができる。また、トータルのＴｇを１５℃～５０℃、特には２０℃～４５℃付近で設計することで、よりバランスのとれた設計が可能となる。 In the ink composition of the present invention, (A) the photopolymerizable compound preferably contains a photopolymerizable monomer having a glass transition temperature of 0°C or lower and a photopolymerizable monomer having a glass transition temperature of 85°C or higher. Here, the amount of each of the photopolymerizable monomer having a glass transition temperature of 0° C. or lower and the photopolymerizable monomer having a glass transition temperature of 85° C. or higher in the ink composition of the present invention is 10% by mass or more. is preferred, and 15% by mass or more is more preferred. When the Tg of the entire coating film is around room temperature, a tough film with high hardness and high molecular weight can be obtained. On the other hand, when the Tg of the coating film as a whole is lower than room temperature, a high-molecular-weight film can be obtained, but the hardness is insufficient, and blocking resistance and abrasion resistance are often difficult. On the other hand, when the Tg of the entire coating film is higher than room temperature, the film is hard and the movement of molecules is restricted, so that the polymerization does not proceed sufficiently, and problems such as stickiness tend to occur. These Tg, polymerizability, and the properties of the resulting coating film are derived from the side chain structure. By blending, it is possible to ensure curability and toughness of the film. Further, by designing the total Tg at 15° C. to 50° C., especially around 20° C. to 45° C., a more balanced design becomes possible.
　本明細書において、光重合性モノマーのガラス転移温度（Ｔｇ）とは、当該光重合性モノマーからなるホモポリマーのガラス転移温度である。
　これらモノマーを組み合わせることによって得られた光重合性インクの硬化塗膜のガラス転移温度は、Ｆｏｘの式を用いて理論値を求めることができる。
　硬化塗膜のガラス転移温度の理論値〔Ｔｇ（Ｋ）〕とは、硬化塗膜を形成する各重合体成分（エチレン性不飽和基を有するモノマー及びオリゴマー）のホモポリマーのガラス転移温度を用いて計算されるものであり、次のフォックス（Ｆｏｘ）の式〔式（１）〕を用いて求めることができる。
　１／Ｔｇ＝（Ｗ１／Ｔｇ１）＋（Ｗ２／Ｔｇ２）＋・・・＋（Ｗｎ／Ｔｇｎ）　・・・式（１）
〔但し、Ｔｇｎは、ｎ種の重合体成分（エチレン性不飽和基を有するモノマー又はオリゴマー）の各ホモポリマーのガラス転移温度（Ｋ）であり、Ｗｎは、前記各重合体成分の質量分率である。Ｗ１＋Ｗ２＋・・・＋Ｗｎ＝１である。〕 As used herein, the glass transition temperature (Tg) of a photopolymerizable monomer is the glass transition temperature of a homopolymer composed of the photopolymerizable monomer.
The theoretical value of the glass transition temperature of the cured coating film of the photopolymerizable ink obtained by combining these monomers can be obtained using the Fox equation.
The theoretical value of the glass transition temperature of the cured coating film [Tg (K)] is the glass transition temperature of the homopolymer of each polymer component (monomer and oligomer having an ethylenically unsaturated group) that forms the cured coating film. and can be obtained using the following Fox equation [equation (1)].
1/Tg=(W1/Tg1)+(W2/Tg2)+...+(Wn/Tgn)...Equation (1)
[However, Tgn is the glass transition temperature (K) of each homopolymer of n polymer components (monomer or oligomer having an ethylenically unsaturated group), and Wn is the mass fraction of each polymer component. is. W1+W2+ . . . +Wn=1. ]
　ガラス転移温度が０℃以下の光重合性モノマーとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシキプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、ポリオキシエチレンモノ（メタ）アクリレート、ポリオキシプロピレンモノ（メタ）アクリレート、ポリオキシブチレンモノ（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、イソデシル（メタ）アクリレート、２－エチルヘキシル－ジグリコール（メタ）アクリレート、ＥＯ（エチレンオキシド）変性２－エチルヘキシル（メタ）アクリレート、エトキシ－ジエチレングリコール（メタ）アクリレート等が挙げられる。 Examples of photopolymerizable monomers having a glass transition temperature of 0° C. or lower include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. acrylates, 6-hydroxyhexyl (meth)acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, isodecyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, EO (ethylene oxide)-modified 2-ethylhexyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate and the like.
　ガラス転移温度が８５℃以上の光重合性モノマーとしては、Ｎ－アクリロイルモルホリン、Ｎ－メタクリロイルモルホリン、ジメチルアクリルアミド、ヒドロキシエチルアクリルアミド、ヒドロキシエチルメタアクリルアミド、イソプロピルアクリルアミド、ジメチルアミノプロピルアクリルアミド、ジメチルアミノプロピルメタアクリルアミド、ダイアセトンアクリルアミド、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート等が挙げられる。 Examples of photopolymerizable monomers having a glass transition temperature of 85° C. or higher include N-acryloylmorpholine, N-methacryloylmorpholine, dimethylacrylamide, hydroxyethylacrylamide, hydroxyethylmethacrylamide, isopropylacrylamide, dimethylaminopropylacrylamide, and dimethylaminopropylmethacrylamide. , diacetone acrylamide, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate and the like.
　本発明のインク組成物において、（Ａ）光重合性化合物は、ホモポリマーのガラス転移点が室温（２３℃）以下で低粘度の光重合性化合物を配合することが好ましい。このような光重合性化合物はインクの粘度を低粘度に保つことができ、吐出安定性に優れるインクの設計を容易にするとともに、硬化性に優れ、インクの共重合性を向上させる効果を有する。このような（Ａ）光重合性化合物としては、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコールアクリレート、フェノキシ－ポリエチレングリコールアクリレート、エトキシ－ジエチレングリコールアクリレート、メトキシ－トリエチレングルコールアクリレート、２－エチルヘキシル－ジグルコールアクリレート、メトキシジプロピレングルコールアクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシブチルアクリレート、テトラヒドロフルフリルアクリレート等を挙げることが出来る。また、さらに硬化性を高める観点より環状構造を含むことが好ましく、本発明においては、塗膜を黄変から守る観点より、エチレンオキサイドを構造単位として含まないテトラヒドロフルフリルアクリレートを含むことが最も好ましい。 In the ink composition of the present invention, (A) the photopolymerizable compound is preferably a photopolymerizable compound whose homopolymer glass transition point is room temperature (23°C) or lower and whose viscosity is low. Such a photopolymerizable compound can keep the viscosity of the ink low, facilitates the design of an ink with excellent ejection stability, has excellent curability, and has the effect of improving the copolymerizability of the ink. . Examples of such (A) photopolymerizable compound include phenoxyethyl (meth)acrylate, phenoxydiethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, and 2-ethylhexyl-diglycol acrylate. , methoxydipropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate and the like. Further, it preferably contains a cyclic structure from the viewpoint of further improving curability, and in the present invention, it most preferably contains tetrahydrofurfuryl acrylate that does not contain ethylene oxide as a structural unit from the viewpoint of protecting the coating film from yellowing. .
　本発明のインク組成物は、エチレンオキサイドを構造単位として含有する化合物を含まないことが好ましい。エチレンオキサイドを構造単位として含有する化合物を用いると、得られる膜に黄変が生じる傾向があるため、耐黄変性を向上させる観点から、エチレンオキサイドを構造単位として含有する化合物を使用しないことが好ましい。また、本発明のインク組成物がエチレンオキサイドを構造単位として含有する化合物を含む場合であっても、本発明のインク組成物中に含まれるエチレンオキサイドを構造単位として含有する化合物の量は１０質量％以下の範囲内であることが好ましく、５質量％以下の範囲内であることがより好ましく、３質量％以下の範囲内であることが更に好ましい。 The ink composition of the invention preferably does not contain a compound containing ethylene oxide as a structural unit. When a compound containing ethylene oxide as a structural unit is used, the obtained film tends to yellow. Therefore, from the viewpoint of improving yellowing resistance, it is preferable not to use a compound containing ethylene oxide as a structural unit. . Further, even when the ink composition of the present invention contains a compound containing ethylene oxide as a structural unit, the amount of the compound containing ethylene oxide as a structural unit contained in the ink composition of the present invention is 10 mass. % or less, more preferably 5 mass % or less, and even more preferably 3 mass % or less.
　エチレンオキサイドを構造単位として含有する化合物としては、フェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、エトキシエチルアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、グリシジル（メタ）アクリレート、アリルグリシジルエーテル、エチレンオキサイド変性の各種アクリレート等が挙げられる。 Compounds containing ethylene oxide as structural units include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, ethoxyethyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, glycidyl (meth)acrylate, allyl glycidyl ether, and various ethylene oxide-modified acrylates. etc.
　（Ｂ）光重合開始剤は、活性エネルギー線を照射されることによって、上述した光重合性化合物の重合を開始させる作用を有する。（Ｂ）光重合開始剤の量は、インク組成物中１～２５質量％であることが好ましく、３～２０質量％であることが更に好ましく、３～１５質量％であることが一層好ましい。（Ｂ）光重合開始剤の含有量が１質量％未満では、膜が硬化不良となることがあり、２５質量％を超えると、低温時に析出物が発生してインクの吐出が不安定になることがある。更に、（Ｂ）光重合開始剤の開始反応を促進させるため、光増感剤等の助剤を併用することも可能である。 (B) The photopolymerization initiator has the effect of initiating the polymerization of the photopolymerizable compound described above when irradiated with an active energy ray. The amount of the photopolymerization initiator (B) in the ink composition is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, even more preferably 3 to 15% by mass. (B) If the content of the photopolymerization initiator is less than 1% by mass, the film may be poorly cured. Sometimes. Furthermore, in order to accelerate the initiation reaction of the photopolymerization initiator (B), an auxiliary agent such as a photosensitizer may be used in combination.
　（Ｂ）光重合開始剤としては、ベンゾフェノン系化合物、アセトフェノン系化合物、チオキサントン系化合物、フォスフィンオキサイド系化合物等が挙げられるが、硬化性の観点から、照射する活性エネルギー線の波長と光重合開始剤の吸収波長ができるだけ重複するものが好ましい。特に、（Ｂ）光重合開始剤は、ＬＥＤ硬化及び硬化時の着色の観点から、アシルホスフィンオキシド系開始剤を含むことが好ましい。（Ｂ）光重合開始剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 (B) Photopolymerization initiators include benzophenone-based compounds, acetophenone-based compounds, thioxanthone-based compounds, phosphine oxide-based compounds, and the like. It is preferred that the absorption wavelengths of the agents overlap as much as possible. In particular, (B) the photopolymerization initiator preferably contains an acylphosphine oxide-based initiator from the viewpoint of LED curing and coloring during curing. (B) A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.
　（Ｃ）光重合開始剤の具体例としては、
２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、
１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、
２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、
ベンゾフェノン、
１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、
２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチルプロピオニル）－ベンジル］－フェニル｝－２－メチル－プロパン－１－オン、
フェニルグリオキシリックアシッドメチルエステル、
２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、
２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン、
２－ジメチルアミノ－２－（４－メチル－ベンジル）－１－（４－モルフォリン－４－イル－フェニル）－ブタン－１－オン、
ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、
ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、
２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、
１，２－オクタンジオン，１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］、
エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）、
２，４－ジエチルチオキサントン、
２－イソプロピルチオキサントン、
２－クロロチオキサントン等が挙げられる。 (C) Specific examples of the photopolymerization initiator include:
2,2-dimethoxy-1,2-diphenylethan-1-one,
1-hydroxy-cyclohexyl-phenyl-ketone,
2-hydroxy-2-methyl-1-phenylpropan-1-one,
benzophenone,
1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one,
2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methyl-propan-1-one,
phenylglyoxylic acid methyl ester,
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,
2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone,
2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one,
bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide,
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)],
Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime),
2,4-diethylthioxanthone,
2-isopropylthioxanthone,
2-chlorothioxanthone and the like.
　これらの中でも、インクの硬化性の観点から、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、及び２，４－ジエチルチオキサントンが好ましく、更にはＬＥＤ硬化及び硬化時の着色の観点から、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、及び２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイドが好ましく、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイドが特に好ましい。 Among these, from the viewpoint of ink curability, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl -phosphine oxide and 2,4-diethylthioxanthone are preferred, and from the viewpoint of LED curing and coloring during curing, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6 -dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferred, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is particularly preferred.
　（Ｃ）紫外線吸収剤は、紫外線を吸収し、紫外線による劣化を防止する作用を有する。（Ｃ）紫外線吸収剤としては、シアノアクリレート系化合物、ベンゾフェノン系化合物、ベンゾエート系化合物、ベンゾトリアゾール系化合物、ヒドロキシフェニルトリアジン系化合物、ベンジリデンカンファー系化合物、無機微粒子等が挙げられる。（Ｃ）紫外線吸収剤は、トリアジン骨格を有するものが好ましく、中でも、紫外線吸収がより短波長にあるヒドロキシフェニルトリアジン系化合物がインクの硬化性の観点から好ましい。また、ヒドロキシフェニルトリアジン系化合物の中でも特に固体のものが好ましく、液体のものよりも流動性が低くブリードアウトしにくい傾向がある。 (C) The ultraviolet absorber has the effect of absorbing ultraviolet rays and preventing deterioration due to ultraviolet rays. (C) UV absorbers include cyanoacrylate compounds, benzophenone compounds, benzoate compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, benzylidene camphor compounds, inorganic fine particles, and the like. The (C) UV absorber preferably has a triazine skeleton, and among them, a hydroxyphenyltriazine-based compound that absorbs UV light at a shorter wavelength is preferable from the viewpoint of ink curability. Among hydroxyphenyltriazine-based compounds, solid ones are particularly preferable, and they tend to have lower fluidity than liquid ones and are less likely to bleed out.
