WO2018168609A1 - Actinic-ray-curable ink composition, layered product obtained using said ink composition, method for forming image on substrate, and production method for printed matter - Google Patents

Actinic-ray-curable ink composition, layered product obtained using said ink composition, method for forming image on substrate, and production method for printed matter Download PDF

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Publication number
WO2018168609A1
WO2018168609A1 PCT/JP2018/008803 JP2018008803W WO2018168609A1 WO 2018168609 A1 WO2018168609 A1 WO 2018168609A1 JP 2018008803 W JP2018008803 W JP 2018008803W WO 2018168609 A1 WO2018168609 A1 WO 2018168609A1
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WO
WIPO (PCT)
Prior art keywords
active energy
energy ray
ink composition
curable ink
resin
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Application number
PCT/JP2018/008803
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French (fr)
Japanese (ja)
Inventor
公淳 宇▲高▼
森田　浩司
保真 齋藤
Original Assignee
株式会社Ｄｎｐファインケミカル
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Publication of WO2018168609A1 publication Critical patent/WO2018168609A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09D11/30—Inkjet printing inks
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • the present invention relates to an active energy ray-curable ink composition used as an inkjet ink, a laminate on which the ink composition is printed, and forms an image and / or an uneven image on a substrate using the ink composition.
  • the present invention relates to an image forming method and a method for producing a printed material using the ink composition.
  • the active energy ray-curable ink composition is composed of an active energy ray polymerizable monomer, a coloring material, and other additives.
  • inkjet printing methods using active energy rays are being actively researched.
  • This method is a method in which liquid ink is applied to paper, plastic, etc., and then cured and crosslinked, for example, by irradiating with ultraviolet rays.
  • it has a quick drying property.
  • the ink jet method does not require a plate at the time of printing, and ink is ejected only to the required image portion and image formation is performed directly on the recording medium, so that the ink can be used efficiently and active energy rays are used.
  • the ink jet printing method used has attracted attention.
  • Patent Document 1 discloses an active energy ray-curable inkjet ink composition containing a predetermined polymerization inhibitor in an active energy ray-curable ink composition.
  • the active energy ray-curable ink composition of Patent Document 1 is an active energy ray-curable ink composition having a low viscosity and excellent curability in both an oxygen-free atmosphere and in the presence of oxygen. It is.
  • an active energy ray-curable ink composition used as an ink jet ink is not simply preferable as its viscosity is low.
  • the optimum viscosity of the active energy ray-curable ink composition varies depending on the specifications of the nozzles in the inkjet printing apparatus and the inkjet printing apparatus. Therefore, the viscosity of the active energy ray-curable ink composition is strictly adjusted so as to be optimal according to the printing apparatus and the specifications of the apparatus (for example, the nozzle of the printing apparatus).
  • the viscosity of the active energy ray-curable ink composition changes with time even if the active energy ray-curable ink composition has a desired viscosity in the initial state of the active energy ray-curable ink composition.
  • the viscosity of the active energy ray-curable ink composition may change during storage of the active energy ray-curable ink composition, in the flow path or in the inkjet head, and the optimum viscosity required by the printing apparatus may not be achieved. there were.
  • the present invention has been made in view of the above circumstances, and the object of the present invention is an active energy ray-curable ink composition whose viscosity can be easily adjusted in an active energy ray-curable ink composition.
  • the present invention also provides an active energy ray-curable ink composition with little change in viscosity over time.
  • the inventors of the present invention have made extensive studies in order to solve the above problems. As long as the active energy ray-curable ink composition contains a non-reactive resin having a predetermined acid value, the above problems can be solved. The present inventors have found that this can be done and have completed the present invention. Specifically, the present invention provides the following.
  • An active energy ray-curable ink composition used as an inkjet ink containing an active energy ray polymerizable monomer and a non-reactive resin which is measured based on JIS K 0070: 1992
  • An active energy ray-curable ink composition, wherein the acid value of the non-reactive resin is 3.0 mgKOH / g or less.
  • the non-reactive resin is at least one resin selected from the group consisting of a cellulose resin, a (meth) acrylic resin, and a polyol resin.
  • the active energy ray-curable ink composition as described.
  • the active energy ray-curable ink composition according to any one of (1) to (6) is allowed to stand at 60 ° C. for 28 days, and the viscosity at 40 ° C. of the active energy ray-curable ink composition before the storage test is measured.
  • Va unit: mPa ⁇ s
  • Vb unit: mPa ⁇ s
  • Va ⁇ 100 unit % Is more than ⁇ 10% and less than 10%.
  • the active energy ray-curable ink composition of the present invention is an active energy ray-curable ink composition whose viscosity can be easily adjusted, and is an active energy ray-curable ink composition with little change in viscosity over time. is there.
  • An active energy ray-curable ink composition according to an embodiment of the present invention is an active energy ray-curable ink composition used as an inkjet ink containing an active energy ray-polymerizable monomer and a non-reactive resin. .
  • an active energy ray-curable ink composition used as an inkjet ink containing an active energy ray-polymerizable monomer and a non-reactive resin.
  • each component which may be contained in the non-reactive resin, the active energy ray polymerizable monomer, and the active energy ray curable ink composition of the present invention will be described.
  • Non-reactive resin The active energy ray-curable ink composition of the present embodiment contains a non-reactive resin.
  • the non-reactive resin means a resin having no functional group capable of radical reaction with the active energy ray polymerizable monomer or the active group of another component.
  • the acid value of the non-reactive resin measured based on JIS K 0070: 1992 concerning this embodiment is 3.0 mgKOH / g or less.
  • the acid value of the non-reactive resin regarding this embodiment is 2.5 mgKOH / g or less, and it is more preferable that it is 2.0 mgKOH / g or less.
  • an active energy ray-curable ink composition used as an ink jet ink is not simply preferable as its viscosity is low.
  • the viscosity of the active energy ray-curable ink composition is strictly adjusted so as to be optimal according to the printing apparatus and the specifications of the apparatus.
  • the viscosity of an active energy ray-curable ink composition used as an ink jet ink in recent years can be easily adjusted so as to be optimal according to the specifications of the printing apparatus and the apparatus, and the viscosity of the ink composition with time It is required to be an active energy ray-curable ink composition with little change.
  • Examples of a method for adjusting the viscosity of the active energy ray-curable ink composition include a method of adding a resin.
  • a resin that does not have a functional group capable of radical reaction with an active energy ray polymerizable monomer or an active group of another component.
  • the viscosity of the active energy ray-curable ink composition changes with time.
  • the active energy ray-curable ink composition of the present embodiment includes (1) an active energy ray-curable ink composition that can be easily adjusted in viscosity by containing a non-reactive resin having a predetermined acid value. And (2) an active energy ray-curable ink composition capable of simultaneously satisfying the two effects of an active energy ray-curable ink composition with little change in viscosity over time.
  • the active energy ray-curable ink composition thus obtained is a novel active energy ray-curable ink composition that has not been conventionally used.
  • the preferred viscosity at 40 ° C. of the active energy ray-curable ink composition varies depending on the specifications of the inkjet printing apparatus and nozzles, but is 20 mPa ⁇ s or less from the viewpoint of ejection stability and the like in the inkjet printing apparatus. Preferably, it is 15 mPa ⁇ s or less.
  • the preferable viscosity of the active energy ray-curable ink composition is preferably 5 mPa ⁇ s or more, and more preferably 7 mPa ⁇ s or more.
  • the viscosity can be measured with a falling ball viscometer based on, for example, DIN EN ISO 12058-1.
  • the active energy ray-curable ink composition with little change in viscosity over time can be evaluated by, for example, the following index.
  • the viscosity Va (unit: mPa ⁇ s) at 40 ° C. of the active energy ray-curable ink composition before the storage test is measured.
  • the active energy ray-curable ink composition is sealed in a brown glass bottle that can block light from the outside.
  • the active energy ray-curable ink composition sealed in a glass bottle is subjected to a storage test at 60 ° C. for 28 days.
  • the viscosity Vb (unit: mPa ⁇ s) at 40 ° C. of the active energy ray-curable ink composition after the storage test is determined.
  • the value of (Vb ⁇ Va) / Va ⁇ 100 is preferably more than ⁇ 10% and less than 10%, more preferably more than ⁇ 8% and less than 8%, more than ⁇ 5% and more than 5%. More preferably, it is less than 2% and even more preferably more than -2% and less than 2%.
  • the non-reactive resin related to the present embodiment is not particularly limited as long as it is a resin that does not have a functional group capable of radical reaction with an active energy ray polymerizable monomer or an active group of another component.
  • the functional group capable of radical reaction with the active energy ray-polymerizable monomer or the active group of another component include a functional group having an ethylenically unsaturated double bond.
  • the non-reactive resin relating to the present embodiment include cellulose acetate alkylate resin, cellulose acetate resin, polyol resin, (meth) acrylic resin, epoxy resin, ketone resin, nitrocellulose resin, phenoxy resin, polyester resin, and vinyl resin.
  • cellulose acetate alkylate resin examples include cellulose acetate butyrate resin (for example, Eastman Chemical Japan, trade name “CAB551-0.01”), cellulose acetate propionate resin, cellulose acetate propionate butyrate. Examples thereof include resins.
  • polyol resin examples include hydrogenated products that are ketone-formaldehyde condensates of TEGO (registered trademark) VARIPLUS SK: Evonik Degussa Japan Co., Ltd.
  • the acrylic resin is an acrylic polymer having no reactive functional group, and examples thereof include an acrylic polymer of Degalan 66 / 02N (EVONIK INDUSTRIES).
  • the content of the non-reactive resin relating to the present embodiment is not particularly limited.
  • the content in the non-reactive resin depends on the number-average molecular weight of the non-reactive resin, but from the viewpoint that the viscosity of the active energy ray-curable ink composition used as the ink for inkjet can be increased to a preferable range.
  • the content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total amount of the active energy ray-curable ink composition.
  • the content in the non-reactive resin depends on the average molecular weight of the non-reactive resin, but from the viewpoint that the viscosity of the active energy ray-curable ink composition used as an ink jet ink can be suppressed within a preferable range.
  • the content is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total amount of the active energy ray-curable ink composition.
  • the number average molecular weight of the non-reactive resin relating to the present embodiment is not particularly limited, but from the viewpoint that the viscosity of the active energy ray-curable ink composition used as an ink jet ink can be within a preferable range. It is preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 30,000 or less. By setting the average molecular weight of the non-reactive resin to 100,000 or less, it is possible to suppress an increase in viscosity in the active energy ray-curable ink composition with respect to the content of the non-reactive resin.
  • the number average molecular weight of the non-reactive resin relating to the present embodiment, is preferably 500 or more, more preferably 1000 or more, and further preferably 5000 or more.
  • the active energy ray-polymerizable monomer according to this embodiment is not particularly limited as long as it can be polymerized by the action of active energy rays and can dissolve or disperse the aforementioned non-reactive resin. It may be a monofunctional monomer having one ethylenically unsaturated double bond in the compound, or may be a polyfunctional monomer having two or more ethylenically unsaturated double bonds in the compound.
  • the monomer of the “active energy ray polymerizable monomer” in the present invention is a concept including a compound also called an oligomer depending on its molecular weight.
  • the structure of the ethylenically unsaturated double bond in the compound having an active energy ray polymerizable monomer is not particularly limited.
  • a (meth) acryloyl group, a vinyl group, an allyl group, etc. are mentioned.
  • the ethylenically unsaturated double bond is preferably a (meth) acryloyl group from the viewpoint of curability in the ink.
  • “(meth) acryloyl group” means both an acryloyl group and a methacryloyl group.
  • the active energy ray-polymerizable monomer has a (meth) acrylate group in the compound because of its low viscosity, excellent curability of the resulting ink, and small shrinkage upon curing. It is preferable that it is a monofunctional (meth) acrylic acid ester having only one in a bifunctional (meth) acrylic acid ester having two (meth) acrylate groups in the compound. Monofunctional (meth) acrylates are particularly suitable for applications requiring flexibility because of their low viscosity and low cure shrinkage. Bifunctional (meth) acrylates are particularly suitable for applications requiring resistance because of their low viscosity and high crosslink density upon curing. In the present specification, “(meth) acrylate” means both acrylate and methacrylate.
  • Monofunctional (meth) acrylate is not particularly limited.
  • the content of these monofunctional (meth) acrylates is preferably 90% by mass or more in the total amount of monofunctional monomers, More preferably, it is 95 mass% or more, and it is still more preferable that it is 99 mass% or more.
  • aromatic hydrocarbon monofunctional (meth) such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, etc. because of its small curing shrinkage and good adhesion to the cured film.
  • the bifunctional (meth) acrylate is not particularly limited.
  • the content of these bifunctional (meth) acrylates is preferably 90% by mass or more based on the total amount of polyfunctional monomers, More preferably, it is 95 mass% or more, and it is still more preferable that it is 99 mass% or more.
  • the content of these (meth) acrylates is determined based on the active energy ray polymerizable monomers.
  • the total amount is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.
  • bifunctional (meth) acrylates dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) are particularly preferred because of their low viscosity and high crosslinking density.
  • One or more selected from the group consisting of acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propoxylated neopentyl glycol diacrylate are preferred.
  • a monofunctional (meth) acrylate and a bifunctional (meth) acrylate can be used in appropriate combination.
  • the content ratio in the case of using a monofunctional (meth) acrylate and a bifunctional (meth) acrylate in combination may be appropriately adjusted according to the application, and is not particularly limited.
  • bifunctional (meth) acrylate is 60 mass% or less with respect to the monofunctional (meth) acrylate whole quantity from the point which makes adhesiveness and film
  • a vinyl group is preferably used, and examples of the monofunctional vinyl monomer include N-vinylcaprolactam and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, and particularly, N-vinylcaprolactam is It is more preferable because of its low viscosity and good adhesion.
  • the bifunctional vinyl monomer triethylene glycol divinyl ether is more preferable because it has a low viscosity and an excellent ability to reduce the viscosity.
  • the active energy ray-polymerizable monomer according to the present embodiment can be used alone or in combination of two or more.
  • the solvent-free type that is, an organic solvent is not included, and thus the compound having an ethylenically unsaturated bond is usually used as a solvent or a dispersion medium. Therefore, in addition to curability and film physical properties after curing, it is preferable to appropriately select and combine them from the viewpoint of being able to be a solvent or a dispersion medium and having ink jet aptitude.