　硬化性の観点から、照射する活性エネルギー線の波長と（Ｃ）紫外線吸収剤の吸収波長が出来るだけ重複しないものが好ましい。本発明のインク組成物において（Ｃ）紫外線吸収剤は、波長３８５ｎｍにおけるモル吸光係数が１．５×１０３（ｌ・ｍｏｌ－１・ｃｍ－１）以下である紫外線吸収剤を少なくとも含むことが好ましく、より好ましくは２．０×１０２（ｌ・ｍｏｌ－１・ｃｍ－１）以下である紫外線吸収剤を少なくとも含む。 From the viewpoint of curability, it is preferable that the wavelength of the irradiated active energy ray and the absorption wavelength of (C) the ultraviolet absorber do not overlap as much as possible. In the ink composition of the present invention, the (C) UV absorber may contain at least a UV absorber having a molar extinction coefficient of 1.5×10 3 (l·mol −1 ·cm −1 ) or less at a wavelength of 385 nm. It preferably contains at least an ultraviolet absorber with a concentration of 2.0×10 2 (l·mol −1 ·cm −1 ) or less.
　本明細書において、紫外線吸収剤のモル吸光係数は、紫外可視吸収スペクトル測定により得られた吸光度を基に、ランベルト・ベールの法則を用いて算出する。紫外可視吸収スペクトルの測定時の溶媒は、アセトニトリルまたはテトラヒドロフランを使用し、５０～１００μＭの濃度で１ｃｍセルを用いて紫外可視吸収スペクトルを測定する。 In this specification, the molar extinction coefficient of an ultraviolet absorber is calculated using Beer-Lambert's law based on the absorbance obtained by ultraviolet-visible absorption spectrum measurement. Acetonitrile or tetrahydrofuran is used as a solvent for the measurement of the UV-visible absorption spectrum, and the UV-visible absorption spectrum is measured using a 1 cm cell at a concentration of 50 to 100 μM.
　（Ｃ）紫外線吸収剤の具体例としては、
２，４－ジヒドロキシベンゾフェノン、
２－ヒドロキシ－４－メトキシベンゾフェノン、
２－ヒドロキシ－４－メトキシベンゾフェノン－５－スルフォニックアシッド、
２－ヒドロキシ－４－オクトキシベンゾフェノン、
２－ヒドロキシ－４－ドデシロキシベンゾフェノン－２－ヒドロキシ－４－ベンジロキシベンゾフェノン、
ビス（５－ベンゾイル－４－ヒドロキシ－２－メトキシフェニル）メタン、
２，２’－ジヒドロキシ－４－メトキシベンゾフェノン、
２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン、
２，２’，４，４’－テトラヒドロキシベンゾフェノン、
２―ヒドロキシ－４－メトキシ－２’－カルボキシベンゾフェノン、
２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール
２－［２’－ヒドロキシ－３’，５’－ビス（α，α－（ジメチルベンジル）フェニル］ベンゾトリアゾール、
２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）ベンゾトリアゾール、
２－（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、
２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、
２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－アミルフェニル）ベンゾトリアゾール、
２－（２’－ヒドロキシ－５’－ｔ－オクチルフェニル）ベンゾトリアゾール、
２，２’－メチレン－ビス［４－（１，１，３，３－テトラメチルブチル）－６－（２Ｎ－ベンゾトリアゾール－２－イル）フェノール］、
メチル－３－［３－ｔ－ブチル－５－（２Ｈ－ベンゾトリアゾール－２－イル）－４－ヒドロキシフェニル］プロピオネートとポリエチレングリコールとの縮合物、
２－（２－ヒドロキシフェニル）ベンゾトリアゾール、
２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、
２，６－ジ－ｔ－ブチルフェニル－３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンゾエート、
ヘキサデシル－３，５－ジ－ｔ－ブチル－４－ヒドロキシベンゾエート等が挙げられる。 (C) As a specific example of the ultraviolet absorber,
2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid,
2-hydroxy-4-octoxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone-2-hydroxy-4-benzyloxybenzophenone,
bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,
2,2′-dihydroxy-4-methoxybenzophenone,
2,2′-dihydroxy-4,4′-dimethoxybenzophenone,
2,2′,4,4′-tetrahydroxybenzophenone,
2-hydroxy-4-methoxy-2'-carboxybenzophenone,
2-(2'-hydroxy-5'-methylphenyl)benzotriazole 2-[2'-hydroxy-3',5'-bis(α,α-(dimethylbenzyl)phenyl]benzotriazole,
2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole,
2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole,
2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole,
2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol],
condensation products of methyl-3-[3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol;
2-(2-hydroxyphenyl)benzotriazole,
2-(2′-hydroxy-5′-methylphenyl)benzotriazole,
2,6-di-t-butylphenyl-3′,5′-di-t-butyl-4′-hydroxybenzoate,
hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and the like.
　本発明のインク組成物中において、（Ｃ）紫外線吸収剤の量は、好ましくは０．１～２０質量％、より好ましくは０．５～１０質量％、さらに好ましくは１～５質量％の範囲内であることが好ましい。紫外線吸収剤の量が多すぎると、膜が十分に硬化しない可能性がある。（Ｃ）紫外線吸収剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよいが、（Ｃ）紫外線吸収剤は、少なくとも２種の紫外線吸収剤を含有することが好ましい。構造が異なる複数種の紫外線吸収剤を用いることで、紫外線吸収剤の効果をより持続させることができる。 In the ink composition of the present invention, the amount of (C) the ultraviolet absorber is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 5% by mass. preferably within If the amount of UV absorber is too high, the film may not cure sufficiently. (C) UV absorbers may be used singly or in combination of two or more, but (C) UV absorbers preferably contain at least two UV absorbers. By using a plurality of types of ultraviolet absorbers having different structures, the effects of the ultraviolet absorbers can be maintained longer.
　本発明のインク組成物において、（Ｃ）紫外線吸収剤は、光重合性化合物との関係において、以下の式（１）で求められる値Ｂが好ましくは１００以上であり、より好ましくは１２０以上であり、さらに好ましくは２００以上である。また、値Ｂの上限は、例えば２００００以下である。
　紫外線吸収剤の分子量（ｇ／ｍｏｌ）／｜紫外線吸収剤のＳＰ値－光重合性化合物の平均ＳＰ値｜＝Ｂ　…　式（１）
　上記式（１）は、紫外線吸収剤（ＵＶＡ）と膜との相溶性（ＳＰ値）及びＵＶＡの分子量より導かれる。上記値Ｂが１００以上であると、ＵＶＡのブリードアウトの抑制効果が高い。上記値Ｂが１００未満である場合、ＵＶＡと光重合性化合物のＳＰ値の差（絶対値）が大きく及び／又はＵＶＡの分子量が低いことから、紫外線吸収剤のブリードアウトの抑制効果が低くなる場合がある。 In the ink composition of the present invention, the UV absorber (C) preferably has a value B determined by the following formula (1) of 100 or more, more preferably 120 or more, in relation to the photopolymerizable compound. Yes, more preferably 200 or more. Also, the upper limit of the value B is, for example, 20000 or less.
Molecular weight of UV absorber (g/mol)/|SP value of UV absorber−Average SP value of photopolymerizable compound|=B Formula (1)
The above formula (1) is derived from the compatibility (SP value) between the ultraviolet absorber (UVA) and the film and the molecular weight of UVA. When the value B is 100 or more, the effect of suppressing UVA bleed out is high. When the value B is less than 100, the difference (absolute value) between the SP values of the UVA and the photopolymerizable compound is large and/or the UVA has a low molecular weight, so the effect of suppressing the bleeding out of the ultraviolet absorber is low. Sometimes.
［ＳＰ値の算出方法］
　本明細書において、紫外線吸収剤及び光重合性化合物のＳＰ値は、ハンセン溶解度パラメータの値であり、Ｙ－ＭＢ法を用いて算出する。 [Calculation method of SP value]
In the present specification, the SP values of UV absorbers and photopolymerizable compounds are Hansen solubility parameter values and are calculated using the Y-MB method.
［平均ＳＰ値の算出方法］
　光重合性化合物がｎ種類の光重合性化合物からなる場合、各光重合性化合物のＳＰ値をそれぞれＳＰ１、ＳＰ２、・・・、ＳＰｎとし、各光重合性化合物の質量分率をＷ１、Ｗ２、・・・、Ｗｎ（Ｗ１＋Ｗ２＋・・・＋Ｗｎ＝１）として、以下の式より求められる。
　　　平均ＳＰ値＝ＳＰ１×Ｗ１＋ＳＰ２×Ｗ２＋・・・＋ＳＰｎ×Ｗｎ [Calculation method of average SP value]
When the photopolymerizable compound consists of n kinds of photopolymerizable compounds, the SP values of each photopolymerizable compound are SP 1 , SP 2 , . W 1 , W 2 , . . . , W n ( W 1 +W 2 + .
Average SP value=SP 1 ×W 1 +SP 2 ×W 2 + . . . +SP n ×W n
　本発明のインク組成物は、（Ｄ）ラジカル捕捉剤を含むことが好ましい。（Ｄ）ラジカル捕捉剤は、フリーラジカル等を捕捉し、光安定性を向上させることができる。また、フリーラジカルと反応し、重合反応が起こることを防止する機能を有する物質（いわゆる重合禁止剤）も、（Ｄ）ラジカル捕捉剤に含まれる。（Ｄ）ラジカル捕捉剤を用いることは、クラックの発生を防止する観点からも好ましい。 The ink composition of the present invention preferably contains (D) a radical scavenger. (D) The radical scavenger can scavenge free radicals and the like to improve photostability. In addition, the (D) radical scavenger also includes a substance that reacts with free radicals and has a function of preventing polymerization reaction from occurring (so-called polymerization inhibitor). (D) Using a radical scavenger is also preferable from the viewpoint of preventing cracks from occurring.
　（Ｄ）ラジカル捕捉剤としては、ヒンダードアミン系化合物、ハイドロキノン系化合物、フェノール系化合物、フェノチアジン系化合物、ニトロソ系化合物、Ｎ－オキシル系化合物等が挙げられ、特にヒンダードアミン系光安定化剤（ＨＡＬＳ）が好ましい。 (D) Radical scavengers include hindered amine-based compounds, hydroquinone-based compounds, phenol-based compounds, phenothiazine-based compounds, nitroso-based compounds, N-oxyl-based compounds, and particularly hindered amine-based light stabilizers (HALS). preferable.
　（Ｄ）ラジカル捕捉剤としては、メチルハイドロキノン（ＭＥＨＱ）及びブチルヒドロキシトルエン（ＢＨＴ）以外のラジカル捕捉剤であることが好ましい。メチルハイドロキノン（ＭＥＨＱ）及びブチルヒドロキシトルエン（ＢＨＴ）は、他のラジカル捕捉剤と比較して、クラックの発生を防止する効果が低い。 (D) The radical scavenger is preferably a radical scavenger other than methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT). Methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT) are less effective in preventing cracks than other radical scavengers.
　（Ｄ）ラジカル捕捉剤の具体例としては、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート、１－｛２－（３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシ）エチル｝－２，２，６，６－テトラメチルピペリジン、８－アセチル－３－ドデシル－７，７，９，９－テトラメチル－１，３，８－トリアザスピロ｛４．５｝デカン－２，４－ジオン等のヒンダードアミン系化合物、フェノール、ｏ－、ｍ－又はｐ－クレゾール、２－ｔ－ブチル－４－メチルフェノール、６－ｔ－ブチル－２,４－ジメチルフェノール、２,６－ジ－ｔ－ブチル－４－メチルフェノール、２－ｔ－ブチルフェノール、４－ｔ－ブチルフェノール、２,４－ジ－ｔ－ブチルフェノール、２－メチル－４－ｔ－ブチルフェノール、４－ｔ－ブチル－２,６－ジメチルフェノール等のフェノール系化合物、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノン、２,５－ジ－ｔ－ブチルハイドロキノン、２－メチル－ｐ－ハイドロキノン、２,３－ジメチルハイドロキノン、トリメチルハイドロキノン４－メチルベンズカテキン、ｔ－ブチルハイドロキノン、３－メチルベンズカテキン、２－メチル－ｐ－ハイドロキノン、２,３－ジメチルハイドロキノン、トリメチルハイドロキノン、ｔ－ブチルハイドロキノン、ベンゾキノン、ｔ－ブチル－ｐ－ベンゾキノン、２，５－ジフェニル－ｐ－ベンゾキノン等のハイドロキノン系化合物、フェノチアジン等のフェノチアジン系化合物、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミンアンモニウム、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミンアルミニウム塩等のニトロソ系化合物、４－ヒドロキシ－２,２,６,６－テトラメチル－ピペリジン－Ｎ－オキシル、４－オキソ－２,２,６,６－テトラメチル－ピペリジン－Ｎ－オキシル、４－メトキシ－２,２,６,６－テトラメチル－ピペリジン－Ｎ－オキシル等のＮ－オキシル系化合物等が挙げられる。 (D) Specific examples of radical scavengers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1-{2-(3-(3,5-di-t-butyl -4-hydroxyphenyl)propionyloxy)ethyl}-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro {4.5} Hindered amine compounds such as decane-2,4-dione, phenol, o-, m- or p-cresol, 2-t-butyl-4-methylphenol, 6-t-butyl-2,4 -dimethylphenol, 2,6-di-t-butyl-4-methylphenol, 2-t-butylphenol, 4-t-butylphenol, 2,4-di-t-butylphenol, 2-methyl-4-t-butylphenol , phenolic compounds such as 4-t-butyl-2,6-dimethylphenol, hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, 2,5-di-t-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3 -dimethylhydroquinone, trimethylhydroquinone 4-methylbenzcatechin, t-butylhydroquinone, 3-methylbenzcatechin, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, benzoquinone, t- Hydroquinone compounds such as butyl-p-benzoquinone and 2,5-diphenyl-p-benzoquinone, phenothiazine compounds such as phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, N-nitroso-N-phenylhydroxylamine aluminum salt nitroso compounds such as 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4- Examples include N-oxyl compounds such as methoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl.