  • the unsaturated double bond equivalent per gram (hereinafter, simply referred to as an unsaturated double bond equivalent (g / eq)) in the active energy ray-polymerizable monomer according to the present embodiment is not particularly limited. It is preferably 50 g / eq or more and 300 g / eq or less, more preferably 100 g / eq or more and 250 g / eq or less from the viewpoint of being small and having a high crosslinking density.
  • the active energy ray polymerizable monomer that can be a solvent or a dispersion medium may be appropriately selected from those that are liquid at room temperature (25 ° C.). For example, those having a molecular weight of 150 to 400 are preferably used.
  • the active energy ray polymerizable monomer that can be a solvent or a dispersion medium is preferably one that does not contain a hydroxyl group or a carboxy group from the viewpoint of preventing gelation of the inkjet ink composition.
  • the acid value of the active energy ray polymerizable monomer measured based on JIS K 0070: 1992 is 1.0 mgKOH / g or less from the point of viscosity stability in the active energy ray polymerizable monomer according to this embodiment. It is preferably 0.5 mgKOH / g or less.
  • preferable active energy ray polymerizable monomers that can be used as a solvent or a dispersion medium include, for example, phenoxyethyl acrylate, isobornyl acrylate, t-butylcyclohexyl acrylate, ethyl carbitol acrylate, dipropylene glycol diacrylate, Examples include propylene glycol diacrylate, 1,9-nonanediol diacrylate, propoxylated neopentyl glycol diacrylate, and triethylene glycol divinyl ether.
  • the content of the active energy ray polymerizable monomer relating to the present embodiment is not particularly limited. From the viewpoint of curability in the cured film, the content of the active energy ray polymerizable monomer in the entire inkjet ink composition of the present embodiment is preferably 30% by mass or more, and more preferably 45% by mass or more. 60% by mass or more is particularly preferable. From the viewpoint of viscosity stability in the active energy ray polymerizable monomer, the content of the active energy ray polymerizable monomer in the entire inkjet ink composition of the present embodiment is more preferably 95% by mass or less, and 90% by mass or less. It is more preferable that
  • the active energy ray-curable ink composition of the present embodiment may contain an active energy ray polymerization initiator (hereinafter sometimes simply referred to as a polymerization initiator) as necessary.
  • Active energy rays are energy rays that can trigger polymerization reactions such as radicals, cations, anions, etc.
  • Light rays such as deep ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and ⁇ rays, electron beams, Any of proton beam, neutron beam and the like may be used, but curing by ultraviolet irradiation is preferable from the viewpoint of curing speed, availability of irradiation apparatus, price and the like.
  • the polymerization initiator is not particularly limited as long as it accelerates the polymerization reaction of the active energy ray-polymerizable monomer in the active energy ray-curable ink composition by irradiation with active energy rays, and a conventionally known polymerization initiator is used. Can be used.
  • polymerization initiator examples include, for example, aromatic ketones containing thioxanthone, ⁇ -aminoalkylphenones, ⁇ -hydroxy ketones, acylphosphine oxides, aromatic onium salts, organic peroxides, thio compounds , Hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
  • the amount of the polymerization initiator related to this embodiment may be an amount that can appropriately initiate the polymerization reaction of the active energy ray polymerizable monomer, and is 1.0% by mass or more based on the entire active energy ray curable ink composition. It is preferable that the content is 3.0% by mass or more. Moreover, it is preferable that it is 20.0 mass% or less with respect to the whole active energy ray curable ink composition.
  • the polymerization initiator is not necessarily essential. For example, when an electron beam is used as the active energy ray, the polymerization initiator may not be used.
  • the active energy ray-curable ink composition of the present embodiment may contain a polymerization inhibitor as necessary.
  • a polymerization inhibitor a phenothiazine polymerization inhibitor and a nitrosamine polymerization inhibitor described in Patent Document 1 are preferably used.
  • a combination of a phenothiazine polymerization inhibitor and a nitrosamine polymerization inhibitor as a polymerization inhibitor it is stable for a long period of time in both an oxygen-free atmosphere and the presence of oxygen, and has excellent curability.
  • An active energy ray-curable inkjet ink composition is obtained.
  • the active energy ray-curable ink composition of the present embodiment may contain a color material as necessary.
  • the cured film can be preferably used as a cured film for decoration.
  • the coloring material may be any inorganic pigment or organic pigment that is usually used in conventional oil-based ink compositions, such as carbon black, cadmium red, molybdenum red, chrome yellow, and cadmium yellow.
  • the preferable dispersed particle diameter of the pigment is preferably 10 nm or more as a volume average particle diameter by a laser scattering method. Further, in the active energy ray-curable ink composition of the present embodiment, a preferable dispersed particle diameter of the pigment is preferably 300 nm or less in terms of a volume average particle diameter by a laser scattering method.
  • the volume average particle size By setting the volume average particle size to 10 nm or more, 300 nm or less, or 10 nm or more and 300 nm or less, light resistance can be maintained and dispersion can be stabilized. Since it is possible to reduce the possibility of head clogging or ejection bending when ink is ejected, a more preferable active energy ray-curable ink composition can be obtained.
  • the content of the pigment in the total amount of the active energy ray-curable ink composition is preferably 0.1% by mass or more in the case of an organic pigment from the viewpoint of achieving both dispersibility and coloring power. 0.2 mass% or more is more preferable. In the case of an organic pigment, 20.0% by mass or less is preferable, and 10.0% by mass or less is more preferable in terms of achieving both dispersibility and coloring power. In the case of an inorganic pigment, 1.0% by mass or more is preferable, and 5.0% by mass or more is more preferable from the viewpoint of achieving both dispersibility and coloring power. Moreover, in the case of an inorganic pigment, 40.0 mass% or less is preferable, and 20.0 mass% or less is more preferable.
  • the active energy ray-curable ink composition of the present embodiment may contain a dispersant as necessary.
  • the dispersant include a polymer dispersant.
  • the main chain of this polymer dispersant is made of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and the polymer dispersant has amino groups, carboxyl groups, sulfone groups, hydroxyl groups, etc. as side chains. It is preferable to have a polar group or a salt thereof.
  • polymer dispersant examples include “DISPERBYK-168”, “DISPERBYK-2013”, “DISPERBYK-2055”, “DISPERBYK-2096”, “DISPERBYK-2155”, “DISPERBYK-2155”, “DISPERBYK-2200” manufactured by BYK Chemie.
  • the active energy ray-curable ink composition of this embodiment may further contain a surface conditioner.
  • the surface conditioner is not particularly limited, but specific examples include “BYK-307”, “BYK-333”, “BYK-354”, “BYK-361N”, “BYK-” manufactured by BYK Chemie having dimethylpolysiloxane.
  • the content of the surface conditioner is preferably 0.1% by mass or more based on the total amount of the ink composition.
  • the content of the surface conditioner is preferably 5.0% by mass or less based on the total amount of the ink composition.
  • the ink composition has preferable wettability with respect to the thermoplastic resin substrate and the like, and recording is performed on the substrate (image formation).
  • the active energy ray-curable ink composition can be spread and spread without causing repellency.
  • the active energy ray-curable ink composition of the present embodiment may contain a matting agent as necessary.
  • a matting agent for example, various powders such as silica, alumina, calcium carbonate and the like can be used. Matting agents may be used alone or in combination of two or more.
  • the active energy ray-curable ink composition of the present embodiment may contain various additives such as a plasticizer, a light stabilizer, and an antioxidant as other additives.
  • the solvent can be added within a range that achieves the object of the present application.
  • the surface tension of the active energy ray-curable ink composition of the present embodiment is preferably 20 mN / m or more at 40 ° C. from the viewpoints of inkjet dischargeability and discharge stability. Further, the surface tension at 40 ° C. is preferably 40 mN / m or less.
  • the laminate is produced by printing the active energy ray-curable ink composition on a substrate, preferably by an ink jet method, and then curing with an active energy ray.
  • a substrate preferably by an ink jet method
  • curing with an active energy ray e.g., a laser beam
  • an image can be formed on a substrate using the active energy ray-curable ink composition of the present embodiment.
  • an ink set of an active energy ray-curable ink composition containing color materials of various shades is prepared, and after printing by an ink jet method, the ink composition is cured to display various images on the substrate.
  • An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an image on a substrate are also within the scope of the present invention.
  • the term “image” means a decorative image that can be recognized through vision including letters, diagrams, figures, symbols, photographs, etc. composed of a single color or a plurality of colors. Also included are patterns made of stone, cloth, sand, geometric patterns, letters, etc.
  • the substrate is not particularly limited, and for example, any of a coated paper, a non-coated paper, an absorbent body such as a fabric, and a non-absorbent substrate can be used.
  • non-coated paper renewed paper, medium-quality paper, high-quality paper, and coated paper as coated paper, art paper, cast paper, lightweight coated paper, fine coated paper, fabric, etc.
  • the body include cotton, synthetic fabric, silk, hemp, fabric, non-woven fabric, leather, etc.
  • the non-absorbent substrate include polyester resin, polypropylene synthetic paper, vinyl chloride resin, polyimide resin, metal, metal Examples thereof include foil-coated paper, glass, synthetic rubber, and natural rubber.
  • Active energy rays for forming a cured film (hereinafter, sometimes referred to as “cured film”) obtained by curing the active energy ray-curable ink composition of the present embodiment are light in a wavelength region at 200 nm or more. Is preferable, and light in a wavelength region of 250 nm or more is more preferable.
  • the active energy ray for forming the cured film is preferably light in a wavelength region at 450 nm or less, and more preferably light in a wavelength region at 430 nm or less.
  • the light source is not particularly limited, and examples thereof include a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, sunlight, and an LED lamp.
  • the thickness of the cured film is preferably 1 ⁇ m or more. Moreover, it is preferable that the thickness of a cured film is 100 micrometers or less. By setting the thickness to 1 ⁇ m or more, the color density of the cured film containing the coloring material is not decreased, and physical properties such as a decrease in design properties, decorativeness, adhesion, and extensibility are improved. By setting the thickness to 100 ⁇ m or less, the ink composition can be sufficiently cured in a shorter time when the ink composition is irradiated with active energy rays, which is more preferable.
  • the method for measuring the thickness of the cured film was obtained by applying the active energy ray-curable ink composition of the present embodiment to a PET film (A4300, manufactured by Toyobo Co., Ltd.) under the same coating conditions as the prepared cured film.
  • the thickness of the cured film can be measured with a micrometer. In this specification, the thickness of the cured film is 10 locations per sample, and the average value of these is the thickness (the average thickness). The same applies to the protective layer and primer described later.
  • the cured film formed by the active energy ray-curable ink composition of the present embodiment can be used as a decorative layer as long as it contains a color material or the like as described above. Furthermore, the cured film can be used as an overcoat layer that protects the cured film by discharging onto the decorative layer without adding a coloring material. Further, it can be used as a primer layer for improving the adhesion between the substrate surface and the cured film. An active energy ray-curable ink composition that forms such a cured film is also within the scope of the present invention.
  • the active energy ray-curable ink composition of the present embodiment forms a decorative layer, an overcoat layer, or a primer layer independently only with a cured film formed by the active energy ray-curable ink composition of the present embodiment. Or a combination of these layers.
  • the active energy ray-curable ink composition of this embodiment in which a coloring material is added to the active energy ray-curable ink composition of this embodiment to form a decorative layer, and no coloring material or the like is added on the decorative layer.
  • An overcoat layer can also be formed by discharging an object.
  • the cured film formed from the active energy ray-curable ink composition of the present embodiment can also be used in combination with a decorative layer, overcoat layer or primer layer formed from a conventionally known ink composition. .
  • an overcoat layer can be formed on the decorative layer using a conventionally known overcoat composition.
  • any method may be used to form these layers. For example, spray coating, towel, sponge, nonwoven fabric, tissue coating, etc. , Dispenser, brush coating, gravure printing, flexographic printing, silk screen printing, inkjet, thermal transfer method, etc. may be used.
  • spray coating, towel, sponge, nonwoven fabric, tissue coating, etc. Dispenser, brush coating, gravure printing, flexographic printing, silk screen printing, inkjet, thermal transfer method, etc.
  • the surface of the cured film in the ink composition of the present embodiment is overcoated with an overcoat layer comprising a conventionally known overcoat agent or the ink composition of the present embodiment.
  • An overcoat layer formed by using as an agent may be further formed.
  • the overcoat layer is not limited to being formed on the surface of the layer made of the cured film of the ink composition, but may be formed directly on the surface of the base material, or formed on the surface of the base material. You may form in the surface of the primer layer mentioned later.
  • the active energy ray-curable ink composition of the present embodiment can be preferably used.
  • the active energy ray-curable ink composition of the present embodiment excellent curability and stretchability can be realized.
  • an overcoat layer is formed with an overcoat agent using the active energy ray-curable ink composition of the present embodiment on a cured film using the active energy ray-curable ink composition of the present embodiment, Since the cured film and the overcoat layer have the same composition, their adhesion is extremely high. Therefore, it is particularly preferable to use the active energy ray-curable ink composition of the present invention as an overcoat agent for a cured film in the active energy ray-curable ink composition of the present embodiment.
  • the thickness of the overcoat layer is preferably 1 ⁇ m or more.
  • the thickness is preferably 1 ⁇ m or more because the cured film can be appropriately protected.
  • the overcoat layer preferably has a thickness of 100 ⁇ m or less. The thickness is preferably 100 ⁇ m or less because the drying time is shortened to form the overcoat layer and the productivity is excellent.
  • the design property is imparted to the overcoat layer by adjusting the discharge amount of the ink composition and the conditions such as the time from the discharge of the ink composition to the irradiation of the active energy ray.
  • the surface after discharging the ink composition, the surface can be made glossy by irradiating active energy rays after a predetermined time has elapsed, and the surface can be quickly irradiated by irradiating active energy rays after discharging. It can be matte.
  • unevenness can be imparted by increasing / decreasing the discharge amount per time depending on the discharge location, and unevenness difference from other locations can be achieved by repeating the ejection of the ink composition and the irradiation of active energy rays at the same location. It can also be granted.
  • An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an uneven image are also within the scope of the present invention.
  • Such an overcoat layer is desirably formed by an ink jet method from the viewpoint of easy condition adjustment.
  • the concavo-convex image is not necessarily limited to what is visually recognized, and includes, for example, a colorless cured film or a cured film having a single color or a plurality of colors, as long as it has a concavo-convex shape. .
  • CAB551-0.01 is CAB551-0.01 (cellulose acetate butyrate resin) manufactured by Eastman Chemical Japan.
  • Degalan 66 / 02N is EVALIK INDUSTRIES's Degalan 66 / 02N (acrylic resin).