　本発明のインク組成物中において、（Ｄ）ラジカル捕捉剤の量は、好ましくは１０質量％以下、より好ましくは７質量％以下、さらに好ましくは５質量％以下の範囲内であることが好ましい。ラジカル捕捉剤の量が多すぎると、硬化不良の原因となる可能性がある。（Ｄ）ラジカル捕捉剤の含有量の下限値は、例えば０．０１質量％以上であり、好ましくは０．１質量％以上、さらに好ましくは０．５質量％以上である。（Ｄ）ラジカル捕捉剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In the ink composition of the present invention, the amount of (D) the radical scavenger is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less. Too much radical scavenger may cause poor curing. (D) The lower limit of the content of the radical scavenger is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. (D) Radical scavengers may be used singly or in combination of two or more.
　本発明のインク組成物において、（Ａ）光重合性化合物の合計光重合性官能基モル数ＡＭと（Ｄ）ラジカル捕捉剤の有効モル数ＤＭの比ＡＭ／ＤＭが1０以上であることが好ましい。ラジカル捕捉剤は、重合に必要なラジカルを補足するため、重合阻害効果を有する。そのため、ラジカル捕捉剤を多く配合すると硬化率が下がることになる。ＡＭ／ＤＭは、発生したラジカルの周囲にいる重合成分とラジカル捕捉剤の比率を表しており、ＡＭ／ＤＭが≧１０であれば、ラジカル捕捉剤が重合に与える影響が十分に小さいと判断される。
　ラジカル捕捉剤における有効モル数は、ラジカルを補足可能な官能基の数を表す。例として１分子中にラジカル捕捉可能な部位が５個ある分子の場合、そのラジカル捕捉剤のモル数が１モルであれば、その有効モル数は５モルとなる。 In the ink composition of the present invention, the ratio AM/DM of the total number of moles of photopolymerizable functional groups AM of (A) the photopolymerizable compound and the number of effective moles DM of (D) the radical scavenger is preferably 10 or more. . A radical scavenger has an effect of inhibiting polymerization because it captures radicals necessary for polymerization. Therefore, if a large amount of radical scavenger is blended, the curing rate will decrease. AM/DM represents the ratio of the polymerizable component and the radical scavenger around the generated radicals, and if AM/DM is ≧10, it is judged that the influence of the radical scavenger on the polymerization is sufficiently small. be.
The effective number of moles in the radical scavenger represents the number of functional groups capable of capturing radicals. For example, in the case of a molecule having five sites capable of scavenging radicals in one molecule, if the number of moles of the radical scavenger is 1 mole, the number of effective moles is 5 moles.
　本発明のインク組成物は、樹脂を含んでもよい。インク組成物に樹脂を配合することで、インクの飛翔性やその安定性を向上させることができる。本発明のインク組成物に用いる樹脂は、活性エネルギー線照射時に反応性を示す官能基を有しない樹脂であることが好ましい。樹脂は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。本発明のインク組成物中において、樹脂の量は５質量％以下であることが好ましい。 The ink composition of the present invention may contain a resin. By blending a resin into the ink composition, it is possible to improve the flying property and stability of the ink. The resin used in the ink composition of the present invention is preferably a resin that does not have a functional group that exhibits reactivity when irradiated with active energy rays. The resin may be used singly or in combination of two or more. In the ink composition of the present invention, the amount of resin is preferably 5% by mass or less.
　樹脂の数平均分子量は、５００，０００以下であることが好ましく、２０，０００以下であることが更に好ましい。本明細書において、数平均分子量は、ゲル浸透クロマトグラフィーで測定した値であり、標準物質にはポリスチレンが使用される。 The number average molecular weight of the resin is preferably 500,000 or less, more preferably 20,000 or less. As used herein, the number average molecular weight is a value measured by gel permeation chromatography, and polystyrene is used as a standard substance.
　樹脂の具体例としては、ポリ酢酸ビニル、塩化ビニル－酢酸ビニル共重合体、塩化ビニル樹脂、塩化ゴム、塩素化ポリエチレン樹脂、塩素化ポリプロピレン樹脂、塩素化エチレン－ビニルアセテート樹脂、アクリル樹脂、ポリスチレン樹脂、 ポリアミド樹脂、 ポリウレタン樹脂、ポリオレフィン樹脂、シリコーン樹脂、フッ素樹脂、エポキシ樹脂、ポリエステル樹脂、ケトン樹脂、フェノール樹脂、ポリビニルアルコール、ポリビニルアルコール誘導体（アニオン変性ポリビニルアルコール等）、セルロース、セルロース誘導体（ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、酢酸セルロース等）、ロジン系樹脂、油性樹脂、石油樹脂、アルキッド樹脂、アルギン酸、アルギン酸誘導体（アルギン酸プロピレングリコールエステル等）等が挙げられる。また、これら樹脂の変性物も含まれる。例えば、水酸基を有する樹脂であれば、ヒドロキシアルキルエーテル化変性、カルボン酸変性などの変性が挙げられる。 Specific examples of resins include polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, chlorinated rubber, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate resin, acrylic resin, and polystyrene resin. , polyamide resin, polyurethane resin, polyolefin resin, silicone resin, fluorine resin, epoxy resin, polyester resin, ketone resin, phenol resin, polyvinyl alcohol, polyvinyl alcohol derivatives (anion-modified polyvinyl alcohol, etc.), cellulose, cellulose derivatives (hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate, etc.), rosin-based resins, oil-based resins, petroleum resins, alkyd resins, alginic acid, alginic acid derivatives (propylene glycol alginic acid, etc.), and the like. Modified products of these resins are also included. For example, in the case of a resin having a hydroxyl group, modifications such as hydroxyalkyl ether modification and carboxylic acid modification can be mentioned.
　本発明のインク組成物は、樹脂として、セルロース誘導体およびポリビニルアルコール誘導体の少なくとも一方を含有することが好ましく、セルロース誘導体を含有することがさらに好ましい。これらの樹脂は、インクの飛翔性やその安定性を向上させる効果が高く、特にセルロース誘導体が好適である。 The ink composition of the present invention preferably contains at least one of a cellulose derivative and a polyvinyl alcohol derivative as a resin, and more preferably contains a cellulose derivative. These resins are highly effective in improving the flight properties and stability of the ink, and cellulose derivatives are particularly suitable.
　セルロース誘導体の例としては、セルロースエーテル、セルロースエステル、ニトロセルロース、硫酸セルロース、リン酸セルロース、硝酸酢酸セルロース等が挙げられる。セルロースエーテルとしては、例えば、メチルセルロース、エチルセルロース、ベンジルセルロース、トリチルセルロース、シアノエチルセルロース、カルボキシメチルセルロース、カルボキシエチルセルロース、アミノエチルセルロース、オキシエチルセルロース（ヒドロキシエチルセルロースとも称する）等が挙げられる。また、セルロースエステルとしては、セルロースアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルロースプロピオネート、セルロースブチレート等が挙げられる。 Examples of cellulose derivatives include cellulose ether, cellulose ester, nitrocellulose, cellulose sulfate, cellulose phosphate, and cellulose acetate nitrate. Cellulose ethers include, for example, methyl cellulose, ethyl cellulose, benzyl cellulose, trityl cellulose, cyanoethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, aminoethyl cellulose, oxyethyl cellulose (also referred to as hydroxyethyl cellulose) and the like. Cellulose esters include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate and the like.
　また、アクリル変性セルロース誘導体、ポリエステル変性セルロース誘導体、及びポリウレタン変性セルロース誘導体も、セルロース誘導体の例として挙げられる。アクリル変性セルロース誘導体は、セルロースエーテル、セルロースエステル等のセルロース誘導体に、例えば、（メタ）アクリレート等のアクリル成分をグラフト重合させて得られる化合物である。ポリエステル変性セルロース誘導体は、セルロースエーテル、セルロースエステル等のセルロース誘導体に、例えば、ポリトリメチレンテレフタレート、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル成分（即ち、主鎖中に複数のエステル結合を有する成分）を結合させて得られる化合物である。ポリウレタン変性セルロース誘導体は、セルロースエーテル、セルロースエステル等のセルロース誘導体の水酸基に、例えば、イソシアネートプレポリマーを反応させて得られる化合物である。 Examples of cellulose derivatives include acrylic-modified cellulose derivatives, polyester-modified cellulose derivatives, and polyurethane-modified cellulose derivatives. Acryl-modified cellulose derivatives are compounds obtained by graft-polymerizing acrylic components such as (meth)acrylates onto cellulose derivatives such as cellulose ethers and cellulose esters. Polyester-modified cellulose derivatives are cellulose derivatives such as cellulose ethers and cellulose esters, and polyester components such as polytrimethylene terephthalate, polyethylene terephthalate and polybutylene terephthalate (that is, components having a plurality of ester bonds in the main chain). It is a compound obtained by binding. A polyurethane-modified cellulose derivative is a compound obtained by reacting, for example, an isocyanate prepolymer with a hydroxyl group of a cellulose derivative such as a cellulose ether or a cellulose ester.
　セルロース誘導体としては、セルロースアセテートアルキレートが好ましく、炭素数が１～６程度のアシル基で置換されているセルロースアセテートアルキレートがより好ましく、セルロースアセテートプロピオネート、およびセルロースアセテートブチレートが更に好ましい。 As the cellulose derivative, cellulose acetate alkylate is preferred, cellulose acetate alkylate substituted with an acyl group having about 1 to 6 carbon atoms is more preferred, and cellulose acetate propionate and cellulose acetate butyrate are even more preferred.
　本発明のインク組成物は、染料や顔料等の着色剤を含有してもよいが、その場合は、耐候性の観点から、顔料を含有することが好ましい。例えば、金属顔料を用いて、メタリックインクとすることも可能である。着色剤の含有量は、例えばインク組成物中０．１～１５質量％である。着色剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The ink composition of the present invention may contain coloring agents such as dyes and pigments, but in that case, it is preferable to contain pigments from the viewpoint of weather resistance. For example, it is also possible to use a metallic pigment to make a metallic ink. The content of the coloring agent is, for example, 0.1 to 15% by mass in the ink composition. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more types.
　着色剤の具体例としては、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１、２、３、４、５、６、７、９、１０、１２、１３、１４、１５、１６、１７、２４、３２、３４、３５、３６、３７、４１、４２、４３、４９、５３、５５、６０、６１、６２、６３、６５、７３、７４、７５、７７、８１、８３、８７、９３、９４、９５、９７、９８、９９、１００、１０１、１０４、１０５、１０６、１０８、１０９、１１０、１１１、１１３、１１４、１１６、１１７、１１９、１２０、１２３、１２４、１２６、１２７、１２８、１２９、１３０、１３３、１３８、１３９、１５０、１５１、１５２、１５３、１５４、１５５、１６５、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７９、１８０、１８１、１８２、１８３、１８４、１８５、１９１、１９３、１９４、１９９、２０５、２０６、２０９、２１２、２１３、２１４、２１５、２１９、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　１、２、３、４、５、１３、１５、１６、１７、１９、２０、２１、２４、３１、３４、３６、３８、４０、４３、４６、４８、４９、５１、６０、６１、６２、６４、６５、６６、６７、６８、６９、７１、７２、７３、７４、８１、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１、２、３、４、５、６、７、８、９、１０、１１、１２、１４、１５、１６、１７、１８、２１、２２、２３、３１、３２、３８、４１、４８、４８：１、４８：２、４８：３、４８：４、４８：５、４９、５２、５２：１、５２：２、５３：１、５４、５７：１、５８、６０：１、６３、６４：１、６８、８１：１、８３、８８、８９、９５、１０１、１０４、１０５、１０８、１１２、１１４、１１９、１２２、１２３、１３６、１４４、１４６、１４７、１４９、１５０、１６４、１６６、１６８、１６９、１７０、１７１、１７２、１７５、１７６、１７７、１７８、１７９、１８０、１８１、１８２、１８３、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１１、２１３、２１４、２１６、２２０、２２０、２２１、２２４、２２６、２３７、２３８、２３９、２４２、２４５、２４７、２４８、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２６０、２６２、２６３、２６４、２６６、２６８、２６９、２７０、２７１、２７２、２７９、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１、２、３、３：１、３：３、５：１、１３、１５、１６、１７、１９、２３、２５、２７、２９、３１、３２、３６、３７、３８、４２、５０、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１、１５、１５：１、１５：２、１５：３、１５：４、１５：５、１５：６、１６、１７：１、２４、２４：１、２５、２６、２７、２８、２９、３６、５６、６０、６１、６２、６３、７５、７９、８０、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　１、４、７、８、１０、１５、１７、２６、３６、５０、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｒｏｗｎ　５、６、２３、２４、２５、３２、４１、４２、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１、６、７、９、１０、１１、２０、２６、２８、３１、３２、３４、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｗｈｉｔｅ　１、２、４、５、６、７、１１、１２、１８、１９、２１、２２、２３、２６、２７、２８、
アルミニウムフレーク、ガラスフレーク、パール顔料及び中空粒子等が挙げられる。 Specific examples of colorants include:
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 32, 34, 35, 36, 37, 41, 42, 43, 49, 53, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 128, 129, 130, 133, 138, 139, 150, 151, 152, 153, 154, 155, 165, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 191, 193, 194, 199, 205, 206, 209, 212, 213, 214, 215, 219,
C. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 24, 31, 34, 36, 38, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41, 48, 48:1, 48:2, 48:3, 48:4, 48:5, 49, 52, 52:1, 52:2, 53:1, 54, 57:1, 58, 60:1, 63, 64:1, 68, 81:1, 83, 88, 89, 95, 101, 104, 105, 108, 112, 114, 119, 122, 123, 136, 144, 146, 147, 149, 150, 164, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 216, 220, 220, 221, 224, 226, 237, 238, 239, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 269, 270, 271, 272, 279,
C. I. Pigment Violet 1, 2, 3, 3:1, 3:3, 5:1, 13, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50,
C. I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17:1, 24, 24:1, 25, 26, 27, 28, 29, 36, 56, 60, 61, 62, 63, 75, 79, 80,
C. I. Pigment Green 1, 4, 7, 8, 10, 15, 17, 26, 36, 50,
C. I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42,
C. I. Pigment Black 1, 6, 7, 9, 10, 11, 20, 26, 28, 31, 32, 34,
C. I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28,
Examples include aluminum flakes, glass flakes, pearl pigments and hollow particles.
　これらの中でも、得られる膜の耐候性と色再現性の観点から、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　７、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：３、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：４、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　２８、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１０１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２０２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２８２、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１９、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｗｈｉｔｅ　６、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　４２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１２０、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３８、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５５、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　２１３が好ましい。 Among these, from the viewpoint of weather resistance and color reproducibility of the obtained film,
C. I. Pigment Black 7,
C. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 28,
C. I. Pigment Red 101, C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 254, C.I. I. Pigment Red 282,
C. I. Pigment Violet 19,
C. I. Pigment White 6,
C. I. Pigment Yellow 42, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 213 is preferred.
　本発明のインク組成物は、機能性付与を目的に種々の化合物を含有してもよく、例えば、得られる膜の高度を高くするために炭酸カルシウム、硫酸バリウム等を含有してもよく、得られる膜に熱線吸収機能を付与するためにインジウム錫複合酸化物、アンチモン錫複合酸化物等を含有してもよく、得られる膜の屈折率を高くするために微粒子酸化チタン、微粒子酸化ジルコニウム等を含有してもよい。 The ink composition of the present invention may contain various compounds for the purpose of imparting functionality. Indium-tin composite oxide, antimony-tin composite oxide, etc. may be contained in order to impart a heat-absorbing function to the film obtained, and fine-particle titanium oxide, fine-particle zirconium oxide, etc. may be added to increase the refractive index of the resulting film. may contain.
　吐出安定性の観点から、インク組成物中に分散している顔料粒子は、体積平均粒子径が０．０５～０．４μｍであり且つ体積最大粒子径が０．２～１μｍであることが好ましい。体積平均粒子径が０．４μｍより大きく且つ体積最大粒子径が１μｍよりも大きいと、インク組成物を安定に吐出することが困難となる傾向がある。なお、体積平均粒子径及び体積最大粒子径は、動的光散乱法を用いた測定機器によって測定できる。 From the viewpoint of ejection stability, the pigment particles dispersed in the ink composition preferably have a volume average particle diameter of 0.05 to 0.4 μm and a maximum volume particle diameter of 0.2 to 1 μm. . When the volume average particle size is larger than 0.4 μm and the volume maximum particle size is larger than 1 μm, it tends to be difficult to stably eject the ink composition. The volume average particle size and the volume maximum particle size can be measured with a measuring instrument using a dynamic light scattering method.
　本発明のインク組成物は、顔料を分散させるために、必要に応じて顔料分散剤を更に含有してもよい。顔料分散剤の含有量は、例えばインク組成物中０．１～５質量％である。顔料分散剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 If necessary, the ink composition of the present invention may further contain a pigment dispersant in order to disperse the pigment. The content of the pigment dispersant is, for example, 0.1 to 5% by mass in the ink composition. Pigment dispersants may be used singly or in combination of two or more.
　顔料分散剤の具体例としては、
ＡＮＴＩ－ＴＥＲＲＡ－Ｕ、ＡＮＴＩ－ＴＥＲＲＡ－Ｕ１００、
ＡＮＴＩ－ＴＥＲＲＡ－２０４、ＡＮＴＩ－ＴＥＲＲＡ－２０５、
ＤＩＳＰＥＲＢＹＫ－１０１、ＤＩＳＰＥＲＢＹＫ－１０２、
ＤＩＳＰＥＲＢＹＫ－１０３、ＤＩＳＰＥＲＢＹＫ－１０６、
ＤＩＳＰＥＲＢＹＫ－１０８、ＤＩＳＰＥＲＢＹＫ－１０９、
ＤＩＳＰＥＲＢＹＫ－１１０、ＤＩＳＰＥＲＢＹＫ－１１１、
ＤＩＳＰＥＲＢＹＫ－１１２、ＤＩＳＰＥＲＢＹＫ－１１６、
ＤＩＳＰＥＲＢＹＫ－１３０、ＤＩＳＰＥＲＢＹＫ－１４０、
ＤＩＳＰＥＲＢＹＫ－１４２、ＤＩＳＰＥＲＢＹＫ－１４５、
ＤＩＳＰＥＲＢＹＫ－１６１、ＤＩＳＰＥＲＢＹＫ－１６２、
ＤＩＳＰＥＲＢＹＫ－１６３、ＤＩＳＰＥＲＢＹＫ－１６４、
ＤＩＳＰＥＲＢＹＫ－１６６、ＤＩＳＰＥＲＢＹＫ－１６７、
ＤＩＳＰＥＲＢＹＫ－１６８、ＤＩＳＰＥＲＢＹＫ－１７０、
ＤＩＳＰＥＲＢＹＫ－１７１、ＤＩＳＰＥＲＢＹＫ－１７４、
ＤＩＳＰＥＲＢＹＫ－１８０、ＤＩＳＰＥＲＢＹＫ－１８２、
ＤＩＳＰＥＲＢＹＫ－１８３、ＤＩＳＰＥＲＢＹＫ－１８４、
ＤＩＳＰＥＲＢＹＫ－１８５、ＤＩＳＰＥＲＢＹＫ－２０００、
ＤＩＳＰＥＲＢＹＫ－２００１、ＤＩＳＰＥＲＢＹＫ－２００８、
ＤＩＳＰＥＲＢＹＫ－２００９、ＤＩＳＰＥＲＢＹＫ－２０２０、
ＤＩＳＰＥＲＢＹＫ－２０２５、ＤＩＳＰＥＲＢＹＫ－２０５０、
ＤＩＳＰＥＲＢＹＫ－２０７０、ＤＩＳＰＥＲＢＹＫ－２０９６、
ＤＩＳＰＥＲＢＹＫ－２１５０、ＤＩＳＰＥＲＢＹＫ－２１５５、
ＤＩＳＰＥＲＢＹＫ－２１６３、ＤＩＳＰＥＲＢＹＫ－２１６４、
ＢＹＫ－Ｐ１０４、ＢＹＫ－Ｐ１０４Ｓ、ＢＹＫ－Ｐ１０５、
ＢＹＫ－９０７６、ＢＹＫ－９０７７、ＢＹＫ－２２０Ｓ、ＢＹＫＪＥＴ－９１５０、ＢＹＫＪＥＴ－９１５１（以上、ビックケミー・ジャパン社製）、
Ｓｏｌｓｐｅｒｓｅ３０００、Ｓｏｌｓｐｅｒｓｅ５０００、
Ｓｏｌｓｐｅｒｓｅ９０００、Ｓｏｌｓｐｅｒｓｅ１１２００、
Ｓｏｌｓｐｅｒｓｅ１３２４０、Ｓｏｌｓｐｅｒｓｅ１３６５０、
Ｓｏｌｓｐｅｒｓｅ１３９４０、Ｓｏｌｓｐｅｒｓｅ１６０００、
Ｓｏｌｓｐｅｒｓｅ１７０００、Ｓｏｌｓｐｅｒｓｅ１８０００、
Ｓｏｌｓｐｅｒｓｅ２００００、Ｓｏｌｓｐｅｒｓｅ２１０００、
Ｓｏｌｓｐｅｒｓｅ２４０００ＳＣ、Ｓｏｌｓｐｅｒｓｅ２４０００ＧＲ、
Ｓｏｌｓｐｅｒｓｅ２６０００、Ｓｏｌｓｐｅｒｓｅ２７０００、
Ｓｏｌｓｐｅｒｓｅ２８０００、Ｓｏｌｓｐｅｒｓｅ３２０００、
Ｓｏｌｓｐｅｒｓｅ３２５００、Ｓｏｌｓｐｅｒｓｅ３２５５０、
Ｓｏｌｓｐｅｒｓｅ３２６００、Ｓｏｌｓｐｅｒｓｅ３３０００、
Ｓｏｌｓｐｅｒｓｅ３４７５０、Ｓｏｌｓｐｅｒｓｅ３５１００、
Ｓｏｌｓｐｅｒｓｅ３５２００、Ｓｏｌｓｐｅｒｓｅ３６０００、
Ｓｏｌｓｐｅｒｓｅ３６６００、Ｓｏｌｓｐｅｒｓｅ３７５００、
Ｓｏｌｓｐｅｒｓｅ３８５００、Ｓｏｌｓｐｅｒｓｅ３９０００、
Ｓｏｌｓｐｅｒｓｅ４１０００、Ｓｏｌｓｐｅｒｓｅ５４０００、
Ｓｏｌｓｐｅｒｓｅ５５０００、Ｓｏｌｓｐｅｒｓｅ５６０００、
Ｓｏｌｓｐｅｒｓｅ７１０００、Ｓｏｌｓｐｅｒｓｅ７６５００、
ＳｏｌｓｐｅｒｓｅＸ３００（以上、ルブリゾール社製）、
ディスパロンＤＡ－７３０１、ディスパロンＤＡ－３２５、ディスパロンＤＡ－３７５、ディスパロンＤＡ－２３４（以上、楠本化成社製）、
フローレンＡＦ－１０００、フローレンＤＯＰＡ－１５Ｂ、フローレンＤＯＰＡ－１５ＢＨＦＳ、フローレンＤＯＰＡ－１７ＨＦ、フローレンＤＯＰＡ－２２、フローレンＤＯＰＡ－３３、フローレンＧ－６００、フローレンＧ－７００、フローレンＧ－７００ＡＭＰ、フローレンＧ－７００ＤＭＥＡ、フローレンＧ－８２０、フローレンＧ－９００、フローレンＧＷ－１５００、フローレンＫＤＧ－２４００、フローレンＮＣ－５００、フローレンＷＫ－１３Ｅ、（以上、共栄社化学社製）、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６１０、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６１０Ｓ、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６３０、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６５０、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６５２、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６５５、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６６２Ｃ、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６７０、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６８５、ＴＥＧＯ　Ｄｉｓｐｅｒｓ７００、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ７１０、ＴＥＧＯ　Ｄｉｓｐｅｒｓ７４０Ｗ、
ＬＩＰＯＴＩＮ　Ａ、ＬＩＰＯＴＩＮ　ＢＬ、
ＬＩＰＯＴＩＮ　ＤＢ、ＬＩＰＯＴＩＮ　ＳＢ（以上、エボニック・デグサ社製）、
ＰＢ８２１、ＰＢ８２２、ＰＮ４１１、ＰＡ１１１（以上、味の素ファインテクノ社製）、
テキサホール９６３、テキサホール９６４、テキサホール９８７、テキサホールＰ６０、テキサホールＰ６１、テキサホールＰ６３、テキサホール３２５０、テキサホールＳＦ７１、テキサホールＵＶ２０、テキサホールＵＶ２１（以上、コグニス社製）、
ＢｏｒｃｈｉＧｅｎＳＮ８８、ＢｏｒｃｈｉＧｅｎ０４５１（以上、ボーシャス社製）等が挙げられる。 Specific examples of pigment dispersants include:
ANTI-TERRA-U, ANTI-TERRA-U100,
ANTI-TERRA-204, ANTI-TERRA-205,
DISPERBYK-101, DISPERBYK-102,
DISPERBYK-103, DISPERBYK-106,
DISPERBYK-108, DISPERBYK-109,
DISPERBYK-110, DISPERBYK-111,
DISPERBYK-112, DISPERBYK-116,
DISPERBYK-130, DISPERBYK-140,
DISPERBYK-142, DISPERBYK-145,
DISPERBYK-161, DISPERBYK-162,
DISPERBYK-163, DISPERBYK-164,
DISPERBYK-166, DISPERBYK-167,
DISPERBYK-168, DISPERBYK-170,
DISPERBYK-171, DISPERBYK-174,
DISPERBYK-180, DISPERBYK-182,
DISPERBYK-183, DISPERBYK-184,
DISPERBYK-185, DISPERBYK-2000,
DISPERBYK-2001, DISPERBYK-2008,
DISPERBYK-2009, DISPERBYK-2020,
DISPERBYK-2025, DISPERBYK-2050,
DISPERBYK-2070, DISPERBYK-2096,
DISPERBYK-2150, DISPERBYK-2155,
DISPERBYK-2163, DISPERBYK-2164,
BYK-P104, BYK-P104S, BYK-P105,
BYK-9076, BYK-9077, BYK-220S, BYKJET-9150, BYKJET-9151 (manufactured by BYK-Chemie Japan),
Solsperse 3000, Solsperse 5000,
Solsperse 9000, Solsperse 11200,
Solsperse 13240, Solsperse 13650,
Solsperse 13940, Solsperse 16000,
Solsperse 17000, Solsperse 18000,
Solsperse 20000, Solsperse 21000,
Solsperse 24000SC, Solsperse 24000GR,
Solsperse 26000, Solsperse 27000,
Solsperse 28000, Solsperse 32000,
Solsperse 32500, Solsperse 32550,
Solsperse 32600, Solsperse 33000,
Solsperse 34750, Solsperse 35100,
Solsperse 35200, Solsperse 36000,
Solsperse 36600, Solsperse 37500,
Solsperse 38500, Solsperse 39000,
Solsperse 41000, Solsperse 54000,
Solsperse 55000, Solsperse 56000,
Solsperse 71000, Solsperse 76500,
Solsperse X300 (manufactured by Lubrizol),
Disparlon DA-7301, Disparlon DA-325, Disparlon DA-375, Disparlon DA-234 (manufactured by Kusumoto Kasei Co., Ltd.),
Floren AF-1000, Floren DOPA-15B, Floren DOPA-15BHFS, Floren DOPA-17HF, Floren DOPA-22, Floren DOPA-33, Floren G-600, Floren G-700, Floren G-700AMP, Floren G-700DMEA, Floren G-820, Floren G-900, Floren GW-1500, Floren KDG-2400, Floren NC-500, Floren WK-13E (manufactured by Kyoeisha Chemical Co., Ltd.),
TEGO Dispers610, TEGO Dispers610S,
TEGO Dispers 630, TEGO Dispers 650,
TEGO Dispers 652, TEGO Dispers 655,
TEGO Dispers662C, TEGO Dispers670,
TEGO Dispers 685, TEGO Dispers 700,
TEGO Dispers710, TEGO Dispers740W,
LIPOTIN A, LIPOTIN BL,
LIPOTIN DB, LIPOTIN SB (manufactured by Evonik Degussa),
PB821, PB822, PN411, PA111 (manufactured by Ajinomoto Fine-Techno Co., Inc.),
Texahall 963, Texahall 964, Texahall 987, Texahall P60, Texahall P61, Texahall P63, Texahall 3250, Texahall SF71, Texahall UV20, Texahall UV21 (manufactured by Cognis),
BorchiGenSN88, BorchiGen0451 (above, manufactured by Bosius) and the like.