  • TEGO VariPlus SK is TEGO VariPlus SK (polyol resin) manufactured by Evonik Degussa Japan.
  • CAB551-0.01 is CAB551-0.01 (cellulose acetate butyrate resin) manufactured by Eastman Chemical Japan.
  • Dianar BR113 is a dialal BR113 (acrylic resin) manufactured by Mitsubishi Rayon Co., Ltd.
  • Degalan 64 / 12N refers to Degalan 64 / 12N (acrylic resin) manufactured by EVONIK INDUSTRIES.
  • TEGO AddBond LTH is TEGO AddBond LTH (modified special polyester) manufactured by Evonik Degussa Japan.
  • Genorad22 is Genorad22 (N-nitroso-N-phenylhydroxylamine aluminum salt solution (active ingredient: about 0.005%)) manufactured by Rahn and is a polymerization inhibitor.
  • ANTAGE TDP is ANTAGE TDP (phenothiazine) manufactured by Kawaguchi Chemical Industry Co., Ltd. and is a polymerization inhibitor.
  • DAIDO UV-CURE APO is DAIDO UV-CURE APO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by Daido Kasei Kogyo Co., Ltd. and is a polymerization initiator.
  • DETX means DOUBLECURE DETX (2,4-diethylthioxanthen-9-one) manufactured by Mitsubishi Corporation Chemical Co., and means a polymerization initiator.
  • Speedcure BMS is Speedcure BMS (4-benzoyl 4′-methyldiphenyl sulfide) manufactured by Lambson and is a polymerization initiator.
  • BYKUV3570 is BYKUV3570 (polyester-modified polydimethylsiloxane solution (active ingredient 70%)) manufactured by Big Chemie Japan, and is a surfactant.
  • Vb Viscosity (Vb) measurement test after storage at 60 ° C. for 28 days> The storage test was performed about the active energy ray hardening-type ink composition of an Example, a comparative example, and a reference example, and the viscosity (Vb) after a storage test was measured. Specifically, with respect to the active energy ray-curable ink compositions of Examples, Comparative Examples, and Reference Examples, approximately 25 ml of a sample sealed in a brown glass bottle with a capacity of 30 ml was sealed at a temperature of 60 ° C. and a storage period of 28. The storage test was conducted.
  • the viscosity was measured by the method similar to said initial viscosity (Va) measurement test.
  • the measurement results are shown in Table 1 (expressed as “viscosity after storage at 60 ° C. for 28 days (Vb)” in Table 1).
  • Table 1 the active energy ray-curable ink composition in which the active energy ray-curable ink composition gelled and the viscosity could not be measured was described as “gelation”.
  • Va) / Va ⁇ 100 is 10% or more or ⁇ 10% or less of the active energy ray-curable ink composition, or the active energy ray-curable ink composition gelled after the storage test is described as “NG”.
  • the active energy ray-curable ink compositions of Examples 1 to 3 containing a non-reactive resin having an acid value of 3.0 mgKOH / g or less are non-reactive resins having an acid value of more than 3.0 mgKOH / g. It can be seen that this is an active energy ray-curable ink composition having higher viscosity stability than the active energy ray-curable ink compositions of Comparative Examples 1 to 3 containing
  • the active energy ray-curable ink composition of Comparative Example 1 containing a non-reactive resin having an acid value of 3.5 mgKOH / g is a viscosity Va at 40 ° C. of the active energy ray-curable ink composition before the storage test.
  • the ratio of viscosity Vb at 40 ° C. of the active energy ray-curable ink composition after storage test and (Vb ⁇ Va) / Va ⁇ 100 (unit:%) greatly exceeds 10%, and viscosity stability It was confirmed that it was an active energy ray-curable ink composition having a low viscosity.
  • the active energy ray-curable ink compositions of Comparative Examples 2 and 3 gelled after the storage test, and similarly, the active energy ray-curable inks having low viscosity stability. It was confirmed to be a composition.
  • the active energy ray-curable ink composition not containing the non-reactive resin itself of the reference example is an active energy ray having low viscosity stability as in the active energy ray-curable ink compositions of Examples 1 to 3. It is a curable ink composition.
  • the initial viscosity (Va) itself is lower than that of the active energy ray-curable ink compositions of Examples 1 to 3. That is, the active energy ray-curable ink compositions of Examples 1 to 3 are optimized according to the printing apparatus and the specifications of the apparatus (for example, the nozzle of the printing apparatus) by containing the non-reactive resin. Thus, it was confirmed that the viscosity can be adjusted strictly.

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Abstract

Provided is an actinic-ray-curable ink composition, the viscosity of which is easy to regulate, and which changes little in viscosity with the lapse of time. The actinic-ray-curable ink composition contains an actinic-ray-polymerizable monomer and a non-reactive resin and is for use as an ink for ink-jet printing. The non-reactive resin has an acid value, as determined in accordance with JIS K 0070:1992, of 3.0 mg-KOH/g or less.

Description

活性エネルギー線硬化型インク組成物、このインク組成物を用いた積層体、基材上に像を形成する像形成方法及び印刷物の製造方法Active energy ray-curable ink composition, laminate using this ink composition, image forming method for forming an image on a substrate, and method for producing printed matter
　本発明は、インクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物、このインク組成物を印刷した積層体、このインク組成物を使用して基材上に画像及び／又は凹凸像を形成する像形成方法、及びこのインク組成物を使用する印刷物の製造方法に関する。 The present invention relates to an active energy ray-curable ink composition used as an inkjet ink, a laminate on which the ink composition is printed, and forms an image and / or an uneven image on a substrate using the ink composition. The present invention relates to an image forming method and a method for producing a printed material using the ink composition.
　従来より、紫外線、電子線その他の活性エネルギー線によって硬化する活性エネルギー線硬化型インク組成物の開発が進められている。活性エネルギー線硬化型インク組成物は速乾性があるため、プラスチック、ガラス、コート紙等、インクを吸収しない又は殆ど吸収しない基材に印字する場合であっても、インクの滲みを防止できる。活性エネルギー線硬化型インク組成物は、活性エネルギー線重合性モノマー、色材その他の添加剤等から構成されている。 Conventionally, development of an active energy ray-curable ink composition that is cured by ultraviolet rays, electron beams, or other active energy rays has been underway. Since the active energy ray-curable ink composition is quick-drying, ink bleeding can be prevented even when printing on a substrate that does not absorb or hardly absorbs ink, such as plastic, glass, and coated paper. The active energy ray-curable ink composition is composed of an active energy ray polymerizable monomer, a coloring material, and other additives.
　又、活性エネルギー線を用いたインクジェット印刷方式が活発に研究されている。この方式は、液状のインクを紙、プラスチックなどに塗布したのち、例えば紫外線を照射することにより、硬化・架橋させる方式であり、従来の熱で乾燥させるインクジェット印刷方式とは異なり、速乾性があり、無溶剤で、インクを吸収しない媒体への印刷が可能であるなどの利点がある。又、インクジェット方式は、印刷時に版を必要とせず、必要とされる画像部のみにインクを吐出し、被記録媒体上に直接画像形成を行うため、インクを効率良く使用でき、活性エネルギー線を用いたインクジェット印刷方式は注目されている。 In addition, inkjet printing methods using active energy rays are being actively researched. This method is a method in which liquid ink is applied to paper, plastic, etc., and then cured and crosslinked, for example, by irradiating with ultraviolet rays. Unlike conventional ink-jet printing methods that dry with heat, it has a quick drying property. There is an advantage that printing on a medium that does not absorb ink and does not absorb ink is possible. In addition, the ink jet method does not require a plate at the time of printing, and ink is ejected only to the required image portion and image formation is performed directly on the recording medium, so that the ink can be used efficiently and active energy rays are used. The ink jet printing method used has attracted attention.
　例えば、特許文献１では、活性エネルギー線硬化型インク組成物に所定の重合禁止剤を含有した活性エネルギー線硬化型インクジェットインク組成物が開示されている。 For example, Patent Document 1 discloses an active energy ray-curable inkjet ink composition containing a predetermined polymerization inhibitor in an active energy ray-curable ink composition.
　特許文献１の活性エネルギー線硬化型インク組成物は、無酸素雰囲気下、及び酸素存在下のいずれの場合においても低粘度であり、且つ、硬化性に優れた、活性エネルギー線硬化型インク組成物である。 The active energy ray-curable ink composition of Patent Document 1 is an active energy ray-curable ink composition having a low viscosity and excellent curability in both an oxygen-free atmosphere and in the presence of oxygen. It is.
特開２０１３－１５９７１６JP2013-159716A
　インクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物であっても、単にその粘度が低い程好ましいというものではない。インクジェット用印刷装置やインクジェット用印刷装置におけるノズルの仕様等によって、最適な活性エネルギー線硬化型インク組成物の粘度は異なる。そのため、活性エネルギー線硬化型インク組成物の粘度は、印刷装置やその装置の仕様（例えば、印刷装置のノズル等）に応じて最適となるように厳密に調整される。 Even an active energy ray-curable ink composition used as an ink jet ink is not simply preferable as its viscosity is low. The optimum viscosity of the active energy ray-curable ink composition varies depending on the specifications of the nozzles in the inkjet printing apparatus and the inkjet printing apparatus. Therefore, the viscosity of the active energy ray-curable ink composition is strictly adjusted so as to be optimal according to the printing apparatus and the specifications of the apparatus (for example, the nozzle of the printing apparatus).
　一方、活性エネルギー線硬化型インク組成物の初期状態では所望となるような粘度の活性エネルギー線硬化型インク組成物であっても、活性エネルギー線硬化型インク組成物の粘度が経時的に変化する場合がある。例えば、活性エネルギー線硬化型インク組成物の保管時又は流路内やインクジェットヘッド内において、活性エネルギー線硬化型インク組成物の粘度が変化し、印刷装置が求める最適な粘度とはならなくなる場合があった。 On the other hand, the viscosity of the active energy ray-curable ink composition changes with time even if the active energy ray-curable ink composition has a desired viscosity in the initial state of the active energy ray-curable ink composition. There is a case. For example, the viscosity of the active energy ray-curable ink composition may change during storage of the active energy ray-curable ink composition, in the flow path or in the inkjet head, and the optimum viscosity required by the printing apparatus may not be achieved. there were.
　本発明は、上記事情に鑑みてなされたものであって、その目的とするところは、活性エネルギー線硬化型インク組成物において、粘度の調整が容易な活性エネルギー線硬化型インク組成物であって、且つ、粘度の経時的な変化が少ない活性エネルギー線硬化型インク組成物を提供することである。 The present invention has been made in view of the above circumstances, and the object of the present invention is an active energy ray-curable ink composition whose viscosity can be easily adjusted in an active energy ray-curable ink composition. The present invention also provides an active energy ray-curable ink composition with little change in viscosity over time.
　本発明者らは、上記課題を解決するために、鋭意研究を重ねたところ、所定の酸価をもつ非反応性樹脂を含有する活性エネルギー線硬化型インク組成物であれば、上記課題を解決できることを見出し、本発明を完成するに至った。具体的には、本発明では、以下のようなものを提供する。 The inventors of the present invention have made extensive studies in order to solve the above problems. As long as the active energy ray-curable ink composition contains a non-reactive resin having a predetermined acid value, the above problems can be solved. The present inventors have found that this can be done and have completed the present invention. Specifically, the present invention provides the following.
　（１）　活性エネルギー線重合性モノマーと、非反応性樹脂と、を含有するインクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物であって、ＪＩＳ　Ｋ　００７０：１９９２に基づいて測定された前記非反応性樹脂の酸価が３．０ｍｇＫＯＨ／ｇ以下である、活性エネルギー線硬化型インク組成物。 (1) An active energy ray-curable ink composition used as an inkjet ink containing an active energy ray polymerizable monomer and a non-reactive resin, which is measured based on JIS K 0070: 1992 An active energy ray-curable ink composition, wherein the acid value of the non-reactive resin is 3.0 mgKOH / g or less.
　（２）　前記非反応性樹脂の含有量が前記活性エネルギー線硬化型インク組成物の全量中０．１質量％以上５質量％以下である、（１）に記載の活性エネルギー線硬化型インク組成物。 (2) The active energy ray-curable ink composition according to (1), wherein the content of the non-reactive resin is 0.1% by mass or more and 5% by mass or less in the total amount of the active energy ray-curable ink composition. object.
　（３）　前記非反応性樹脂の数平均分子量が１０万以下である、（１）又は（２）に記載の活性エネルギー線硬化型インク組成物。 (3) The active energy ray-curable ink composition according to (1) or (2), wherein the number average molecular weight of the non-reactive resin is 100,000 or less.
　（４）　前記非反応性樹脂がセルロース系樹脂、（メタ）アクリル系樹脂、及びポリオール系樹脂からなる群より選択される少なくとも１種の樹脂である、（１）から（３）のいずれかに記載の活性エネルギー線硬化型インク組成物。 (4) In any one of (1) to (3), the non-reactive resin is at least one resin selected from the group consisting of a cellulose resin, a (meth) acrylic resin, and a polyol resin. The active energy ray-curable ink composition as described.
　（５）　前記活性エネルギー線重合性モノマーの少なくとも１種は（メタ）アクリル酸エステルである、（１）から（４）のいずれかに記載の活性エネルギー線硬化型インク組成物。 (5) The active energy ray-curable ink composition according to any one of (1) to (4), wherein at least one of the active energy ray polymerizable monomers is (meth) acrylic acid ester.
　（６）　ＪＩＳ　Ｋ　００７０：１９９２に基づいて測定された前記活性エネルギー線重合性モノマーの酸価が、１．０ｍｇＫＯＨ／ｇ以下である、（１）から（５）のいずれかに記載の活性エネルギー線硬化型インク組成物。 (6) The active energy according to any one of (1) to (5), wherein an acid value of the active energy ray polymerizable monomer measured based on JIS K 0070: 1992 is 1.0 mgKOH / g or less. Line curable ink composition.
　（７）　（１）から（６）のいずれかに記載の活性エネルギー線硬化型インク組成物を６０℃２８日放置し、保管試験前の前記活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖａ（単位はｍＰａ・ｓ）と保管試験後の前記活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖｂ（単位はｍＰａ・ｓ）の比である（Ｖｂ－Ｖａ）／Ｖａ×１００（単位は％）が－１０％超１０％未満である、活性エネルギー線硬化型インク組成物。 (7) The active energy ray-curable ink composition according to any one of (1) to (6) is allowed to stand at 60 ° C. for 28 days, and the viscosity at 40 ° C. of the active energy ray-curable ink composition before the storage test is measured. Va (unit: mPa · s) and viscosity Vb (unit: mPa · s) at 40 ° C. of the active energy ray-curable ink composition after the storage test (Vb−Va) / Va × 100 (unit %) Is more than −10% and less than 10%.