　本発明のインク組成物は、濡れ性の向上等の観点から、表面調整剤を更に含有してもよい。本明細書において、表面調整剤とは、分子構造中に親水性部位と疎水性部位を有し、添加することによりインク組成物の表面張力を調整し得る物質のことを意味する。 The ink composition of the present invention may further contain a surface modifier from the viewpoint of improving wettability. As used herein, a surface modifier means a substance that has a hydrophilic site and a hydrophobic site in its molecular structure and that can be added to adjust the surface tension of the ink composition.
　本発明のインク組成物に使用できる表面調整剤としては、具体的に、ジアルキルスルホコハク酸塩類、アルキルナフタレンスルホン酸塩類、脂肪酸塩類等のアニオン性表面調整剤、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリルエーテル類、アセチレングリコール類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類等のノニオン性表面調整剤、アルキルアミン塩類、第４級アンモニウム塩類等のカチオン性表面調整剤、アクリル系表面調整剤、シリコン系表面調整剤、およびフッ素系表面調整剤などが挙げられる。特に、シリコン系表面調整剤、アクリル系表面調整剤であることが好ましく、ビックケミー社、エボニック社、東レ・ダウコーニング社等の市販品を使用することができる。さらにシリコン系表面調整剤の場合、ポリエーテル変性シリコーンオイルであり、かつＨＬＢが７．６～１２であることが好ましい。 Specific examples of surface modifiers that can be used in the ink composition of the present invention include anionic surface modifiers such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene nonionic surface conditioners such as alkylallyl ethers, acetylene glycols, and polyoxyethylene/polyoxypropylene block copolymers; cationic surface conditioners such as alkylamine salts and quaternary ammonium salts; acrylic surface conditioners; Examples include silicon-based surface conditioners and fluorine-based surface conditioners. In particular, silicon-based surface conditioners and acrylic-based surface conditioners are preferred, and commercially available products such as BYK-Chemie, Evonik, and Dow Corning Toray can be used. Furthermore, in the case of a silicone-based surface conditioner, it is preferably a polyether-modified silicone oil and has an HLB of 7.6 to 12.
　表面調整剤の量は、使用目的により適宜選択し得るが、例えばインク組成物中０．０１～１質量％であることが好ましい。表面調整剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The amount of the surface modifier can be appropriately selected depending on the purpose of use, but is preferably 0.01 to 1% by mass in the ink composition, for example. The surface conditioners may be used singly or in combination of two or more.
　表面調整剤の具体例としては、
ＢＹＫ－３００、ＢＹＫ－３０２、ＢＹＫ－３０６、ＢＹＫ－３０７、ＢＹＫ－３１０、ＢＹＫ－３１３、ＢＹＫ－３１５Ｎ、ＢＹＫ－３２０、ＢＹＫ－３２２、ＢＹＫ－３２３、ＢＹＫ－３２５、ＢＹＫ－３２６、ＢＹＫ－３３０、ＢＹＫ－３３１、ＢＹＫ－３３３、ＢＹＫ－３４２、ＢＹＫ－３４５、ＢＹＫ－３４６、ＢＹＫ－３４７、ＢＹＫ－３４８、ＢＹＫ－３４９、ＢＹＫ－３５０、ＢＹＫ－３５４、ＢＹＫ－３５５、ＢＹＫ－３５６、ＢＹＫ－３５８Ｎ、ＢＹＫ－３６１Ｎ、ＢＹＫ－３７０、ＢＹＫ－３７５、ＢＹＫ－３７７、ＢＹＫ－３７８、ＢＹＫ－３８１、ＢＹＫ－３９２、ＢＹＫ－３９４、ＢＹＫ－３９９、ＢＹＫ－３４４０、ＢＹＫ－３４４１、ＢＹＫ－３４５５、ＢＹＫ－３５５０、ＢＹＫ－３５６０、ＢＹＫ－３５６５、ＢＹＫ－３７６０、ＢＹＫ－ＤＹＮＷＥＴ　８００Ｎ、ＢＹＫ－ＳＩＬＣＬＥＡＮ　３７００、ＢＹＫ－ＳＩＬＣＬＥＡＮ　３７０１、ＢＹＫ－ＳＩＬＣＬＥＡＮ　３７２０、ＢＹＫ－ＵＶ３５００、ＢＹＫ－ＵＶ３５０５、ＢＹＫ－ＵＶ３５１０、ＢＹＫ－ＵＶ３５３０、ＢＹＫ－ＵＶ３５３５、ＢＹＫ－ＵＶ３５７０、ＢＹＫ－ＵＶ３５７５、ＢＹＫ－ＵＶ３５７６（以上、ビックケミー・ジャパン社製）、
ＴＥＧＯ　Ｆｌｏｗ　３００、ＴＥＧＯ　Ｆｌｏｗ　３７０、ＴＥＧＯ　Ｆｌｏｗ　４２５、ＴＥＧＯ　Ｆｌｏｗ　ＡＴＦ　２、ＴＥＧＯ　Ｆｌｏｗ　ＺＦＳ　４６０、ＴＥＧＯ　Ｇｌｉｄｅ　１００、ＴＥＧＯ　Ｇｌｉｄｅ　１１０、ＴＥＧＯ　Ｇｌｉｄｅ　１３０、ＴＥＧＯ　Ｇｌｉｄｅ　４０６、ＴＥＧＯ　Ｇｌｉｄｅ　４１０、ＴＥＧＯ　Ｇｌｉｄｅ　４１１、ＴＥＧＯ　Ｇｌｉｄｅ　４１５、ＴＥＧＯ　Ｇｌｉｄｅ　４３２、ＴＥＧＯ　Ｇｌｉｄｅ　４３５、ＴＥＧＯ　Ｇｌｉｄｅ　４４０、ＴＥＧＯ　Ｇｌｉｄｅ　４５０、ＴＥＧＯ　Ｇｌｉｄｅ　４８２、ＴＥＧＯ　ＧｌｉｄｅＡ　１１５、ＴＥＧＯ　ＧｌｉｄｅＢ　１４８４、ＴＥＧＯ　ＧｌｉｄｅＺＧ　４００（以上、エボニック　ジャパン社製）、
５０１Ｗ　ＡＤＤＩＴＩＶＥ、ＦＺ－２１０４、ＦＺ－２１１０、ＦＺ－２１２３、ＦＺ－２１６４、ＦＺ－２１９１、ＦＺ－２２０３、ＦＺ－２２１５、ＦＺ－２２２２、ＦＺ－５６０９、Ｌ－７００１、Ｌ－７００２、Ｌ－７６０４、ＯＦＸ－０１９３、ＯＦＸ－０３０９　ＦＬＵＩＤ、ＯＦＸ－５２１１　ＦＬＵＩＤ、ＳＦ　８４１０　ＦＬＵＩＤ、ＳＨ３７７１、ＳＨ　３７４６　ＦＬＵＩＤ、ＳＨ　８４００　ＦＬＵＩＤ、ＳＨ　８７００　ＦＬＵＩＤ、Ｙ－７００６（以上、東レ・ダウコーニング社製）、
ＫＦ－３５１Ａ、ＫＦ－３５２Ａ、ＫＦ－３５３、ＫＦ－３５４Ｌ、ＫＦ－３５５Ａ、ＫＦ－６１５Ａ、ＫＦ－６４０、ＫＦ－６４２、ＫＦ－６４３、ＫＦ－６４４、ＫＦ－９４５、ＫＦ－６００４、ＫＦ－６０１１、ＫＦ－６０１２、ＫＦ－６０１５、ＫＦ－６０１７、ＫＦ－６０２０、ＫＦ－６２０４、Ｘ－２２－２５１６、Ｘ－２２－４５１５（以上、信越化学工業社製）等が挙げられる。 Specific examples of surface conditioners include:
BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-325, BYK-326, BYK- 330, BYK-331, BYK-333, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-370, BYK-375, BYK-377, BYK-378, BYK-381, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYK- 3455, BYK-3550, BYK-3560, BYK-3565, BYK-3760, BYK-DYNWET 800N, BYK-SILCLEAN 3700, BYK-SILCLEAN 3701, BYK-SILCLEAN 3720, BYK-UV3500, BYK-UV3503, BYK-UV10YK- BYK-UV3530, BYK-UV3535, BYK-UV3570, BYK-UV3575, BYK-UV3576 (manufactured by BYK-Chemie Japan),
ＴＥＧＯ Ｆｌｏｗ ３００、ＴＥＧＯ Ｆｌｏｗ ３７０、ＴＥＧＯ Ｆｌｏｗ ４２５、ＴＥＧＯ Ｆｌｏｗ ＡＴＦ ２、ＴＥＧＯ Ｆｌｏｗ ＺＦＳ ４６０、ＴＥＧＯ Ｇｌｉｄｅ １００、ＴＥＧＯ Ｇｌｉｄｅ １１０、ＴＥＧＯ Ｇｌｉｄｅ １３０、ＴＥＧＯ Ｇｌｉｄｅ ４０６、ＴＥＧＯ Ｇｌｉｄｅ ４１０、ＴＥＧＯ Ｇｌｉｄｅ ４１１、ＴＥＧＯ Ｇｌｉｄｅ ４１５、 TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 482, TEGO Glide A 115, TEGO Glide B 1484, TEGO Glide ZG 400 (manufactured by Evonik Japan),
501W ADDITIVE, FZ-2104, FZ-2110, FZ-2123, FZ-2164, FZ-2191, FZ-2203, FZ-2215, FZ-2222, FZ-5609, L-7001, L-7002, L-7604 , OFX-0193, OFX-0309 FLUID, OFX-5211 FLUID, SF 8410 FLUID, SH3771, SH 3746 FLUID, SH 8400 FLUID, SH 8700 FLUID, Y-7006 (manufactured by Dow Corning Toray Co., Ltd.),
KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-640, KF-642, KF-643, KF-644, KF-945, KF-6004, KF- 6011, KF-6012, KF-6015, KF-6017, KF-6020, KF-6204, X-22-2516, X-22-4515 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
　これらの中でも、構造およびＨＬＢの観点から、５０１Ｗ　ＡＤＤＩＴＩＶＥ、ＦＺ－２１０４、ＦＺ－２１２３、ＦＺ－２２１５、Ｌ－７００２、ＯＦＸ－０３０９　ＦＬＵＩＤ、ＯＦＸ－５２１１　ＦＬＵＩＤ、ＳＨ　８４００　ＦＬＵＩＤ、ＫＦ－３５１Ａ、ＫＦ－３５３、ＫＦ－３５５Ａ、ＫＦ－６１５Ａ、ＫＦ－６４２、ＫＦ－６４４、ＫＦ－６００４、ＫＦ－６０１１、ＫＦ－６２０４が好ましい。 Among these, in terms of structure and HLB, 501W ADDITIVE, FZ-2104, FZ-2123, FZ-2215, L-7002, OFX-0309 FLUID, OFX-5211 FLUID, SH8400 FLUID, KF-351A, KF- 353, KF-355A, KF-615A, KF-642, KF-644, KF-6004, KF-6011, KF-6204 are preferred.
　本発明のインク組成物は、その他の成分として、酸化防止剤、可塑剤、防錆剤、溶剤、充填剤、消泡剤、荷電制御剤、応力緩和剤、浸透剤、導光材、光輝材、磁性材、蛍光体、抗菌剤、抗ウイルス剤、防藻剤等の添加剤を必要に応じて使用してもよい。 The ink composition of the present invention contains, as other components, an antioxidant, a plasticizer, a rust inhibitor, a solvent, a filler, an antifoaming agent, a charge control agent, a stress relaxation agent, a penetrating agent, a light guide material, and a glitter material. , a magnetic material, a fluorescent substance, an antibacterial agent, an antiviral agent, an anti-algae agent, and the like may be used as necessary.
　本発明のインク組成物は、必要に応じて適宜選択される各種成分を混合し、必要に応じて、使用するインクジェットプリントヘッドのノズル径の約１／１０以下のポアサイズを持つフィルターを用い、得られた混合物を濾過することによって、調製できる。 The ink composition of the present invention is obtained by mixing various components appropriately selected as necessary, and optionally using a filter having a pore size of about 1/10 or less of the nozzle diameter of the ink jet print head to be used. can be prepared by filtering the resulting mixture.
　本発明のインク組成物は、その４０℃における粘度が、５～２５ｍＰａ・ｓであることが好ましく、５～１５ｍＰａ・ｓであることが更に好ましい。４０℃におけるインク粘度が上記特定した範囲内にあれば、良好な吐出安定性が得られる。なお、インク粘度は、コーンプレート型粘度計を用いて測定できる。 The ink composition of the present invention preferably has a viscosity at 40°C of 5 to 25 mPa·s, more preferably 5 to 15 mPa·s. If the ink viscosity at 40° C. is within the specified range, good ejection stability can be obtained. Ink viscosity can be measured using a cone-plate viscometer.
　本発明のインク組成物は、その２５℃における表面張力が２０～３５ｍＮ／ｍであることが好ましく、２３～２８ｍＮ／ｍであることが更に好ましい。２５℃におけるインク表面張力が上記特定した範囲内にあれば、良好な吐出安定性が得られる。インク表面張力は、プレート法により測定できる。 The ink composition of the present invention preferably has a surface tension of 20 to 35 mN/m at 25°C, more preferably 23 to 28 mN/m. If the surface tension of the ink at 25° C. is within the specified range, good ejection stability can be obtained. Ink surface tension can be measured by the plate method.
　本発明のインク組成物は、クリアインクであることが好ましい。本明細書において、クリアインクは、厚さ３０μｍの膜を形成した際の波長３８０～８００ｎｍの範囲における光線透過率が８０％以上となるクリアインクを指し、該光線透過率は好ましくは９０％以上、より好ましくは９５％以上、更に好ましくは９７％以上である。本明細書において、光線透過率は、ＪＩＳ　Ｋ７３６１－１：１９９７「プラスチック－透明材料の全光線透過率の試験方法－第１部：シングルビーム法」に準拠して測定される。 The ink composition of the present invention is preferably clear ink. In this specification, clear ink refers to a clear ink having a light transmittance of 80% or more in a wavelength range of 380 to 800 nm when a film having a thickness of 30 μm is formed, and the light transmittance is preferably 90% or more. , more preferably 95% or more, and still more preferably 97% or more. In this specification, the light transmittance is measured according to JIS K7361-1:1997 "Plastics-Testing method for total light transmittance of transparent materials-Part 1: Single beam method".
　本発明のインク組成物は、表面保護のために使用されることが好ましく、表面保護形成用インク組成物として好適である。具体的に、本発明のインク組成物は、加飾層、特には染料や有機顔料を含む加飾層の表面を保護するためのクリアインクであることが好ましい。加飾層は、例えば、塗料、インク（例えば印刷インキ、インクジェットインク）及び粉体トナーの内の少なくとも１種によって形成される加飾層である。 The ink composition of the present invention is preferably used for surface protection, and is suitable as an ink composition for forming surface protection. Specifically, the ink composition of the present invention is preferably a clear ink for protecting the surface of a decorative layer, particularly a decorative layer containing a dye or an organic pigment. The decorative layer is, for example, a decorative layer formed of at least one of paint, ink (eg, printing ink, inkjet ink), and powder toner.
　本発明のインク組成物から形成される膜のガラス転移温度は、１５～５０℃であることが好ましい。ガラス転移点を１５℃以上とすることで、表面保護層形成用インクとして求められる耐ブロッキング性の確保が容易になる。また、ガラス転移点を５０℃以下とすることで、インクを加温せず、室温で吐出、硬化した際にも十分な重合性を確保しやすくなり、得られた塗膜の耐候性や耐擦過性向上に寄与する。なお、インクを加温して印刷、硬化する際の好ましいガラス転移点は６０℃以下である。 The glass transition temperature of the film formed from the ink composition of the present invention is preferably 15 to 50°C. By setting the glass transition point to 15° C. or higher, it becomes easy to secure anti-blocking property required for the ink for forming a surface protective layer. In addition, by setting the glass transition point to 50 ° C. or less, it becomes easy to secure sufficient polymerizability even when the ink is discharged and cured at room temperature without heating, and the weather resistance and resistance of the resulting coating film. Contributes to improving abrasion resistance. The preferred glass transition point for heating the ink for printing and curing is 60° C. or lower.
　本明細書において、インク組成物から形成される膜のガラス転移温度（Ｔｇ）は、ＦＯＸの式を用いて算出される。 In this specification, the glass transition temperature (Tg) of the film formed from the ink composition is calculated using the FOX formula.
　本発明の別の態様は、本発明のインク組成物を用いた印刷方法である。本発明の印刷方法は、加飾層の表面に、上述した本発明のインク組成物で印刷（好ましくはインクジェット印刷）を行うことを特徴とする。本発明のインク組成物の説明において記載した内容については、本発明の印刷方法にも当てはまることである。 Another aspect of the present invention is a printing method using the ink composition of the present invention. The printing method of the present invention is characterized by performing printing (preferably inkjet printing) on the surface of the decorative layer with the ink composition of the present invention described above. The contents described in the description of the ink composition of the present invention also apply to the printing method of the present invention.
　本発明の印刷方法の一実施態様において、加飾層は、染料や顔料等の着色剤を含み、色付けされた層であり、これによって加飾が行われている。加飾層は、例えば、塗料、インク（例えば印刷インキ、インクジェットインク）及び粉体トナーの内の少なくとも１種によって形成される加飾層である。 In one embodiment of the printing method of the present invention, the decorative layer is a colored layer containing coloring agents such as dyes and pigments, and is used for decoration. The decorative layer is, for example, a decorative layer formed of at least one of paint, ink (eg, printing ink, inkjet ink), and powder toner.
　加飾層は、着色剤の他、樹脂、紫外線吸収剤、ラジカル捕捉剤、酸化防止剤、可塑剤、防錆剤、防藻剤、抗菌剤、抗ウイルス剤、充填剤、荷電制御剤、導光材、光輝材、磁性材、蛍光体、ワックス等を必要に応じて含むことができる。 In addition to colorants, the decorative layer contains resins, ultraviolet absorbers, radical scavengers, antioxidants, plasticizers, antirust agents, anti-algae agents, antibacterial agents, antiviral agents, fillers, charge control agents, conductors. Luminescent materials, luster materials, magnetic materials, phosphors, waxes, and the like can be included as necessary.
　本発明の印刷方法の一実施態様において、加飾層は、基材や基材上に形成される下塗り層などの表面の少なくとも一部に形成されている。 In one embodiment of the printing method of the present invention, the decorative layer is formed on at least part of the surface of the base material and the undercoat layer formed on the base material.
　ここで、基材としては、特に限定されるものではないが、工業ラインで用いられる基材が好適に挙げられる。基材の形状としては、例えば、フィルム状、シート状、板状等がある。基材の材質としては、例えば、エポキシ樹脂、ＡＢＳ樹脂、ポリカーボネート、ポリ塩化ビニル、ポリスチレン、アクリル樹脂、特にはポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンテレフタラート（ＰＥＴ）、ポリプロピレン（ＰＰ）等のプラスチック、鉄、ステンレス、アルミニウム等の金属、木材、セメント、コンクリート、石膏、ケイ酸カルシウム、炭酸カルシウム、ガラス等が挙げられる。基材の具体例としては、塩ビシート、ターポリン、プラダン（プラスチック製ダンボール）、アクリル板、フレキシブルボード、ケイ酸カルシウム板、石膏スラグバーライト板、炭酸カルシウム板、木片セメント板、プレキャストコンクリート板、軽量発泡コンクリート（ＡＬＣ）板、石膏ボード、タイル、及びガラス板等が挙げられる。 Here, although the base material is not particularly limited, base materials used in industrial lines are suitable. The shape of the substrate includes, for example, a film shape, a sheet shape, a plate shape, and the like. Examples of materials for the substrate include plastics such as epoxy resin, ABS resin, polycarbonate, polyvinyl chloride, polystyrene, acrylic resin, particularly polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP), etc. Examples include metals such as iron, stainless steel and aluminum, wood, cement, concrete, gypsum, calcium silicate, calcium carbonate, and glass. Specific examples of base materials include PVC sheet, tarpaulin, plastic cardboard (cardboard made of plastic), acrylic board, flexible board, calcium silicate board, gypsum slag barite board, calcium carbonate board, wood chip cement board, precast concrete board, lightweight Examples include foamed concrete (ALC) boards, gypsum boards, tiles, and glass boards.
　また、加飾層の付着性や発色性を向上させる観点から、基材は表面処理がなされていてもよい。例えば、基材は、その表面に下塗り層を有していてもよい。 In addition, from the viewpoint of improving the adhesion and color development of the decorative layer, the base material may be surface-treated. For example, the substrate may have a primer layer on its surface.
　本発明の印刷方法において、印刷は、インクジェット印刷方式にて行われることが好適であるものの、これに限定されず、グラビア印刷方式、オフセット印刷方式、フレキソ印刷方式、スクリーン印刷方式、コーター方式、スプレー方式等の各種印刷方法によって行うことも可能である。 In the printing method of the present invention, printing is preferably carried out by an inkjet printing method, but is not limited thereto, and gravure printing, offset printing, flexographic printing, screen printing, coater method, spray printing, etc. It is also possible to carry out by various printing methods such as a system.
　インクジェット印刷には、種々のインクジェットプリンタに使用することができる。インクジェットプリンタとしては、例えば、荷電制御方式又はピエゾ方式によりインク組成物を噴出させるインクジェットプリンタが挙げられる。また、大型インクジェットプリンタ、具体例としては工業ラインで生産される物品への印刷を目的としたインクジェットプリンタも好適に使用できる。 For inkjet printing, it can be used for various inkjet printers. Examples of inkjet printers include inkjet printers that eject an ink composition by a charge control method or a piezo method. In addition, a large-sized inkjet printer, as a specific example, an inkjet printer for the purpose of printing on articles produced on an industrial line can also be suitably used.
　本発明の印刷方法の一実施態様においては、本発明のインク組成物を用いた印刷によって、加飾層を覆う層が形成される。この層はクリア層であることが好ましい。本明細書において、クリア層は、厚さ３０μｍである場合に波長３８０～８００ｎｍの範囲における光線透過率が８０％以上、好ましくは９０％以上、より好ましくは９５％以上、更に好ましくは９７％以上である膜であり、上述したクリアインクから形成することが可能である。 In one embodiment of the printing method of the present invention, a layer covering the decorative layer is formed by printing using the ink composition of the present invention. This layer is preferably a clear layer. In this specification, the clear layer has a light transmittance of 80% or more, preferably 90% or more, more preferably 95% or more, and still more preferably 97% or more in the wavelength range of 380 to 800 nm when the thickness is 30 μm. and can be formed from the clear ink described above.
　本発明の印刷方法の一実施態様において、基材や基材上に形成される下塗り層などの表面の一部に加飾層が存在しない箇所がある場合には、本発明のインク組成物から形成される層は、基材や基材上に形成される下塗り層などの表面に形成されてもよい。 In one embodiment of the printing method of the present invention, when there is a portion where the decorative layer does not exist on a part of the surface of the base material or the undercoat layer formed on the base material, the ink composition of the present invention can be used. The layer to be formed may be formed on the surface of a base material or an undercoat layer formed on the base material.
　本発明のインク組成物を用いた印刷により形成される層は、紫外線等の活性エネルギー線の照射により硬化されることになる。活性エネルギー線の光源としては、高圧水銀ランプ、メタルハライドランプ、ＬＥＤランプ等を使用できる。また、この層を硬化させるために照射する活性エネルギー線の波長は、光重合開始剤の吸収波長と重複していることが好ましく、活性エネルギー線の主波長が３５０～４００ｎｍであることが好ましい。なお、活性エネルギー線の積算光量は１００～２０００ｍＪ／ｃｍ２の範囲にあることが好ましい。 A layer formed by printing using the ink composition of the present invention is cured by irradiation with active energy rays such as ultraviolet rays. A high-pressure mercury lamp, a metal halide lamp, an LED lamp, or the like can be used as a light source for active energy rays. The wavelength of the active energy ray irradiated to cure this layer preferably overlaps with the absorption wavelength of the photopolymerization initiator, and the dominant wavelength of the active energy ray is preferably 350 to 400 nm. It is preferable that the integrated amount of active energy rays is in the range of 100 to 2000 mJ/cm 2 .
　本発明のインク組成物は、インクジェット印刷の吐出条件やその後の硬化条件を適宜選択することで、グロス調、マット調等の表面仕上げ加工を行うことができる。例えば、インク組成物が拡がった後、時間を置いて硬化すればグロス調になり、インク滴がレンズ状のまま硬化すればマット調になる。 The ink composition of the present invention can be subjected to surface finishing such as gloss tone and matte tone by appropriately selecting ejection conditions for inkjet printing and subsequent curing conditions. For example, if the ink composition spreads and then cures after a period of time, it will have a gloss finish, and if the ink droplets remain in the form of a lens and harden, it will have a matte finish.
　本発明の別の態様は、本発明のインク組成物を用いた印刷物である。本発明の印刷物は、加飾層と、加飾層上に位置する層とを備え、ここで、加飾層上に位置する層は、上述した本発明のインク組成物により形成される層であり、クリア層であることが好ましい。本発明のインク組成物および本発明の印刷方法の説明において記載した内容については、本発明の印刷物にも当てはまることである。 Another aspect of the present invention is a printed matter using the ink composition of the present invention. The printed matter of the present invention comprises a decorative layer and a layer positioned on the decorative layer, wherein the layer positioned on the decorative layer is a layer formed from the ink composition of the present invention described above. and preferably a clear layer. The contents described in the description of the ink composition of the present invention and the printing method of the present invention also apply to the printed matter of the present invention.