　（８）　基材上に、（１）から（７）のいずれかに記載の活性エネルギー線硬化型インク組成物の硬化膜であるインク硬化膜層が形成された積層体。 (8) A laminate in which an ink cured film layer that is a cured film of the active energy ray-curable ink composition according to any one of (1) to (7) is formed on a substrate.
　（９）　（１）から（７）のいずれかに記載の活性エネルギー線硬化型インク組成物を使用して基材上に画像及び／又は凹凸像を形成する像形成方法。 (9) An image forming method for forming an image and / or an uneven image on a substrate using the active energy ray-curable ink composition according to any one of (1) to (7).
　（１０）　（１）から（７）のいずれかに記載の活性エネルギー線硬化型インク組成物を使用して基材上に画像及び／又は凹凸像を形成する印刷物の製造方法。 (10) A method for producing a printed material, wherein an image and / or a concavo-convex image is formed on a substrate using the active energy ray-curable ink composition according to any one of (1) to (7).
　本発明の活性エネルギー線硬化型インク組成物は、粘度の調整が容易な活性エネルギー線硬化型インク組成物であって、且つ、粘度の経時的な変化が少ない活性エネルギー線硬化型インク組成物である。 The active energy ray-curable ink composition of the present invention is an active energy ray-curable ink composition whose viscosity can be easily adjusted, and is an active energy ray-curable ink composition with little change in viscosity over time. is there.
　以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the present invention. be able to.
　＜活性エネルギー線硬化型インク組成物＞
　本発明の一実施形態の活性エネルギー線硬化型インク組成物は、活性エネルギー線重合性モノマーと、非反応性樹脂と、を含有するインクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物である。以下、非反応性樹脂、活性エネルギー線重合性モノマー、及び本発明の活性エネルギー線硬化型インク組成物に含まれていてもよい各成分について各々説明する。 <Active energy ray-curable ink composition>
An active energy ray-curable ink composition according to an embodiment of the present invention is an active energy ray-curable ink composition used as an inkjet ink containing an active energy ray-polymerizable monomer and a non-reactive resin. . Hereinafter, each component which may be contained in the non-reactive resin, the active energy ray polymerizable monomer, and the active energy ray curable ink composition of the present invention will be described.
　［非反応性樹脂］
　本実施形態の活性エネルギー線硬化型インク組成物には、非反応性樹脂を含有する。ここで、本明細書において、非反応性樹脂とは、活性エネルギー線重合性モノマー又は他成分の活性基とラジカル反応が可能な官能基を有していない樹脂を意味する。 [Non-reactive resin]
The active energy ray-curable ink composition of the present embodiment contains a non-reactive resin. Here, in the present specification, the non-reactive resin means a resin having no functional group capable of radical reaction with the active energy ray polymerizable monomer or the active group of another component.
　又、本実施形態に関するＪＩＳ　Ｋ　００７０：１９９２に基づいて測定された非反応性樹脂の酸価は、３．０ｍｇＫＯＨ／ｇ以下である。酸価が３．０ｍｇＫＯＨ／ｇ以下の非反応性樹脂を活性エネルギー線硬化型インク組成物に含有することにより、活性エネルギー線硬化型インク組成物の粘度が経時的に変化することを抑制することができる。尚、本実施形態に関する非反応性樹脂の酸価は、２．５ｍｇＫＯＨ／ｇ以下であることが好ましく、２．０ｍｇＫＯＨ／ｇ以下であることがより好ましい。 Moreover, the acid value of the non-reactive resin measured based on JIS K 0070: 1992 concerning this embodiment is 3.0 mgKOH / g or less. By containing a non-reactive resin having an acid value of 3.0 mgKOH / g or less in the active energy ray-curable ink composition, the viscosity of the active energy ray-curable ink composition is prevented from changing over time. Can do. In addition, it is preferable that the acid value of the non-reactive resin regarding this embodiment is 2.5 mgKOH / g or less, and it is more preferable that it is 2.0 mgKOH / g or less.
　インクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物であっても、単にその粘度が低い程好ましいというものではない。活性エネルギー線硬化型インク組成物の粘度は、印刷装置やその装置の仕様に応じて最適となるように厳密に調整される。 Even an active energy ray-curable ink composition used as an ink jet ink is not simply preferable as its viscosity is low. The viscosity of the active energy ray-curable ink composition is strictly adjusted so as to be optimal according to the printing apparatus and the specifications of the apparatus.
　近年のインクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物の粘度は、印刷装置やその装置の仕様に応じて最適となるように粘度の調整が容易であって、且つ、粘度の経時的な変化が少ない活性エネルギー線硬化型インク組成物であることが求められる。 The viscosity of an active energy ray-curable ink composition used as an ink jet ink in recent years can be easily adjusted so as to be optimal according to the specifications of the printing apparatus and the apparatus, and the viscosity of the ink composition with time It is required to be an active energy ray-curable ink composition with little change.
　活性エネルギー線硬化型インク組成物の粘度を調整する方法として、樹脂を添加する方法を挙げることができる。しかしながら、本発明者らの知見によれば、活性エネルギー線重合性モノマー又は他成分の活性基とラジカル反応が可能な官能基を有していない非反応性樹脂であった場合であっても、活性エネルギー線硬化型インク組成物の粘度が経時的に変化する場合があった。 Examples of a method for adjusting the viscosity of the active energy ray-curable ink composition include a method of adding a resin. However, according to the knowledge of the present inventors, even if it is a non-reactive resin that does not have a functional group capable of radical reaction with an active energy ray polymerizable monomer or an active group of another component, In some cases, the viscosity of the active energy ray-curable ink composition changes with time.
　本実施形態の活性エネルギー線硬化型インク組成物は、所定値の酸価をもつ非反応性樹脂を含有されることにより、（１）粘度の調整が容易な活性エネルギー線硬化型インク組成物であって、（２）粘度の経時的な変化が少ない活性エネルギー線硬化型インク組成物、との２つの効果を同時に満たすことのできる活性エネルギー線硬化型インク組成物である。 The active energy ray-curable ink composition of the present embodiment includes (1) an active energy ray-curable ink composition that can be easily adjusted in viscosity by containing a non-reactive resin having a predetermined acid value. And (2) an active energy ray-curable ink composition capable of simultaneously satisfying the two effects of an active energy ray-curable ink composition with little change in viscosity over time.
　酸価が３．０ｍｇＫＯＨ／ｇ以下の非反応性樹脂を用いることにより活性エネルギー線硬化型インク組成物の粘度の経時的な変化が少なくなる理由は必ずしも明らかではない。しかしながら、酸価の高い樹脂が含有されている場合には、活性エネルギー線硬化型インク組成物の保管中に、酸価の高い樹脂の一部で架橋反応が進行し、分子量が増加し、活性エネルギー線硬化型インク組成物の粘度が増加するものと考えられる。 The reason why the change with time in the viscosity of the active energy ray-curable ink composition is reduced by using a non-reactive resin having an acid value of 3.0 mgKOH / g or less is not necessarily clear. However, when a resin with a high acid value is contained, during the storage of the active energy ray-curable ink composition, a crosslinking reaction proceeds with a part of the resin with a high acid value, the molecular weight increases, and the activity increases. It is considered that the viscosity of the energy beam curable ink composition increases.
　樹脂を含有することにより、エネルギー線硬化型インク組成物の粘度を調整する思想は従来にもあったが、本発明者らは、その樹脂の酸価に着目し、その樹脂の酸価を調整した活性エネルギー線硬化型インク組成物は、従来にはない新規の活性エネルギー線硬化型インク組成物である。 Although the idea of adjusting the viscosity of the energy ray curable ink composition by containing a resin has been in the past, the present inventors focused on the acid value of the resin and adjusted the acid value of the resin. The active energy ray-curable ink composition thus obtained is a novel active energy ray-curable ink composition that has not been conventionally used.
　活性エネルギー線硬化型インク組成物の４０℃における好ましい粘度は、インクジェット用印刷装置やノズルの仕様等によって異なるが、インクジェット用印刷装置における吐出安定性等の観点から、２０ｍＰａ・ｓ以下であることが好ましく、１５ｍＰａ・ｓ以下であることがより好ましい。又、活性エネルギー線硬化型インク組成物の好ましい粘度は、５ｍＰａ・ｓ以上であることが好ましく、７ｍＰａ・ｓ以上であることがより好ましい。尚、粘度は、例えば、ＤＩＮ　ＥＮ　ＩＳＯ　１２０５８－１に基づいて、落球粘度計によって測定することができる。 The preferred viscosity at 40 ° C. of the active energy ray-curable ink composition varies depending on the specifications of the inkjet printing apparatus and nozzles, but is 20 mPa · s or less from the viewpoint of ejection stability and the like in the inkjet printing apparatus. Preferably, it is 15 mPa · s or less. The preferable viscosity of the active energy ray-curable ink composition is preferably 5 mPa · s or more, and more preferably 7 mPa · s or more. The viscosity can be measured with a falling ball viscometer based on, for example, DIN EN ISO 12058-1.
　又、粘度の経時的な変化が少ない活性エネルギー線硬化型インク組成物とは、例えば、以下の指標により評価することができる。その指標とは、まず、保管試験前における活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖａ（単位はｍＰａ・ｓ）を測定する。そして、その活性エネルギー線硬化型インク組成物について、外部からの光を遮断可能な褐色等のガラス瓶に入れ密閉する。そして、ガラス瓶に密閉した活性エネルギー線硬化型インク組成物について６０℃２８日間保管試験を行う。保管試験後における活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖｂ（単位はｍＰａ・ｓ）を求める。そして、その比である（Ｖｂ－Ｖａ）／Ｖａ×１００（単位は％）を計算し、この数字が０％に近いほど粘度が経時的な変化が少ない活性エネルギー線硬化型インク組成物であるといえる。 In addition, the active energy ray-curable ink composition with little change in viscosity over time can be evaluated by, for example, the following index. First, the viscosity Va (unit: mPa · s) at 40 ° C. of the active energy ray-curable ink composition before the storage test is measured. Then, the active energy ray-curable ink composition is sealed in a brown glass bottle that can block light from the outside. The active energy ray-curable ink composition sealed in a glass bottle is subjected to a storage test at 60 ° C. for 28 days. The viscosity Vb (unit: mPa · s) at 40 ° C. of the active energy ray-curable ink composition after the storage test is determined. Then, the ratio (Vb−Va) / Va × 100 (unit:%) is calculated, and the closer this number is to 0%, the less the change in viscosity with time is the active energy ray-curable ink composition. It can be said.
　（Ｖｂ－Ｖａ）／Ｖａ×１００の値は、具体的には、－１０％超１０％未満であることが好ましく、－８％超８％未満であることがより好ましく、－５％超５％未満であることが更に好ましく、－２％超２％未満であることがなおいっそう好ましい。 Specifically, the value of (Vb−Va) / Va × 100 is preferably more than −10% and less than 10%, more preferably more than −8% and less than 8%, more than −5% and more than 5%. More preferably, it is less than 2% and even more preferably more than -2% and less than 2%.
　本実施形態に関する非反応性樹脂は、活性エネルギー線重合性モノマー又は他成分の活性基とラジカル反応が可能な官能基を有していない樹脂であれば特に限定されるものではない。活性エネルギー線重合性モノマー又は他成分の活性基とラジカル反応が可能な官能基とは、例えば、エチレン性不飽和二重結合を有する官能基を挙げることができる。本実施形態に関する非反応性樹脂としては、例えば、セルロースアセテートアルキレート樹脂、セルロースアセテート樹脂、ポリオール樹脂、（メタ）アクリル樹脂、エポキシ樹脂、ケトン樹脂、ニトロセルロース樹脂、フェノキシ樹脂、ポリエステル樹脂、ビニル樹脂、ビニルエステル樹脂、オキセタン樹脂、アリル樹脂、フェノール樹脂、キシレン樹脂、フラン樹脂、ケイ素樹脂、ジシクロペンタジエン樹脂、エピスルフィド樹脂、エン－チオール樹脂、ポリアゾメチン樹脂、アミノ樹脂、シアネート樹脂、イソシアネート樹脂、ポリイミド樹脂等を挙げることができる。 The non-reactive resin related to the present embodiment is not particularly limited as long as it is a resin that does not have a functional group capable of radical reaction with an active energy ray polymerizable monomer or an active group of another component. Examples of the functional group capable of radical reaction with the active energy ray-polymerizable monomer or the active group of another component include a functional group having an ethylenically unsaturated double bond. Examples of the non-reactive resin relating to the present embodiment include cellulose acetate alkylate resin, cellulose acetate resin, polyol resin, (meth) acrylic resin, epoxy resin, ketone resin, nitrocellulose resin, phenoxy resin, polyester resin, and vinyl resin. , Vinyl ester resin, oxetane resin, allyl resin, phenol resin, xylene resin, furan resin, silicon resin, dicyclopentadiene resin, episulfide resin, ene-thiol resin, polyazomethine resin, amino resin, cyanate resin, isocyanate resin, polyimide Examples thereof include resins.
　セルロースアセテートアルキレート樹脂としては、例えば、セルロースアセテートブチレート樹脂（例えば、イーストマン　ケミカル　ジャパン社製、商品名「ＣＡＢ５５１－０．０１」）、セルロースアセテートプロピオネート樹脂、セルロースアセテートプロピオネートブチレート樹脂等を挙げることができる。 Examples of the cellulose acetate alkylate resin include cellulose acetate butyrate resin (for example, Eastman Chemical Japan, trade name “CAB551-0.01”), cellulose acetate propionate resin, cellulose acetate propionate butyrate. Examples thereof include resins.
　ポリオール樹脂としては、例えば、ＴＥＧＯ（登録商標）ＶＡＲＩＰＬＵＳ　ＳＫ：エボニックデグサジャパン（株）の、ケトン－ホルムアルデヒド縮合体である水素添加物を挙げることができる。 Examples of the polyol resin include hydrogenated products that are ketone-formaldehyde condensates of TEGO (registered trademark) VARIPLUS SK: Evonik Degussa Japan Co., Ltd.
　アクリル樹脂としては、反応性の官能基を有しないアクリル重合体であり、例えば、Ｄｅｇａｌａｎ６６／０２Ｎ（ＥＶＯＮＩＫ　ＩＮＤＵＳＴＲＩＥＳ社製）の、アクリル重合体を挙げることができる。 The acrylic resin is an acrylic polymer having no reactive functional group, and examples thereof include an acrylic polymer of Degalan 66 / 02N (EVONIK INDUSTRIES).