　本発明の印刷物の一実施態様において、加飾層は、基材や基材上に位置する下塗り層などの表面の少なくとも一部に配置されている。すなわち、本発明の印刷物は、基材と、基材上に位置する加飾層と、加飾層上に位置し、本発明のインク組成物により形成される層とを備える印刷物とすることができ、また、基材と、基材上に位置する下塗り層、下塗り層上に位置する加飾層と、加飾層上に位置し、本発明のインク組成物により形成される層とを備える印刷物とすることもできる。 In one embodiment of the printed matter of the present invention, the decorative layer is arranged on at least part of the surface of the base material or the undercoat layer positioned on the base material. That is, the printed matter of the present invention can be a printed matter comprising a base material, a decorative layer positioned on the base material, and a layer positioned on the decorative layer and formed from the ink composition of the present invention. and comprises a substrate, an undercoat layer positioned on the substrate, a decorative layer positioned on the undercoat layer, and a layer positioned on the decorative layer and formed from the ink composition of the present invention. It can also be printed.
　本発明の印刷物の一実施態様において、本発明のインク組成物により形成される層は、加飾層の少なくとも一部を覆う層であるが、本発明のインク組成物により形成される層は、加飾層の表面全体を覆う層であることが好ましい。 In one embodiment of the printed matter of the present invention, the layer formed by the ink composition of the present invention is a layer covering at least a part of the decorative layer, and the layer formed by the ink composition of the present invention It is preferably a layer that covers the entire surface of the decorative layer.
　本発明の印刷物の一実施態様において、基材や下塗り層などの表面の一部に加飾層が存在しない箇所がある場合には、本発明のインク組成物より形成される層は、基材や下塗り層などの表面に配置されていてもよい。 In one embodiment of the printed matter of the present invention, when there is a portion where the decorative layer does not exist on the surface of the base material or the undercoat layer, the layer formed from the ink composition of the present invention is or an undercoat layer.
　以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.
＜インク調製方法＞
　表１～５に示す成分を表１～５に示す量（質量部）で含有する混合物を撹拌・溶解させ均一にした後、濾過を行い、実施例１～４３及び比較例１～１０に示す活性エネルギー線硬化型インクジェットインクを調製した。 <Ink preparation method>
A mixture containing the components shown in Tables 1 to 5 in the amounts (parts by mass) shown in Tables 1 to 5 was stirred and dissolved to make it uniform, and then filtered, and shown in Examples 1 to 43 and Comparative Examples 1 to 10. An active energy ray-curable inkjet ink was prepared.
　　以下に、表に示される成分の詳細を示す。
　＜光重合性化合物＞
　化合物名／製品名（メーカー）、分子量（ｇ／ｍｏｌ）、Ｔｇ（Ｋ）
１）　アクリロイルモルホリン（ＫＪケミカルズ株式会社）、１４１、４１８
２）　Ｎ－ビニルカプロラクタム（ＢＡＳＦ）、１３９、３６３
３）　(３－エチルオキセタン－３－イル)メチルアクリレート（大阪有機化学工業株式会社）、１７０、２７５
４）　(２－メチル－２－エチル－１，３－ジオキソラン－４－イル)メチルアクリレート（大阪有機化学工業株式会社）、２００、２６６
５）　環状トリメチロールプロパンホルマールアクリレート（大阪有機化学工業株式会社）、２００、３００
６）　テトラヒドロフルフリルアクリレート（共栄社化学株式会社）、１５６、２６１
７）　イソボルニルアクリレート（共栄社化学株式会社）、２０８、３６１
８）　アダマンチルアクリレート（大阪有機化学工業株式会社）、２０６、４２６
９）　ジシクロペンタニルアクリレート（昭和電工マテリアルズ株式会社）、２０６、３９３
１０）　ジシクロペンテニルアクリレート（昭和電工マテリアルズ株式会社）、２０４、３９３
１１）　４－ｔｅｒｔＢｕシクロヘキシルアクリレート（Ｓａｒｔｏｍｅｒ）、２１０、３０７
１２）　トリシクロデカンジメタノールジアクリレート（共栄社化学株式会社）、３０４、３８３
１３）　ＥＢＥＣＲＹＬ８００（ダイセル・オルネクス株式会社）、＜５０００、非開示
１４）　アロニックス　Ｍ－６２５０（東亞合成株式会社）、＜５０００、３１８
１５）　アロニックス　Ｍ－８１００（東亞合成株式会社）、＜５０００、４３６
１６）　アロニックス　Ｍ－７１００（東亞合成株式会社）、＜５０００、３７８
１７）　フェノキシエチルアクリレート（共栄社化学株式会社）、１９２、２７８
１８）　フェノキシジエチレングリコールアクリレート（共栄社化学株式会社）、２３６、２６０
１９）　ベンジルアクリレート（共栄社化学株式会社）、１６２、２７９
２０）　ヒドロキシエチルアクリレート（共栄社化学株式会社）、１１６、２５８
２１）　ラウリルアクリレート（共栄社化学株式会社）、２４０、２７０
２２）　１，６－ヘキサンジオールジアクリレート（共栄社化学株式会社）、２２６、３３６
２３）　ペンタエリスリトールトリアクリレート（共栄社化学株式会社）、２９８、３０５
２４）　ジペンタエリスリトールヘキサアクリレート（共栄社化学株式会社）、５７８、３８３
２５）　ＥＢＥＣＲＹＬ８４０２（ダイセル・オルネクス株式会社）、＜５０００、２８７
＜光重合開始剤＞
　化合物名（メーカー）、分子量（ｇ／ｍｏｌ）
２６）　２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド（ＢＡＳＦ）、３４８
２７）　ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（ＢＡＳＦ）、４１９
＜紫外線吸収剤＞
製品名（メーカー）、分子量（ｇ／ｍｏｌ）
２８）　Ｔｉｎｕｖｉｎ ４００（ＢＡＳＦ）、６４７
２９）　Ｔｉｎｕｖｉｎ ４０５（ＢＡＳＦ）、５８４
３０）　Ｔｉｎｕｖｉｎ ４７９（ＢＡＳＦ）、非開示
３１）　Ｔｉｎｕｖｉｎ ９００（ＢＡＳＦ）、４４８
３２）　Ｔｉｎｕｖｉｎ ＰＳ（ＢＡＳＦ）、２６７
＜ラジカル捕捉剤＞
化合物名／製品名（メーカー）、分子量（ｇ／ｍｏｌ）、官能基数
３３）　ＥＶＥＲＳＯＲＢ　９０（Ｅｖｅｒｌｉｇｈｔ Ｃｈｅｍｉｃａｌ）、４８１、２
３４）　Ｔｉｎｕｖｉｎ　１２３（ＢＡＳＦ）、７３７、２
３５）　メチルハイドロキノン（精工化学株式会社）、１２４、１
３６）　ジブチルヒドロキシトルエン（東京化成工業株式会社）、２２０、２
＜樹脂＞
製品名（メーカー）、樹脂系統
３７）　ＣＡＢ５５１－００．１（Ｅａｓｔｍａｎ）、セルロースアセテートブチレート
３８）　エスレック　ＢＬ－２（積水化学株式会社）、ポリビニルアセタール
３９）　ＡｄｄＢｏｎｄ　ＬＴＨ（Ｅｖｏｎｉｋ）、変性ポリエステル Below are the details of the ingredients shown in the table.
<Photopolymerizable compound>
Compound name/product name (manufacturer), molecular weight (g/mol), Tg (K)
1) Acryloylmorpholine (KJ Chemicals Co., Ltd.), 141, 418
2) N-vinylcaprolactam (BASF), 139, 363
3) (3-ethyloxetan-3-yl)methyl acrylate (Osaka Organic Chemical Industry Co., Ltd.), 170, 275
4) (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (Osaka Organic Chemical Industry Co., Ltd.), 200, 266
5) Cyclic trimethylolpropane formal acrylate (Osaka Organic Chemical Industry Co., Ltd.), 200, 300
6) Tetrahydrofurfuryl acrylate (Kyoeisha Chemical Co., Ltd.), 156, 261
7) Isobornyl acrylate (Kyoeisha Chemical Co., Ltd.), 208, 361
8) Adamantyl acrylate (Osaka Organic Chemical Industry Co., Ltd.), 206, 426
9) Dicyclopentanyl acrylate (Showa Denko Materials Co., Ltd.), 206, 393
10) Dicyclopentenyl acrylate (Showa Denko Materials Co., Ltd.), 204, 393
11) 4-tertBu cyclohexyl acrylate (Sartomer), 210, 307
12) Tricyclodecane dimethanol diacrylate (Kyoeisha Chemical Co., Ltd.), 304, 383
13) EBECRYL800 (Daicel Allnex Co., Ltd.), <5000, undisclosed 14) Aronix M-6250 (Toagosei Co., Ltd.), <5000, 318
15) Aronix M-8100 (Toagosei Co., Ltd.), <5000, 436
16) Aronix M-7100 (Toagosei Co., Ltd.), <5000, 378
17) Phenoxyethyl acrylate (Kyoeisha Chemical Co., Ltd.), 192, 278
18) Phenoxydiethylene glycol acrylate (Kyoeisha Chemical Co., Ltd.), 236, 260
19) Benzyl Acrylate (Kyoeisha Chemical Co., Ltd.), 162, 279
20) Hydroxyethyl acrylate (Kyoeisha Chemical Co., Ltd.), 116, 258
21) Lauryl acrylate (Kyoeisha Chemical Co., Ltd.), 240, 270
22) 1,6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd.), 226, 336
23) Pentaerythritol triacrylate (Kyoeisha Chemical Co., Ltd.), 298, 305
24) Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd.), 578, 383
25) EBECRYL8402 (Daicel Allnex Co., Ltd.), <5000, 287
<Photoinitiator>
Compound name (manufacturer), molecular weight (g/mol)
26) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF), 348
27) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BASF), 419
<Ultraviolet absorber>
Product name (manufacturer), molecular weight (g/mol)
28) Tinuvin 400 (BASF), 647
29) Tinuvin 405 (BASF), 584
30) Tinuvin 479 (BASF), undisclosed 31) Tinuvin 900 (BASF), 448
32) Tinuvin PS (BASF), 267
<Radical Scavenger>
Compound name/product name (manufacturer), molecular weight (g/mol), number of functional groups: 33) EVERSORB 90 (Everlight Chemical), 481, 2
34) Tinuvin 123 (BASF), 737, 2
35) Methyl hydroquinone (Seiko Chemical Co., Ltd.), 124, 1
36) Dibutyl hydroxytoluene (Tokyo Chemical Industry Co., Ltd.), 220, 2
<Resin>
Product name (manufacturer), resin system 37) CAB551-00.1 (Eastman), cellulose acetate butyrate 38) S-lec BL-2 (Sekisui Chemical Co., Ltd.), polyvinyl acetal 39) AddBond LTH (Evonik), modified polyester
＜吐出安定性＞
　活性エネルギー線硬化型インクジェットインク組成物を用いたインクジェットプリンタによって画像を基材上に印刷し、その吐出安定性を下記の基準に従い目視で評価した。なお、インクジェットプリンタの印字ヘッドから基材までの距離を１．５ｍｍに設定して印刷を行った。結果を表１～５に示す。
［評価基準］
◎：ノズル詰まりを起こすことなく、所定の位置に印刷することが容易にでき、吐出量、硬化タイミングの調節によって任意の印刷面が得られる。
○：ノズル詰まりを起こすことなく、所定の位置に印刷することができるが、吐出量、硬化タイミングの調整に制限を要する。
△：ノズル詰まりは発生しないが、わずかに飛行曲りが発生する。
×：ノズル詰まりが発生して、吐出に抜けが生じ、更には、インクを所定の位置に付着できず、綺麗な印刷面を得ることができない。 <Ejection stability>
An image was printed on the substrate by an inkjet printer using the active energy ray-curable inkjet ink composition, and the ejection stability was visually evaluated according to the following criteria. The printing was performed by setting the distance from the print head of the inkjet printer to the base material to 1.5 mm. The results are shown in Tables 1-5.
[Evaluation criteria]
⊚: Nozzle clogging is not caused and printing can be easily performed at a predetermined position, and an arbitrary printed surface can be obtained by adjusting the discharge amount and curing timing.
◯: Printing can be performed at a predetermined position without causing nozzle clogging, but restrictions are required in adjusting the discharge amount and curing timing.
Δ: No nozzle clogging, but slight flight deflection.
x: Nozzle clogging occurs, ejection failure occurs, and ink cannot adhere to a predetermined position, making it impossible to obtain a clean printed surface.
＜耐候性試験１．耐黄変性＞
　促進耐候性（ＪＩＳ　Ｋ　５６００－７－７：２００８に準拠）
　アルミニウム基材上に、ポリ塩化ビニル製のシートを張り、その上にバーコーター＃１０にて実施例１～４３及び比較例１～１０に示す活性エネルギー線硬化型インクジェットインクを塗布した後、活性エネルギー線（主波長３８５ｎｍ）を照射して充分に硬化させた硬化膜上のＬ＊ａ＊ｂ＊測色値と、促進耐候性試験を１５００時間後の測色値との色差ΔＥを求め、以下の基準に基づいて評価した。結果を表１～５に示す。
［評価基準］
◎：試験前の測色値との色差ΔＥが２未満
○：試験前の測色値との色差ΔＥが２以上３未満
△：試験前の測色値との色差ΔＥが３以上５未満
×：試験前の測色値との色差ΔＥが５以上 <Weather resistance test 1. Yellowing resistance>
Accelerated weather resistance (based on JIS K 5600-7-7:2008)
On the aluminum substrate, a sheet made of polyvinyl chloride was applied, and the active energy ray-curable inkjet inks shown in Examples 1 to 43 and Comparative Examples 1 to 10 were applied thereon with a bar coater #10, and then activated. Determine the color difference ΔE between the L*a*b* colorimetric value on the cured film sufficiently cured by irradiation with energy rays (main wavelength 385 nm) and the colorimetric value after 1500 hours of the accelerated weather resistance test, It was evaluated based on the following criteria. The results are shown in Tables 1-5.
[Evaluation criteria]
◎: Color difference ΔE from the colorimetric values before the test is less than 2 ○: Color difference ΔE from the colorimetric values before the test is 2 or more and less than 3 △: Color difference ΔE from the colorimetric values before the test is 3 or more and less than 5 × : The color difference ΔE from the colorimetric value before the test is 5 or more
＜耐候性試験２．耐クラック性＞
　促進耐候性（ＪＩＳ　Ｋ　５６００－７－７：２００８に準拠）
　＜耐候性試験１．耐黄変性＞と同様の方法で硬化膜を作製し、促進耐候性試験を実施した。
　試験時間１５００時間まで実施した後、以下の基準に基づいて、塗膜外観を目視で評価した。結果を表１～５に示す。
［評価基準］
◎：試験時間１５００時間後もクラックが全くない。
〇：試験時間１２００－１５００時間にクラックが発生。
△：試験時間１０００－１２００時間後にクラックが発生。
×：試験時間１０００時間前にクラックが発生。 <Weather resistance test 2. Crack resistance>
Accelerated weather resistance (based on JIS K 5600-7-7:2008)
<Weather resistance test 1. A cured film was prepared in the same manner as in Yellowing resistance>, and an accelerated weather resistance test was performed.
After conducting the test up to 1500 hours, the appearance of the coating film was visually evaluated based on the following criteria. The results are shown in Tables 1-5.
[Evaluation criteria]
⊚: No cracks at all even after 1500 hours of test time.
◯: Cracks occurred at the test time of 1200 to 1500 hours.
Δ: Cracks occurred after 1000 to 1200 hours of test time.
x: Cracks occurred 1000 hours before the test time.
＜耐ブロッキング性＞
　実施例１～４３、比較例１～１０のインクについて、各々エステルフィルムＥ５０００（東洋紡株式会社製）上にバーコーター #10を用いてインクを塗布した後、活性エネルギー線（主波長３８５ｎｍ）を照射して充分に硬化させ、印刷物を作製した。印刷物の硬化膜全体が覆われるように、未印刷のエステルフィルムＥ５０００を硬化膜上部に重ねた。更に、上部から０．２００ｇ／ｃｍ２の加重を加え、２５℃雰囲気下で１日間放置し、下記の基準により、耐ブロッキング性を評価した。結果を表１～５に示す。
［評価基準］
◎：完全に滑らかにフィルム同士が剥がれ、膜潰れ等の外観異常がない
○：フィルム同士がやや音を立てて剥がれるが、膜潰れ等の外観異常がない
△：フィルム同士を剥がした際に、僅かに膜潰れがある
×：フィルム同士を剥がした際に、塗膜の剥離が発生する <Blocking resistance>
For the inks of Examples 1 to 43 and Comparative Examples 1 to 10, each ink was applied onto an ester film E5000 (manufactured by Toyobo Co., Ltd.) using a bar coater #10, and then irradiated with an active energy ray (main wavelength 385 nm). and sufficiently hardened to produce a printed matter. An unprinted ester film E5000 was placed on top of the cured film so as to cover the entire cured film of the print. Further, a weight of 0.200 g/cm 2 was applied from the top, and the film was allowed to stand in an atmosphere of 25° C. for 1 day, and the blocking resistance was evaluated according to the following criteria. The results are shown in Tables 1-5.
[Evaluation criteria]
◎: The films are peeled off completely smoothly, and there is no appearance abnormality such as film crushing ○: The films are peeled off with a slight noise, but there is no appearance abnormality such as film crushing △: When the films are peeled off, There is a slight film collapse ×: When the films are peeled off, peeling of the coating film occurs
＜付着性＞
　上記耐候性試験１と同様の方法で得た印刷物について、印刷層に１ｍｍ幅１００マスのクロスカットを施した。その後、クロスカット面を中心として９０°に折り曲げ、セロハンテープを十分に接着させて、セロハンテープを剥がし、付着性の評価を以下に示す基準に従って行った。結果を表１～５に示す。
［評価基準］
◎：カット部に剥離が確認されない。
○：カット部に５％未満の剥離が確認された。
△：カット部に５％以上２０％未満の剥離が確認された。
×：カット部に２０％以上の剥離が確認された。 <Adhesion>
A printed matter obtained in the same manner as in weather resistance test 1 was subjected to a cross cut of 100 squares with a width of 1 mm on the printed layer. Thereafter, the cross-cut surface was bent at 90°, the cellophane tape was sufficiently adhered, the cellophane tape was peeled off, and the adhesion was evaluated according to the following criteria. The results are shown in Tables 1-5.
[Evaluation criteria]
A: Peeling is not observed at the cut portion.
◯: Less than 5% peeling was observed at the cut portion.
Δ: Peeling of 5% or more and less than 20% was confirmed at the cut portion.
x: Peeling of 20% or more was confirmed at the cut portion.
＜延伸性＞
　実施例１～４３、比較例１～１０のインクについて、背面に剥離紙が付いたポリ塩化ビニル製のシート上にバーコーター #10を用いてインクを塗布した後、活性エネルギー線（主波長３８５ｎｍ）を照射して充分に硬化させ、印刷物を作製した。その後、縦５０ｍｍ×横１０ｍｍにカットし、背面の剥離紙を剥がし測定用試料を得た。
　測定用試料について、２３℃にて島津製作所社製精密万能試験機オートグラフＡＧ－１　１００ｋＮを用い、ロードセル：１００Ｎ、測定温度：２３℃、引っ張り速度：２０ｍｍ／ｍｉｎの速度で引っ張り試験を行って、以下の算出式で塗膜の伸び率を算出した。破断の判定は目視で行い、目視にてヒビが確認された時点で破断とした。結果を表１～５に示す。
｛（引っ張り試験での破断時の測定用試料長さ－試験前の測定用試料長さ）／（試験前の測定用試料長さ）｝×１００＝延伸率（％）
［評価基準］
○：１００％以上
△：５０％以上、１００％未満
×：５０％未満 <Stretchability>
For the inks of Examples 1 to 43 and Comparative Examples 1 to 10, the ink was applied using a bar coater #10 on a polyvinyl chloride sheet with release paper on the back, and then exposed to an active energy ray (dominant wavelength 385 nm ) was irradiated and sufficiently cured to produce a printed matter. After that, it was cut into a size of 50 mm long and 10 mm wide, and the release paper on the back was peeled off to obtain a sample for measurement.
The sample for measurement was subjected to a tensile test at 23° C. using a precision universal testing machine Autograph AG-1 100 kN manufactured by Shimadzu Corporation, load cell: 100 N, measurement temperature: 23° C., tensile speed: 20 mm / min. , the elongation rate of the coating film was calculated by the following formula. Determination of rupture was made visually, and when cracks were visually confirmed, it was regarded as rupture. The results are shown in Tables 1-5.
{(Measurement sample length at break in tensile test−Measurement sample length before test)/(Measurement sample length before test)}×100=Elongation rate (%)
[Evaluation criteria]
○: 100% or more △: 50% or more, less than 100% ×: less than 50%
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-I000010
　表中の「（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物／インク組成物」は、インク組成物中における（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物の割合（質量％）を示す。
　表中の「（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性／インク組成物」は、インク組成物中における（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物の割合（質量％）を示す。
　表中の「（Ａ３）ポリエステル構造を有する多官能光重合性化合物／インク組成物」は、インク組成物中における（Ａ３）ポリエステル構造を有する２官能以上の多官能光重合性化合物の割合（質量％）を示す。
　表中の「単官能重合性化合物／光重合性化合物」は、光重合性化合物中における単官能光重合性化合物の割合（質量％）を示す。 "(A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure/ink composition" in the table is (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure in the ink composition. Shows the ratio (mass%) of.
"(A2) monofunctional photopolymerizable/ink composition having a heteroatom-free cyclic structure" in the table refers to (A2) monofunctional photopolymerizable having a heteroatom-free cyclic structure in the ink composition. The ratio (% by mass) of the compound is shown.
"(A3) polyfunctional photopolymerizable compound having a polyester structure/ink composition" in the table indicates the proportion (mass %).
"Monofunctional polymerizable compound/photopolymerizable compound" in the table indicates the proportion (% by mass) of the monofunctional photopolymerizable compound in the photopolymerizable compound.

Claims (9)

  1. （Ａ）光重合性化合物、（Ｂ）光重合開始剤、（Ｃ）紫外線吸収剤を含む、表面保護層形成用インク組成物であって、（Ａ）光重合性化合物が（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物と（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物を少なくとも含み、（Ａ）光重合性化合物中の単官能光重合性化合物の割合が７５～９５質量％の範囲内であることを特徴とする、表面保護層形成用インク組成物。（ただし、（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物および（Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物を構成する前記環状構造は、芳香環を有しない環状構造である。） An ink composition for forming a surface protective layer comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) an ultraviolet absorber, wherein (A) the photopolymerizable compound comprises (A1) a heteroatom A monofunctional photopolymerizable compound having a cyclic structure containing at least (A2) a monofunctional photopolymerizable compound having a heteroatom-free cyclic structure, and (A) a monofunctional photopolymerizable compound in the photopolymerizable compound is in the range of 75 to 95% by mass, an ink composition for forming a surface protective layer. (However, (A1) the monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure and (A2) the cyclic structure constituting the monofunctional photopolymerizable compound having a heteroatom-free cyclic structure is an aromatic ring. It is a cyclic structure that does not have.)
  2. （Ａ）光重合性化合物が（Ａ３）ポリエステル構造を有する２官能以上の多官能光重合性化合物を含むことを特徴とする、請求項１に記載の表面保護層形成用インク組成物。 2. The ink composition for forming a surface protective layer according to claim 1, wherein (A) the photopolymerizable compound contains (A3) a bifunctional or higher polyfunctional photopolymerizable compound having a polyester structure.
  3. インク組成物中の（Ａ１）ヘテロ原子を含む環状構造を有する単官能光重合性化合物の量が３０～９０質量％の範囲内であることを特徴とする、請求項１または２に記載の表面保護層形成用インク組成物。 The surface according to claim 1 or 2, wherein the amount of (A1) a monofunctional photopolymerizable compound having a heteroatom-containing cyclic structure in the ink composition is in the range of 30 to 90% by mass. An ink composition for forming a protective layer.
  4. （Ａ２）ヘテロ原子を含まない環状構造を有する単官能光重合性化合物が、イソボルニル（メタ）アクリレートを含まないことを特徴とする、請求項１～３のいずれかに記載の表面保護層形成用インク組成物。 (A2) for forming a surface protective layer according to any one of claims 1 to 3, wherein the monofunctional photopolymerizable compound having a heteroatom-free cyclic structure does not contain isobornyl (meth)acrylate. ink composition.
  5. （Ｃ）紫外線吸収剤が、波長３８５ｎｍにおけるモル吸光係数が１．５×１０３（ｌ・ｍｏｌ－１・ｃｍ－１）以下である紫外線吸収剤を少なくとも含むことを特徴とする、請求項１～４のいずれかに記載の表面保護層形成用インク組成物。 Claim 1, wherein (C) the ultraviolet absorber contains at least an ultraviolet absorber having a molar extinction coefficient of 1.5×10 3 (l·mol −1 ·cm −1 ) or less at a wavelength of 385 nm. 5. The ink composition for forming a surface protective layer according to any one of items 1 to 4.
  6. さらにメチルハイドロキノン（ＭＥＨＱ）及びブチルヒドロキシトルエン（ＢＨＴ）以外の（Ｄ）ラジカル捕捉剤を含有することを特徴とする、請求項１～５のいずれかに記載の表面保護層形成用インク組成物。 6. The ink composition for forming a surface protective layer according to any one of claims 1 to 5, further comprising (D) a radical scavenger other than methylhydroquinone (MEHQ) and butylhydroxytoluene (BHT).
  7. （Ｄ）ラジカル捕捉剤が、ヒンダードアミン系化合物を含むことを特徴とする、請求項６に記載の表面保護層形成用インク組成物。 7. The ink composition for forming a surface protective layer according to claim 6, wherein (D) the radical scavenger contains a hindered amine compound.
  8. （Ａ）光重合性化合物の合計光重合性官能基モル数ＡＭと（Ｄ）ラジカル捕捉剤のモル数ＤＭの比ＡＭ／ＤＭが１０以上であることを特徴とする、請求項６または７に記載の表面保護層形成用インク組成物。 (A) the total number of moles of photopolymerizable functional groups AM of the photopolymerizable compound and (D) the number of moles DM of the radical scavenger, wherein the ratio AM/DM is 10 or more; The ink composition for forming a surface protective layer described above.
  9. さらに樹脂を含有することを特徴とする、請求項１～８のいずれかに記載の表面保護層形成用インク組成物。 9. The ink composition for forming a surface protective layer according to any one of claims 1 to 8, further comprising a resin.
PCT/JP2022/015558 2021-03-31 2022-03-29 Ink composition for forming surface-protecting layers WO2022210740A1 (en)

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JP2010522795A (en) * 2007-03-27 2010-07-08 セリコル リミテッド Printing ink
JP2012197385A (en) * 2011-03-23 2012-10-18 Seiren Co Ltd Ultraviolet curing ink for steel sheet decorating, method for decorating steel sheet, and decorated decorative steel sheet
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