　上記のセルロースアセテートアルキレート樹脂、セルロースアセテート樹脂、ポリオール樹脂、（メタ）アクリル樹脂、エポキシ樹脂、ケトン樹脂、ニトロセルロース樹脂、フェノキシ樹脂、ポリエステル樹脂、ビニル樹脂、ビニルエステル樹脂、オキセタン樹脂、アリル樹脂、フェノール樹脂、キシレン樹脂、フラン樹脂、ケイ素樹脂、ジシクロペンタジエン樹脂、エピスルフィド樹脂、エン－チオール樹脂、ポリアゾメチン樹脂、アミノ樹脂、シアネート樹脂、イソシアネート樹脂、ポリイミド樹脂等の樹脂を非反応性樹脂として活性エネルギー線硬化型インク組成物に含有される場合、上記のセルロースアセテートアルキレート樹脂、セルロースアセテート樹脂、ポリオール樹脂、アクリル樹脂（メタ）アクリル樹脂、エポキシ樹脂、ケトン樹脂、ニトロセルロース樹脂、フェノキシ樹脂、ポリエステル樹脂、ビニル樹脂、ビニルエステル樹脂、オキセタン樹脂、アリル樹脂、フェノール樹脂、キシレン樹脂、フラン樹脂、ケイ素樹脂、ジシクロペンタジエン樹脂、エピスルフィド樹脂、エン－チオール樹脂、ポリアゾメチン樹脂、アミノ樹脂、シアネート樹脂、イソシアネート樹脂、ポリイミド樹脂等の樹脂の含有量は、非反応性樹脂全量中９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることが更に好ましい。 Cellulose acetate alkylate resin, cellulose acetate resin, polyol resin, (meth) acrylic resin, epoxy resin, ketone resin, nitrocellulose resin, phenoxy resin, polyester resin, vinyl resin, vinyl ester resin, oxetane resin, allyl resin, Active as a non-reactive resin such as phenol resin, xylene resin, furan resin, silicon resin, dicyclopentadiene resin, episulfide resin, ene-thiol resin, polyazomethine resin, amino resin, cyanate resin, isocyanate resin, polyimide resin When contained in the energy ray curable ink composition, the above cellulose acetate alkylate resin, cellulose acetate resin, polyol resin, acrylic resin (meth) acrylic resin, epoxy resin Ketone resin, nitrocellulose resin, phenoxy resin, polyester resin, vinyl resin, vinyl ester resin, oxetane resin, allyl resin, phenol resin, xylene resin, furan resin, silicon resin, dicyclopentadiene resin, episulfide resin, ene-thiol resin The content of the resin such as polyazomethine resin, amino resin, cyanate resin, isocyanate resin, polyimide resin is preferably 90% by mass or more, more preferably 95% by mass or more in the total amount of the non-reactive resin. 99% by mass or more is more preferable.
　本実施形態に関する非反応性樹脂の含有量は、特に制限されるものではない。非反応性樹脂における含有量は、非反応性樹脂の数平均分子量にもよるが、インクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物の粘度を好ましい範囲に上昇させることができるという観点から、活性エネルギー線硬化型インク組成物の全量中０．１質量％以上であることが好ましく、０．２質量％以上であることがより好ましい。非反応性樹脂における含有量は、非反応性樹脂の平均分子量にもよるが、インクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物の粘度を好ましい範囲に抑制させることができるという観点から、活性エネルギー線硬化型インク組成物の全量中５質量％以下であることが好ましく、３質量％以下であることがより好ましい。 The content of the non-reactive resin relating to the present embodiment is not particularly limited. The content in the non-reactive resin depends on the number-average molecular weight of the non-reactive resin, but from the viewpoint that the viscosity of the active energy ray-curable ink composition used as the ink for inkjet can be increased to a preferable range. The content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total amount of the active energy ray-curable ink composition. The content in the non-reactive resin depends on the average molecular weight of the non-reactive resin, but from the viewpoint that the viscosity of the active energy ray-curable ink composition used as an ink jet ink can be suppressed within a preferable range. The content is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total amount of the active energy ray-curable ink composition.
　本実施形態に関する非反応性樹脂の数平均分子量は、特に制限されるものではないが、インクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物の粘度を好ましい範囲にすることができるという観点から、１０万以下であることが好ましく、７万以下であることがより好ましく、３万以下であることが更に好ましい。非反応性樹脂の平均分子量を１０万以下とすることにより、非反応性樹脂の含有量に対する活性エネルギー線硬化型インク組成物における粘度の上昇量を抑制することができる。そのため、活性エネルギー線硬化型インク組成物における粘度の調整が容易となり、印刷装置やその装置の仕様に応じて最適となるように厳密に粘度を調整することが容易となる。本実施形態に関する非反応性樹脂の数平均分子量において、数平均分子量は、５００以上であることが好ましく、１０００以上であることがより好ましく、５０００以上であることが更に好ましい。 The number average molecular weight of the non-reactive resin relating to the present embodiment is not particularly limited, but from the viewpoint that the viscosity of the active energy ray-curable ink composition used as an ink jet ink can be within a preferable range. It is preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 30,000 or less. By setting the average molecular weight of the non-reactive resin to 100,000 or less, it is possible to suppress an increase in viscosity in the active energy ray-curable ink composition with respect to the content of the non-reactive resin. Therefore, it becomes easy to adjust the viscosity of the active energy ray-curable ink composition, and it becomes easy to strictly adjust the viscosity so as to be optimal according to the printing apparatus and the specifications of the apparatus. In the number average molecular weight of the non-reactive resin relating to the present embodiment, the number average molecular weight is preferably 500 or more, more preferably 1000 or more, and further preferably 5000 or more.
　［活性エネルギー線重合性モノマー］
　本実施形態に関する活性エネルギー線重合性モノマーは、活性エネルギー線の作用によって重合可能なものであり、且つ先述した非反応性樹脂を溶解又は分散することのできるものであれば特に限定されない。エチレン性不飽和二重結合が化合物中に１個有する単官能モノマーであってもよいし、エチレン性不飽和二重結合が化合物中に２個以上する多官能モノマーであってもよい。なお、本発明における「活性エネルギー線重合性モノマー」のモノマーとは、その分子量によってはオリゴマーとも称される化合物をも含む概念である。 [Active energy ray polymerizable monomer]
The active energy ray-polymerizable monomer according to this embodiment is not particularly limited as long as it can be polymerized by the action of active energy rays and can dissolve or disperse the aforementioned non-reactive resin. It may be a monofunctional monomer having one ethylenically unsaturated double bond in the compound, or may be a polyfunctional monomer having two or more ethylenically unsaturated double bonds in the compound. In addition, the monomer of the “active energy ray polymerizable monomer” in the present invention is a concept including a compound also called an oligomer depending on its molecular weight.
　活性エネルギー線重合性モノマーを有する化合物におけるエチレン性不飽和二重結合の構造は、特に限定されない。例えば、（メタ）アクリロイル基、ビニル基、アリル基等が挙げられる。中でも、エチレン性不飽和二重結合が（メタ）アクリロイル基であることが、インクにおける硬化性の点から好ましい。尚、本明細書において、「（メタ）アクリロイル基」は、アクリロイル基とメタクリロイル基との両方を意味する。 The structure of the ethylenically unsaturated double bond in the compound having an active energy ray polymerizable monomer is not particularly limited. For example, a (meth) acryloyl group, a vinyl group, an allyl group, etc. are mentioned. Among these, the ethylenically unsaturated double bond is preferably a (meth) acryloyl group from the viewpoint of curability in the ink. In the present specification, “(meth) acryloyl group” means both an acryloyl group and a methacryloyl group.
　本発明においては、活性エネルギー線重合性モノマーとしては、中でも、低粘度であって、得られるインクの硬化性に優れ、且つ、硬化時の収縮が小さい点から、（メタ）アクリレート基を化合物中に１個のみ有する単官能（メタ）アクリル酸エステル、又は（メタ）アクリレート基を化合物中に２個有する二官能（メタ）アクリル酸エステルであることが好ましい。単官能（メタ）アクリレートは、低粘度で、且つ、硬化収縮が小さいため柔軟性を要する用途に特に適している。又、二官能（メタ）アクリレートは、低粘度で、且つ、硬化時に架橋密度が高くなるため、耐性を要する用途に特に適している。尚、本明細書において、「（メタ）アクリレート」は、アクリレートとメタクリレートとの両方を意味する。 In the present invention, the active energy ray-polymerizable monomer has a (meth) acrylate group in the compound because of its low viscosity, excellent curability of the resulting ink, and small shrinkage upon curing. It is preferable that it is a monofunctional (meth) acrylic acid ester having only one in a bifunctional (meth) acrylic acid ester having two (meth) acrylate groups in the compound. Monofunctional (meth) acrylates are particularly suitable for applications requiring flexibility because of their low viscosity and low cure shrinkage. Bifunctional (meth) acrylates are particularly suitable for applications requiring resistance because of their low viscosity and high crosslink density upon curing. In the present specification, “(meth) acrylate” means both acrylate and methacrylate.
　単官能（メタ）アクリレートは特に限定されない。例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソデシル（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）メチルアクリレート、テトラヒドロフルフリル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、３，３，５－トリメチルシクロヘキシル（メタ）アクリレート、ｔｅｒｔ－ブチルシクロへキシル（メタ）アクリレート、ノルボルニル（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、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、１－アダマンチル（メタ）アクリレート、アリル（メタ）アクリレート、２，２’－オキシビス（メチレン）ビス－２－プロペノエート、エチルカルビトール（メタ）アクリレート、グリシジル（メタ）アクリレート、２－ヒドロキシルエチル（メタ）アクリレート、２－ヒドロキシプロピル（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、ｔ－ブチル（メタ）アクリレート、イソノニル（メタ）アクリレート、ノニル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、環状トリメチロールプロパンホルマール（メタ）アクリレート、２－ジメチルアミノエチル（メタ）アクリレート、アクリロイルモルフォリン、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、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、トリデシル（メタ）アクリレート、２，２，２－とリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロオクチル（メタ）アクリレート等が挙げられる。尚、これらの単官能（メタ）アクリレートを活性エネルギー線重合性モノマーとして含有する場合、これらの単官能（メタ）アクリレートの含有量は、単官能モノマー全量中９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることが更に好ましい。 Monofunctional (meth) acrylate is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, (2-methyl -2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, tetrahydrofurfuryl (meth) acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxy Ethyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, ethyl carbitol (meth) acrylate Glycidyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, t-butyl (meth) Acrylate, isononyl (meth) acrylate, nonyl (meth) acrylate, methoxyethyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, acryloylmorpholine, N-acryloyloxyethyl Hexahydrophthalimide, stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, 2,2,2- and trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( And (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, and the like. When these monofunctional (meth) acrylates are contained as active energy ray polymerizable monomers, the content of these monofunctional (meth) acrylates is preferably 90% by mass or more in the total amount of monofunctional monomers, More preferably, it is 95 mass% or more, and it is still more preferable that it is 99 mass% or more.
　中でも、硬化収縮が小さく、硬化膜との密着性が良好な点から、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート等の芳香族炭化水素単官能（メタ）アクリレート、及び、イソボルニル（メタ）アクリレート、シクロへキシル（メタ）アクリレート、３，３，５－トリメチルシクロヘキシル（メタ）アクリレート、ｔｅｒｔ－ブチルシクロへキシル（メタ）アクリレート、ノルボルニル（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、ジシクロペンタニル（メタ）アクリレート等の脂環式炭化水素単官能（メタ）アクリレート、及び、（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、環状トリメチロールプロパンホルマール（メタ）アクリレート等の複素環化合物が好ましい。 Among them, aromatic hydrocarbon monofunctional (meth) such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, etc. because of its small curing shrinkage and good adhesion to the cured film. Acrylate and isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, alicyclic hydrocarbon monofunctional (meth) acrylate such as dicyclopentanyl (meth) acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate , Cyclic trimethyl Heterocyclic compounds such Lumpur propane formal (meth) acrylate.
　二官能（メタ）アクリレートは特に限定されない。例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（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、トリプロピレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、長鎖脂肪族ジ（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、１，６－ヘキサンジオールジ（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、ネオペンチルグリコールジ（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、ステアリン酸変性ペンタエリスリトールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、グリセロールジ（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、テトラエチレングリコールジ（メタ）アクリレート、テトラメチレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、プロポキシ化ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（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、ポリプロピレンジ（メタ）アクリレート、トリグリセロールジ（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、メトキシ化シクロヘキシルジ（メタ）アクリレート、アクリル化イソシアヌレート、ビス（アクリロキシネオペンチルグリコール）アジペート、ビスフェノールＡジ（メタ）アクリレート、テトラブロモビスフェノールＡジ（メタ）アクリレート、ビスフェノールＳジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、フタル酸ジ（メタ）アクリレート、リン酸ジ（メタ）アクリレート、亜鉛ジ（メタ）アクリレート等が挙げられる。尚、これらの二官能（メタ）アクリレートを活性エネルギー線重合性モノマーとして含有する場合、これらの二官能（メタ）アクリレートの含有量は、多官能モノマー全量中９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることが更に好ましい。 The bifunctional (meth) acrylate is not particularly limited. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain aliphatic di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalin Acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, triethylene Recall di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylation Cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (me ) Acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) acrylate, di (meth) acrylate phthalate, di (meth) acrylate phosphate, zinc di (meth) An acrylate etc. are mentioned. In addition, when these bifunctional (meth) acrylates are contained as active energy ray polymerizable monomers, the content of these bifunctional (meth) acrylates is preferably 90% by mass or more based on the total amount of polyfunctional monomers, More preferably, it is 95 mass% or more, and it is still more preferable that it is 99 mass% or more.
　尚、上述したこれらの単官能（メタ）アクリレート及びこれらの二官能（メタ）アクリレートを活性エネルギー線重合性モノマーとして含有する場合、これらの（メタ）アクリレートの含有量は、活性エネルギー線重合性モノマー全量中９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることが更に好ましい。 In addition, when these monofunctional (meth) acrylates and bifunctional (meth) acrylates described above are contained as active energy ray polymerizable monomers, the content of these (meth) acrylates is determined based on the active energy ray polymerizable monomers. The total amount is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.
　二官能（メタ）アクリレートとしては、低粘度且つ架橋密度が高くなる点から、中でも、ジプロピレングリコールジ（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、１，６－ヘキサンジオールジ（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、テトラエチレングリコールジ（メタ）アクリレート、及びプロポキシ化ネオペンチルグリコールジアクリレートからなる群から選択される１種以上であることが好ましい。 Among the bifunctional (meth) acrylates, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) are particularly preferred because of their low viscosity and high crosslinking density. One or more selected from the group consisting of acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propoxylated neopentyl glycol diacrylate are preferred.
　又、単官能（メタ）アクリレートと、二官能（メタ）アクリレートを適宜組み合わせて用いることもできる。単官能（メタ）アクリレートと、二官能（メタ）アクリレートを組み合わせて用いる場合の含有比率は、用途に応じて適宜調整すれば良く、特に限定されない。中でも、硬化膜の密着性と膜強度を両立させる点から、単官能（メタ）アクリレート全量に対して、二官能（メタ）アクリレートが６０質量％以下であることが好ましく、５０質量％以下であることがより好ましい。 Moreover, a monofunctional (meth) acrylate and a bifunctional (meth) acrylate can be used in appropriate combination. The content ratio in the case of using a monofunctional (meth) acrylate and a bifunctional (meth) acrylate in combination may be appropriately adjusted according to the application, and is not particularly limited. Especially, it is preferable that bifunctional (meth) acrylate is 60 mass% or less with respect to the monofunctional (meth) acrylate whole quantity from the point which makes adhesiveness and film | membrane intensity | strength of cured film compatible, and is 50 mass% or less. It is more preferable.
　アクリロイル基以外では、ビニル基が好ましく用いられ、単官能ビニルモノマーとしてはＮ－ビニルカプロラクタム、（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチル等が挙げられ、特に、Ｎ－ビニルカプロラクタムが低粘度且つ密着性良好であるためより好ましい。二官能ビニルモノマーとしては、トリエチレングリコールジビニルエーテルが低粘度且つ粘度を低下させる能力に長けているためより好ましい。 In addition to the acryloyl group, a vinyl group is preferably used, and examples of the monofunctional vinyl monomer include N-vinylcaprolactam and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, and particularly, N-vinylcaprolactam is It is more preferable because of its low viscosity and good adhesion. As the bifunctional vinyl monomer, triethylene glycol divinyl ether is more preferable because it has a low viscosity and an excellent ability to reduce the viscosity.
　本実施形態に関する活性エネルギー線重合性モノマーは、１種単独で、又は２種以上組み合わせて用いることができる。本実施形態のインクジェットインク組成物においては、無溶剤型、すなわち有機溶剤を含まないことが好ましいため、通常、当該エチレン性不飽和結合を有する化合物が溶媒又は分散媒の代わりとなる。そのため、硬化性や、硬化後における膜物性の他に、溶媒又は分散媒となり得、且つ、インクジェット適性を有する観点から、適宜選択して組み合わせることが好ましい。 The active energy ray-polymerizable monomer according to the present embodiment can be used alone or in combination of two or more. In the ink-jet ink composition of the present embodiment, it is preferable that the solvent-free type, that is, an organic solvent is not included, and thus the compound having an ethylenically unsaturated bond is usually used as a solvent or a dispersion medium. Therefore, in addition to curability and film physical properties after curing, it is preferable to appropriately select and combine them from the viewpoint of being able to be a solvent or a dispersion medium and having ink jet aptitude.
　又、本実施形態に関する活性エネルギー線重合性モノマーにおける１ｇ当たりの不飽和二重結合当量（以下、単に不飽和二重結合当量（ｇ／ｅｑ）とする）は、特に限定されないが、硬化収縮が小さく、且つ、架橋密度が高くなる点から、５０ｇ／ｅｑ以上３００ｇ／ｅｑ以下であることが好ましく、１００ｇ／ｅｑ以上２５０ｇ／ｅｑ以下であることがより好ましい。 Further, the unsaturated double bond equivalent per gram (hereinafter, simply referred to as an unsaturated double bond equivalent (g / eq)) in the active energy ray-polymerizable monomer according to the present embodiment is not particularly limited. It is preferably 50 g / eq or more and 300 g / eq or less, more preferably 100 g / eq or more and 250 g / eq or less from the viewpoint of being small and having a high crosslinking density.
　溶媒又は分散媒となり得る活性エネルギー線重合性モノマーとしては、室温（２５℃）で液状であるものの中から適宜選択すれば良く、例えば、分子量が１５０以上４００以下のものが好適に用いられる。 The active energy ray polymerizable monomer that can be a solvent or a dispersion medium may be appropriately selected from those that are liquid at room temperature (25 ° C.). For example, those having a molecular weight of 150 to 400 are preferably used.
　又、溶媒又は分散媒となり得る活性エネルギー線重合性モノマーは、中でも、インクジェットインク組成物のゲル化を防ぐ観点から、水酸基やカルボキシ基を含まないものが好ましい。 In addition, the active energy ray polymerizable monomer that can be a solvent or a dispersion medium is preferably one that does not contain a hydroxyl group or a carboxy group from the viewpoint of preventing gelation of the inkjet ink composition.
　又、本実施形態に関する活性エネルギー線重合性モノマーにおける粘度安定性の点から、ＪＩＳ　Ｋ　００７０：１９９２に基づいて測定された活性エネルギー線重合性モノマーの酸価は、１．０ｍｇＫＯＨ／ｇ以下であることが好ましく、０．５ｍｇＫＯＨ／ｇ以下であることがより好ましい。 Moreover, the acid value of the active energy ray polymerizable monomer measured based on JIS K 0070: 1992 is 1.0 mgKOH / g or less from the point of viscosity stability in the active energy ray polymerizable monomer according to this embodiment. It is preferably 0.5 mgKOH / g or less.
　溶媒又は分散媒となり得る活性エネルギー線重合性モノマーとして、好ましいものの具体例としては、例えば、フェノキシエチルアクリレート、イソボルニルアクリレート、ｔ－ブチルシクロヘキシルアクリレート、エチルカルビトールアクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、１，９－ノナンジオールジアクリレート、プロポキシ化ネオペンチルグリコールジアクリレート、トリエチレングリコールジビニルエーテル等が挙げられる。 Specific examples of preferable active energy ray polymerizable monomers that can be used as a solvent or a dispersion medium include, for example, phenoxyethyl acrylate, isobornyl acrylate, t-butylcyclohexyl acrylate, ethyl carbitol acrylate, dipropylene glycol diacrylate, Examples include propylene glycol diacrylate, 1,9-nonanediol diacrylate, propoxylated neopentyl glycol diacrylate, and triethylene glycol divinyl ether.
　本実施形態に関する活性エネルギー線重合性モノマーの含有量は、特に限定されない。硬化膜における硬化性の点から、本実施形態のインクジェットインク組成物全体における活性エネルギー線重合性モノマーにおける含有量は、３０質量％以上であることが好ましく、４５質量％以上であることがより好ましく、６０質量％以上であることが特に好ましい。活性エネルギー線重合性モノマーにおける粘度安定性の点から、本実施形態のインクジェットインク組成物全体における活性エネルギー線重合性モノマーの含有量は、９５質量％以下であることがより好ましく、９０質量％以下であることがより好ましい。 The content of the active energy ray polymerizable monomer relating to the present embodiment is not particularly limited. From the viewpoint of curability in the cured film, the content of the active energy ray polymerizable monomer in the entire inkjet ink composition of the present embodiment is preferably 30% by mass or more, and more preferably 45% by mass or more. 60% by mass or more is particularly preferable. From the viewpoint of viscosity stability in the active energy ray polymerizable monomer, the content of the active energy ray polymerizable monomer in the entire inkjet ink composition of the present embodiment is more preferably 95% by mass or less, and 90% by mass or less. It is more preferable that
　［活性エネルギー線重合開始剤］
　本実施形態の活性エネルギー線硬化型インク組成物は、必要に応じて活性エネルギー線重合開始剤（以下、単に重合開始剤と表記することがある。）を含有しても良い。活性エネルギー線は、ラジカル、カチオン、アニオン等の重合反応を契機し得るエネルギー線であれば、遠紫外線、紫外線、近紫外線、赤外線等の光線、Ｘ線、γ線等の電磁波や、電子線、プロトン線、中性子線等のいずれであっても良いが、硬化速度、照射装置の入手容易さ、価格等の観点において、紫外線照射による硬化が好ましい。重合開始剤としては、活性エネルギー線の照射により活性エネルギー線硬化型インク組成物中の活性エネルギー線重合性モノマーの重合反応を促進するものであれば特に限定されず、従来公知の重合開始剤を用いることができる。重合開始剤の具体例として、例えば、チオキサントン等を含む芳香族ケトン類、α－アミノアルキルフェノン類、α－ヒドロキシケトン類、アシルフォスフィンオキサイド類、芳香族オニウム塩類、有機過酸化物、チオ化合物、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、及びアルキルアミン化合物等が挙げられる。 [Active energy ray polymerization initiator]
The active energy ray-curable ink composition of the present embodiment may contain an active energy ray polymerization initiator (hereinafter sometimes simply referred to as a polymerization initiator) as necessary. Active energy rays are energy rays that can trigger polymerization reactions such as radicals, cations, anions, etc. Light rays such as deep ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, Any of proton beam, neutron beam and the like may be used, but curing by ultraviolet irradiation is preferable from the viewpoint of curing speed, availability of irradiation apparatus, price and the like. The polymerization initiator is not particularly limited as long as it accelerates the polymerization reaction of the active energy ray-polymerizable monomer in the active energy ray-curable ink composition by irradiation with active energy rays, and a conventionally known polymerization initiator is used. Can be used. Specific examples of the polymerization initiator include, for example, aromatic ketones containing thioxanthone, α-aminoalkylphenones, α-hydroxy ketones, acylphosphine oxides, aromatic onium salts, organic peroxides, thio compounds , Hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
　本実施形態に関する重合開始剤の量は、活性エネルギー線重合性モノマーの重合反応を適切に開始できる量であれば良く、活性エネルギー線硬化型インク組成物全体に対して１．０質量％以上であることが好ましく、３．０質量％以上であることがより好ましい。又、活性エネルギー線硬化型インク組成物全体に対して２０．０質量％以下であることが好ましい。なお、本発明においては、重合開始剤は必ずしも必須でなく、例えば活性エネルギー線として電子線を用いる場合には重合開始剤は用いなくてもよい。 The amount of the polymerization initiator related to this embodiment may be an amount that can appropriately initiate the polymerization reaction of the active energy ray polymerizable monomer, and is 1.0% by mass or more based on the entire active energy ray curable ink composition. It is preferable that the content is 3.0% by mass or more. Moreover, it is preferable that it is 20.0 mass% or less with respect to the whole active energy ray curable ink composition. In the present invention, the polymerization initiator is not necessarily essential. For example, when an electron beam is used as the active energy ray, the polymerization initiator may not be used.
［重合禁止剤］
　本実施形態の活性エネルギー線硬化型インク組成物は、必要に応じて重合禁止剤を含有してもよい。重合禁止剤は、特許文献１に記載のフェノチアジン類重合禁止剤及びニトロソアミン類重合禁止剤を用いることが好ましい。重合禁止剤としてフェノチアジン類重合禁止剤及びニトロソアミン類重合禁止剤を組み合わせて用いることにより、無酸素雰囲気下、及び酸素存在下のいずれの場合においても長期間安定で、且つ、硬化性に優れた、活性エネルギー線硬化型インクジェットインク組成物が得られる。 [Polymerization inhibitor]
The active energy ray-curable ink composition of the present embodiment may contain a polymerization inhibitor as necessary. As the polymerization inhibitor, a phenothiazine polymerization inhibitor and a nitrosamine polymerization inhibitor described in Patent Document 1 are preferably used. By using a combination of a phenothiazine polymerization inhibitor and a nitrosamine polymerization inhibitor as a polymerization inhibitor, it is stable for a long period of time in both an oxygen-free atmosphere and the presence of oxygen, and has excellent curability. An active energy ray-curable inkjet ink composition is obtained.
　［色材］
　本実施形態の活性エネルギー線硬化型インク組成物は、必要に応じて色材を含有しても良い。色材を含有することで、硬化膜を加飾用の硬化膜として好ましく用いることができる。色材は、従来の油性インク組成物に通常用いられている無機顔料又は有機顔料であればどのようなものであっても良く、例えば、カーボンブラック、カドミウムレッド、モリブデンレッド、クロムイエロー、カドミウムイエロー、チタンイエロー、酸化チタン、酸化クロム、ビリジアン、チタンコバルトグリーン、ウルトラマリンブルー、プルシアンブルー、コバルトブルー、ジケトピロロピロール、アンスラキノン、ベンズイミダゾロン、アンスラピリミジン、アゾ系顔料、フタロシアニン系顔料、キナクリドン系顔料、イソインドリノン系顔料、ジオキサジン系顔料、スレン系顔料、ペリレン系顔料、ペリノン系顔料、チオインジゴ系顔料、キノフタロン系顔料、金属錯体顔料、アルミペースト、シリカ、炭酸カルシウム、炭酸マグネシウム、クレー、沈降性硫酸バリウム、パール顔料等が挙げられる。 [Color material]
The active energy ray-curable ink composition of the present embodiment may contain a color material as necessary. By containing a color material, the cured film can be preferably used as a cured film for decoration. The coloring material may be any inorganic pigment or organic pigment that is usually used in conventional oil-based ink compositions, such as carbon black, cadmium red, molybdenum red, chrome yellow, and cadmium yellow. , Titanium yellow, titanium oxide, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, diketopyrrolopyrrole, anthraquinone, benzimidazolone, anthrapyrimidine, azo pigment, phthalocyanine pigment, quinacridone Pigment, isoindolinone pigment, dioxazine pigment, selenium pigment, perylene pigment, perinone pigment, thioindigo pigment, quinophthalone pigment, metal complex pigment, aluminum paste, silica, calcium carbonate, magnesium carbonate Beam, clay, precipitated barium sulfate, pearl pigments, and the like.
　本実施形態の活性エネルギー線硬化型インク組成物において顔料の好ましい分散粒径は、レーザー散乱法による体積平均粒径で１０ｎｍ以上であることが好ましい。又、本実施形態の活性エネルギー線硬化型インク組成物において顔料の好ましい分散粒径は、レーザー散乱法による体積平均粒径で３００ｎｍ以下であることが好ましい。体積平均粒径を１０ｎｍ以上、３００ｎｍ以下、又は１０ｎｍ以上３００ｎｍ以下にすることで、耐光性を維持することが可能となることや、分散の安定化が可能となり顔料の沈降やインクジェット記録装置でインクジェットインクを吐出する際でのヘッド詰まりや吐出曲がりが発生する可能性を軽減することが可能となるため、より好ましい活性エネルギー線硬化型インク組成物とすることができる。 In the active energy ray-curable ink composition of the present embodiment, the preferable dispersed particle diameter of the pigment is preferably 10 nm or more as a volume average particle diameter by a laser scattering method. Further, in the active energy ray-curable ink composition of the present embodiment, a preferable dispersed particle diameter of the pigment is preferably 300 nm or less in terms of a volume average particle diameter by a laser scattering method. By setting the volume average particle size to 10 nm or more, 300 nm or less, or 10 nm or more and 300 nm or less, light resistance can be maintained and dispersion can be stabilized. Since it is possible to reduce the possibility of head clogging or ejection bending when ink is ejected, a more preferable active energy ray-curable ink composition can be obtained.
　本実施形態において、顔料を用いる場合、その含有量は適宜調整されれば良い。顔料の種類によっても異なるが、活性エネルギー線硬化型インク組成物全量における、顔料の含有量は、分散性と着色力を両立する点から、有機顔料の場合、０．１質量％以上が好ましく、０．２質量％以上がより好ましい。又、分散性と着色力を両立する点から、有機顔料の場合、２０．０質量％以下が好ましく、１０．０質量％以下がより好ましい。又、分散性と着色力を両立する点から、無機顔料の場合、１．０質量％以上が好ましく、５．０質量％以上がより好ましい。又、無機顔料の場合、４０．０質量％以下が好ましく、２０．０質量％以下がより好ましい。 In this embodiment, when a pigment is used, its content may be adjusted as appropriate. Although it varies depending on the type of pigment, the content of the pigment in the total amount of the active energy ray-curable ink composition is preferably 0.1% by mass or more in the case of an organic pigment from the viewpoint of achieving both dispersibility and coloring power. 0.2 mass% or more is more preferable. In the case of an organic pigment, 20.0% by mass or less is preferable, and 10.0% by mass or less is more preferable in terms of achieving both dispersibility and coloring power. In the case of an inorganic pigment, 1.0% by mass or more is preferable, and 5.0% by mass or more is more preferable from the viewpoint of achieving both dispersibility and coloring power. Moreover, in the case of an inorganic pigment, 40.0 mass% or less is preferable, and 20.0 mass% or less is more preferable.
　［分散剤］
　本実施形態の活性エネルギー線硬化型インク組成物は、必要に応じて分散剤を含有しても良い。分散剤としては例えば高分子分散剤が挙げられる。この高分子分散剤の主鎖はポリエステル系、ポリアクリル系、ポリウレタン系、ポリアミン系、ポリカプロラクトン系等からなり、高分子分散剤は、側鎖としてアミノ基、カルボキシル基、スルホン基、ヒドロキシル基等の極性基やこれらの塩を有するのが好ましい。 [Dispersant]
The active energy ray-curable ink composition of the present embodiment may contain a dispersant as necessary. Examples of the dispersant include a polymer dispersant. The main chain of this polymer dispersant is made of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and the polymer dispersant has amino groups, carboxyl groups, sulfone groups, hydroxyl groups, etc. as side chains. It is preferable to have a polar group or a salt thereof.
　高分子分散剤としては、ビックケミー社製「ＤＩＳＰＥＲＢＹＫ－１６８」、「ＤＩＳＰＥＲＢＹＫ－２０１３」、「ＤＩＳＰＥＲＢＹＫ－２０５５」、「ＤＩＳＰＥＲＢＹＫ－２０９６」、「ＤＩＳＰＥＲＢＹＫ－２１５２」、「ＤＩＳＰＥＲＢＹＫ－２１５５」、「ＤＩＳＰＥＲＢＹＫ－２２００」、「ＢＹＫ－９０７６」、「ＢＹＫ－９０７７」、「ＢＹＫＪＥＴ－９１４２」、「ＢＹＫＪＥＴ－９１５０」、「ＢＹＫＪＥＴ－９１５１」、「ＢＹＫＪＥＴ－９１５２」；ビーエーエスエフ社製「Ｄｉｓｐｅｘ　Ｕｌｔｒａ　ＦＡ　４４２０」、「Ｄｉｓｐｅｘ　Ｕｌｔｒａ　ＦＡ　４４２５」、「Ｅｆｋａ　ＰＸ　４７０１」、「Ｅｆｋａ　ＰＸ　４７３１」、「Ｅｆｋａ　ＰＸ　４７３２」、「Ｅｆｋａ　ＰＸ　４７３３」；ルーブリゾール社製「ソルスパース（ＳＯＬＳＰＥＲＳＥ）３０００」、ソルスパース５０００」、「ソルスパース９０００」、「ソルスパース１２０００」、「ソルスパース１３２４０」、「ソルスパース１３９４０」、「ソルスパース１７０００」、「ソルスパース２２０００」、「ソルスパース２４０００」、「ソルスパース２６０００」、「ソルスパース２８０００」、「ソルスパース３２０００」、「ソルスパース３３０００」、「ソルスパース３６０００」、「ソルスパース３９０００」、「ソルスパース４１０００」、「ソルスパース７１０００」；楠本化成社製「ディスパロン　ＤＡ－３２５」、「ディスパロン　ＤＡ－３７５」、「ディスパロン　ＤＡ－２３４」、「ディスパロン　ＤＡ－５５０」；味の素ファインテクノ社製「アジスパーＰＢ８２１」、「アジスパーＰＢ８２２」、「アジスパーＰＢ８２４」、「アジスパーＰＢ８８１」；共栄社化学社製、「フローレンＧ－７００」、「フローレンＫＤＧ－２４００」、「フローレンＧＷ－１５００」；エボニックデグサジャパン社製「ＴＥＧＯ　Ｄｉｓｐｅｒｓ６８５」、「ＴＥＧＯ　Ｄｉｓｐｅｒｓ６９０」等が挙げられる。 Examples of the polymer dispersant include “DISPERBYK-168”, “DISPERBYK-2013”, “DISPERBYK-2055”, “DISPERBYK-2096”, “DISPERBYK-2155”, “DISPERBYK-2155”, “DISPERBYK-2200” manufactured by BYK Chemie. ”,“ BYK-9076 ”,“ BYK-9077 ”,“ BYKJET-9142 ”,“ BYKJET-9150 ”,“ BYKJET-9151 ”,“ BYKJET-9152 ”;“ Dispex Ultra FA 4420 ”manufactured by BASF, Dispex Ultra FA 4425, "Efka PX 4701", "Efka PX 4731", "Efka PX 4732", "Efka PX 4733"; “SOLSPERSE 3000”, “SOL SPERSE 5000”, “SOL SPERSE 9000”, “SOL SPERSE 12000”, “SOL SPERSE 13240”, “SOL SPERSE 13940”, “SOL SPERSE 17000”, “SOL SPERSE 22000”, “SOL SPERS 24000”, “Sol Sparse 26000”, “Sol Sparse 28000”, “Sol Sparse 32000”, “Sol Sparse 33000”, “Sol Sparse 39000”, “Sol Sparse 39000”, “Sol Sparse 41000”, “Sol Sparse 71000”; “Disparon DA-325” manufactured by Enomoto Kasei Co., Ltd. , “Disparon DA-375”, “Disparon DA-234”, “Disparon DA-550”; Ajinomoto Fine Techno “Ajisper PB821”, “Azisper PB822”, “Azisper PB824”, “Azisper PB881” manufactured by Kyoeisha Chemical Co., Ltd., “Floren G-700”, “Floren KDG-2400”, “Floren GW-1500”; Evonik Degussa Japan “TEGO Dispers 685”, “TEGO Dispers 690”, etc., manufactured by the company are listed.
　［表面調整剤］
　本実施形態の活性エネルギー線硬化型インク組成物は、更に表面調整剤を含有していても良い。表面調整剤としては特に限定されないが、具体例としては、ジメチルポリシロキサンを有するビックケミー社製「ＢＹＫ－３０７」、「ＢＹＫ－３３３」、「ＢＹＫ－３５４」、「ＢＹＫ－３６１Ｎ」、「ＢＹＫ－３７７」、「ＢＹＫ－３７８」、「ＢＹＫ－３４５５」、「ＢＹＫ－ＵＶ３５００」、「ＢＹＫ－ＵＶ３５０５」、「ＢＹＫ－ＵＶ３５１０」、「ＢＹＫ－ＵＶ３５３５」、「ＢＹＫ－ＵＶ３５７０」；エボニックデグサジャパン社製「ＴＥＧＯ　Ｆｌｏｗ４２５」、「ＴＥＧＯ　Ｇｌｉｄｅ１００」、「ＴＥＧＯ　Ｇｌｉｄｅ１１０」、「ＴＥＧＯ　Ｇｌｉｄｅ１３０」、「ＴＥＧＯ　Ｇｌｉｄｅ４３２」、「ＴＥＧＯ　Ｇｌｉｄｅ４３５」、「ＴＥＧＯ　Ｇｌｉｄｅ４４０」、「ＴＥＧＯ　Ｇｌｉｄｅ４５０」、「ＴＥＧＯ　ＧｌｉｄｅＺＧ４００」、「ＴＥＧＯ　Ｔｗｉｎ４０００」、「ＴＥＧＯ　Ｔｗｉｎ４２００」、「ＴＥＧＯ　Ｗｅｔ２７０」、「ＴＥＧＯ　Ｒａｄ２０１０」、「ＴＥＧＯ　Ｒａｄ２０１０」「ＴＥＧＯ　Ｒａｄ２１００」、「ＴＥＧＯ　Ｒａｄ２２００Ｎ」、「ＴＥＧＯ　Ｒａｄ２２５０」「ＴＥＧＯ　Ｒａｄ２３００」、「ＴＥＧＯ　Ｒａｄ２５００」、「ＴＥＧＯ　Ｒａｄ２７００」；共栄社化学社製「ポリフローＫＬ－４０１」、「ポリフローＫＬ－４０２」、「ポリフローＫＬ－４０３」、「ポリフローＫＬ－４０４」；アクリルポリマー系では、共栄社化学社製「ポリフローＮｏ．７５」、「ポリフローＮｏ．７７」、「ポリフローＮｏ．９０」、「ポリフローＮｏ．９５」、「ポリフローＮｏ．９９Ｃ」；エボニックデグサジャパン社製「ＴＥＧＯ　Ｗｅｔ５００」等が挙げられる。 [Surface conditioner]
The active energy ray-curable ink composition of this embodiment may further contain a surface conditioner. The surface conditioner is not particularly limited, but specific examples include “BYK-307”, “BYK-333”, “BYK-354”, “BYK-361N”, “BYK-” manufactured by BYK Chemie having dimethylpolysiloxane. 377 ”,“ BYK-378 ”,“ BYK-3455 ”,“ BYK-UV3500 ”,“ BYK-UV3505 ”,“ BYK-UV3510 ”,“ BYK-UV3535 ”,“ BYK-UV3570 ”; manufactured by Evonik Degussa Japan “TEGO Flow 425”, “TEGO Glide 100”, “TEGO Glide 110”, “TEGO Glide 130”, “TEGO Glide 432”, “TEGO Glide 435”, “TEGO Glide 440”, “TEGO Glide 450”, “TEGO Glide 450”, “TEGO G G400, TEGO Twin4000, TEGO Twin4200, TEGO Wet270, TEGO Rad2010, TEGO Rad2010, TEGO Rad2100, TEGO Rad2200N, TEGO Rad2250, TEGOTE2G “TEGO Rad2700”; “Polyflow KL-401”, “Polyflow KL-402”, “Polyflow KL-403”, “Polyflow KL-404” manufactured by Kyoeisha Chemical Co., Ltd .; .75 ”,“ Polyflow No. 77 ”,“ Polyflow No. 90 ”,“ Polyflow No. 95 ”,“ Polyflow No. 99C ”;“ TEGO W ”manufactured by Evonik Degussa Japan t500 "and the like.
　表面調整剤の含有量は、インク組成物全量中０．１質量％以上であることが好ましい。又、表面調整剤の含有量は、インク組成物全量中５．０質量％以下であることが好ましい。０．１質量％以上、又は、５．０質量％以下とすることで、インク組成物が熱可塑性樹脂基材等に対し好ましい濡れ性を有することとなり、基材上に記録する（像を形成する）際に活性エネルギー線硬化型インク組成物がハジキを生じることなく濡れ広がることが可能となるため、特に好ましい活性エネルギー線硬化型インク組成物とすることができる。 The content of the surface conditioner is preferably 0.1% by mass or more based on the total amount of the ink composition. The content of the surface conditioner is preferably 5.0% by mass or less based on the total amount of the ink composition. By setting the content to 0.1% by mass or more or 5.0% by mass or less, the ink composition has preferable wettability with respect to the thermoplastic resin substrate and the like, and recording is performed on the substrate (image formation). In this case, the active energy ray-curable ink composition can be spread and spread without causing repellency.
　［艶消し剤］
　本実施形態の活性エネルギー線硬化型インク組成物は、必要に応じて、艶消し剤を含有しても良い。艶消し剤としては、例えば、シリカ、アルミナ、炭酸カルシウムなどの各種粉粒体を使用することができる。艶消し剤は、単独で又は２種以上組み合わせて使用しても良い。 [Delustering agent]
The active energy ray-curable ink composition of the present embodiment may contain a matting agent as necessary. As the matting agent, for example, various powders such as silica, alumina, calcium carbonate and the like can be used. Matting agents may be used alone or in combination of two or more.
　［その他の添加剤］
　又、本実施形態の活性エネルギー線硬化型インク組成物は、その他の添加剤として、可塑剤、光安定化剤、酸化防止剤等、種々の添加剤を含有していても良い。溶剤は本願の目的を達成する範囲内で添加することもできる。 [Other additives]
Moreover, the active energy ray-curable ink composition of the present embodiment may contain various additives such as a plasticizer, a light stabilizer, and an antioxidant as other additives. The solvent can be added within a range that achieves the object of the present application.
　又、本実施形態の活性エネルギー線硬化型インク組成物の表面張力は、インクジェットの吐出性、吐出安定性の点から、４０℃での表面張力が２０ｍＮ／ｍ以上であることが好ましい。又、４０℃での表面張力が４０ｍＮ／ｍ以下であることが好ましい。 In addition, the surface tension of the active energy ray-curable ink composition of the present embodiment is preferably 20 mN / m or more at 40 ° C. from the viewpoints of inkjet dischargeability and discharge stability. Further, the surface tension at 40 ° C. is preferably 40 mN / m or less.
　＜積層体の製造方法＞
　本実施形態において積層体の製造は、上記活性エネルギー線硬化型インク組成物を、基材上へ好ましくはインクジェット方式で印刷した後、活性エネルギー線で硬化することによって行われる。又、インクジェット方式で印刷する際にインクジェットヘッドを加熱した状態で印刷しても良いし、室温のまま印刷しても良い。 <Method for producing laminate>
In the present embodiment, the laminate is produced by printing the active energy ray-curable ink composition on a substrate, preferably by an ink jet method, and then curing with an active energy ray. Moreover, when printing by an inkjet system, you may print in the state which heated the inkjet head, and may print with room temperature.
　なお、本実施形態の活性エネルギー線硬化型インク組成物を使用して基材に画像を形成することができる。例えば、様々な色合いの色材をそれぞれ含有させた活性エネルギー線硬化型インク組成物のインクセットを用意し、インクジェット方式により印刷後、インク組成物を硬化することによって、基材に様々な画像を形成することができる。このような硬化膜を形成する活性エネルギー線硬化型インク組成物や基材上に画像を形成する像形成方法も本発明の範囲である。尚、本明細書において「画像」とは、単色又は複数の色からなる文字、図表、図形、記号、写真等を含む視覚を通じて認識することができる装飾的な像を意味し、例えば、木目、石目、布目、砂目、幾何学模様、文字などからなる絵柄等も含まれる。 Note that an image can be formed on a substrate using the active energy ray-curable ink composition of the present embodiment. For example, an ink set of an active energy ray-curable ink composition containing color materials of various shades is prepared, and after printing by an ink jet method, the ink composition is cured to display various images on the substrate. Can be formed. An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an image on a substrate are also within the scope of the present invention. In the present specification, the term “image” means a decorative image that can be recognized through vision including letters, diagrams, figures, symbols, photographs, etc. composed of a single color or a plurality of colors. Also included are patterns made of stone, cloth, sand, geometric patterns, letters, etc.
　［基材］
　基材は特に限定されず、例えば塗工紙、非塗工紙、布帛等の吸収体、非吸収性基材のいずれも使用することができる。具体的には、非塗工紙としては、更紙、中質紙、上質紙、塗工紙としては、コート紙、アート紙、キャスト紙、軽量コート紙、微塗工紙、布帛等の吸収体としては、綿、化繊織物、絹、麻、布帛、不織布、皮革等を例示でき、非吸収性基材としては、ポリエステル系樹脂、ポリプロピレン系合成紙、塩化ビニル樹脂、ポリイミド樹脂、金属、金属箔コート紙、ガラス、合成ゴム、天然ゴム等を例示できる。 [Base material]
The substrate is not particularly limited, and for example, any of a coated paper, a non-coated paper, an absorbent body such as a fabric, and a non-absorbent substrate can be used. Specifically, as non-coated paper, renewed paper, medium-quality paper, high-quality paper, and coated paper as coated paper, art paper, cast paper, lightweight coated paper, fine coated paper, fabric, etc. Examples of the body include cotton, synthetic fabric, silk, hemp, fabric, non-woven fabric, leather, etc. Examples of the non-absorbent substrate include polyester resin, polypropylene synthetic paper, vinyl chloride resin, polyimide resin, metal, metal Examples thereof include foil-coated paper, glass, synthetic rubber, and natural rubber.
　［活性エネルギー線による硬化］
　本実施形態の活性エネルギー線硬化型インク組成物を硬化させた硬化膜（以下、「硬化膜」と表記することがある。）を形成するための活性エネルギー線は、２００ｎｍ以上における波長域の光が好ましく、２５０ｎｍ以上における波長域の光がより好ましい。硬化膜を形成するための活性エネルギー線は、４５０ｎｍ以下における波長域の光が好ましく、４３０ｎｍ以下における波長域の光がより好ましい。光源は、特に限定されるものではなく、例えば、高圧水銀ランプ、メタルハライドランプ、低圧水銀ランプ、超高圧水銀ランプ、紫外線レーザー、太陽光、ＬＥＤランプ等が挙げられる。これらの光源を用い、積算光量が１００ｍＪ／ｃｍ２以上、好ましくは２００ｍＪ／ｃｍ２以上になるように活性エネルギー線を照射することにより、インク組成物を瞬時に硬化させることができる。 [Curing with active energy rays]
Active energy rays for forming a cured film (hereinafter, sometimes referred to as “cured film”) obtained by curing the active energy ray-curable ink composition of the present embodiment are light in a wavelength region at 200 nm or more. Is preferable, and light in a wavelength region of 250 nm or more is more preferable. The active energy ray for forming the cured film is preferably light in a wavelength region at 450 nm or less, and more preferably light in a wavelength region at 430 nm or less. The light source is not particularly limited, and examples thereof include a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, sunlight, and an LED lamp. By using these light sources and irradiating active energy rays so that the integrated light quantity is 100 mJ / cm 2 or more, preferably 200 mJ / cm 2 or more, the ink composition can be cured instantaneously.
　硬化膜の厚さは、１μｍ以上であることが好ましい。又、硬化膜の厚さは、１００μｍ以下であることが好ましい。１μｍ以上にすることで、色材を含有する硬化膜の色濃度が薄くなることなく、意匠性や装飾性の低下や密着性、伸長性等の物性が向上するため、より好ましい。１００μｍ以下にすることで、インク組成物に対して活性エネルギー線を照射した際に、インク組成物をより短時間で充分に硬化することができるようになるため、より好ましい。 The thickness of the cured film is preferably 1 μm or more. Moreover, it is preferable that the thickness of a cured film is 100 micrometers or less. By setting the thickness to 1 μm or more, the color density of the cured film containing the coloring material is not decreased, and physical properties such as a decrease in design properties, decorativeness, adhesion, and extensibility are improved. By setting the thickness to 100 μm or less, the ink composition can be sufficiently cured in a shorter time when the ink composition is irradiated with active energy rays, which is more preferable.
　硬化膜における厚さの測定方法は、作製した硬化膜と同様の塗布条件でＰＥＴフィルム（東洋紡績社製、Ａ４３００）に本実施形態の活性エネルギー線硬化型インク組成物を塗布し、得られた硬化膜の厚さをマイクロメーターにより測定することができる。尚、本明細書において、硬化膜の厚さとは１サンプルにつき１０箇所行い、これらの平均値を厚さ（平均厚さとする）。後述の保護層及びプライマーについても同様のものとする。 The method for measuring the thickness of the cured film was obtained by applying the active energy ray-curable ink composition of the present embodiment to a PET film (A4300, manufactured by Toyobo Co., Ltd.) under the same coating conditions as the prepared cured film. The thickness of the cured film can be measured with a micrometer. In this specification, the thickness of the cured film is 10 locations per sample, and the average value of these is the thickness (the average thickness). The same applies to the protective layer and primer described later.
　［硬化膜］
　本実施形態の活性エネルギー線硬化型インク組成物により形成される硬化膜は、前述したように色材等を含有していれば加飾層として用いることができる。更に、色材を添加せずに加飾層上に吐出することにより、本硬化膜は、硬化膜を保護するオーバーコート層として利用することもできる。更に、基材表面と硬化膜との間に形成することで両者の密着性を向上させるためのプライマー層としても利用することができる。このような硬化膜を形成する活性エネルギー線硬化型インク組成物も本発明の範囲である。 [Curing film]
The cured film formed by the active energy ray-curable ink composition of the present embodiment can be used as a decorative layer as long as it contains a color material or the like as described above. Furthermore, the cured film can be used as an overcoat layer that protects the cured film by discharging onto the decorative layer without adding a coloring material. Further, it can be used as a primer layer for improving the adhesion between the substrate surface and the cured film. An active energy ray-curable ink composition that forms such a cured film is also within the scope of the present invention.
　本実施形態の活性エネルギー線硬化型インク組成物は、本実施形態の活性エネルギー線硬化型インク組成物により形成される硬化膜のみで加飾層、オーバーコート層又はプライマー層をそれぞれ単独で形成することもできるし、又はこれらの層を複数組み合わせて形成することもできる。例えば本実施形態の活性エネルギー線硬化型インク組成物に色材等を加え加飾層を形成し、その加飾層上に色材等を加えていない本実施形態の活性エネルギー線硬化型インク組成物を吐出することでオーバーコート層を形成することもできる。又、本実施形態の活性エネルギー線硬化型インク組成物により形成される硬化膜を、従来公知のインク組成物により形成される加飾層、オーバーコート層又はプライマー層と組み合わせて使用することもできる。例えば本実施形態の活性エネルギー線硬化型インク組成物を加飾層として利用した場合に、その加飾層上に従来公知のオーバーコート組成物を用いてオーバーコート層を形成することもできる。 The active energy ray-curable ink composition of the present embodiment forms a decorative layer, an overcoat layer, or a primer layer independently only with a cured film formed by the active energy ray-curable ink composition of the present embodiment. Or a combination of these layers. For example, the active energy ray-curable ink composition of this embodiment in which a coloring material is added to the active energy ray-curable ink composition of this embodiment to form a decorative layer, and no coloring material or the like is added on the decorative layer. An overcoat layer can also be formed by discharging an object. The cured film formed from the active energy ray-curable ink composition of the present embodiment can also be used in combination with a decorative layer, overcoat layer or primer layer formed from a conventionally known ink composition. . For example, when the active energy ray-curable ink composition of the present embodiment is used as a decorative layer, an overcoat layer can be formed on the decorative layer using a conventionally known overcoat composition.
　基材にオーバーコート層やプライマー層を形成する場合、これらの層を形成する方法としてはどのような方法であっても良く、例えば、スプレー塗布、タオル、スポンジ、不織布、ティッシュ等を用いた塗布、ディスペンサー、刷毛塗り、グラビア印刷、フレキソ印刷、シルクスクリーン印刷、インクジェット、熱転写方式等のいずれであっても良い。尚、色材等を加えていない本実施形態の活性エネルギー線硬化型インク組成物を吐出することでオーバーコート層を形成する場合には、インクジェットによってこれらの層を形成することが好ましい。 When an overcoat layer or a primer layer is formed on a substrate, any method may be used to form these layers. For example, spray coating, towel, sponge, nonwoven fabric, tissue coating, etc. , Dispenser, brush coating, gravure printing, flexographic printing, silk screen printing, inkjet, thermal transfer method, etc. may be used. In addition, when forming an overcoat layer by ejecting the active energy ray-curable ink composition of the present embodiment to which no coloring material is added, it is preferable to form these layers by inkjet.
　［オーバーコート層］
　積層体の耐久性をより向上させることを目的に、本実施形態のインク組成物における硬化膜の表面に、従来公知のオーバーコート剤からなるオーバーコート層又は本実施形態のインク組成物をオーバーコート剤として用いて形成されるオーバーコート層が更に形成されていても良い。なお、オーバーコート層は、インク組成物の硬化膜からなる層の表面に形成される場合に限らず、基材の表面に直接形成されていても良いし、基材の表面に形成された、後述するプライマー層の表面に形成されていても良い。 [Overcoat layer]
For the purpose of further improving the durability of the laminate, the surface of the cured film in the ink composition of the present embodiment is overcoated with an overcoat layer comprising a conventionally known overcoat agent or the ink composition of the present embodiment. An overcoat layer formed by using as an agent may be further formed. The overcoat layer is not limited to being formed on the surface of the layer made of the cured film of the ink composition, but may be formed directly on the surface of the base material, or formed on the surface of the base material. You may form in the surface of the primer layer mentioned later.
　オーバーコート剤としては、本実施形態の活性エネルギー線硬化型インク組成物を好ましく用いることができる。本実施形態の活性エネルギー線硬化型インク組成物を用いることで、優れた硬化性と延伸性とを実現することができる。更に、例えば本実施形態の活性エネルギー線硬化型インク組成物を用いた硬化膜に本実施形態の活性エネルギー線硬化型インク組成物を用いたオーバーコート剤によりオーバーコート層を形成した場合には、当該硬化膜と当該オーバーコート層は同様の組成であるため、これらの密着性は極めて高い。そのため、本実施形態の活性エネルギー線硬化型インク組成物における硬化膜用のオーバーコート剤として本発明の活性エネルギー線硬化型インク組成物を用いることが特に好ましい。 As the overcoat agent, the active energy ray-curable ink composition of the present embodiment can be preferably used. By using the active energy ray-curable ink composition of the present embodiment, excellent curability and stretchability can be realized. Further, for example, when an overcoat layer is formed with an overcoat agent using the active energy ray-curable ink composition of the present embodiment on a cured film using the active energy ray-curable ink composition of the present embodiment, Since the cured film and the overcoat layer have the same composition, their adhesion is extremely high. Therefore, it is particularly preferable to use the active energy ray-curable ink composition of the present invention as an overcoat agent for a cured film in the active energy ray-curable ink composition of the present embodiment.
　オーバーコート層の厚さは、１μｍ以上であることが好ましい。１μｍ以上とすることで、硬化膜を適切に保護することができるため好ましい。又、オーバーコート層の厚さは、１００μｍ以下であることが好ましい。１００μｍ以下とすることで、オーバーコート層を形成するために乾燥時間が短縮され、生産性に優れたものとすることができるため好ましい。 The thickness of the overcoat layer is preferably 1 μm or more. The thickness is preferably 1 μm or more because the cured film can be appropriately protected. The overcoat layer preferably has a thickness of 100 μm or less. The thickness is preferably 100 μm or less because the drying time is shortened to form the overcoat layer and the productivity is excellent.
　又、オーバーコート層を形成する際にインク組成物の吐出量やインク組成物を吐出してから活性エネルギー線照射までにおける時間等の条件を調節することで、オーバーコート層に意匠性を付与することもできる。例えば、表面を艶消し調やグロス調にすることや、表面の膜厚をあえて不均一にすることで凹凸が付けられた立体的で意匠性の高いオーバーコート層を形成することもできる。具体的には、インク組成物を吐出後、所定時間経過後に活性エネルギー線を照射することで表面をグロス調にすることができ、又吐出後、速やかに活性エネルギー線を照射することで表面を艶消し調とすることができる。又１回の吐出量を吐出箇所によって増減させることで凹凸を付与することもできるし、又同一箇所でインク組成物の吐出と活性エネルギー線の照射とを繰り返すことで他箇所との凹凸差を付与することもできる。このような硬化膜を形成する活性エネルギー線硬化型インク組成物や凹凸像を形成する像形成方法も本発明の範囲である。なお、そのようなオーバーコート層は条件調整が容易である点からインクジェット方式で形成することが望ましい。凹凸像とは、必ずしも視覚を通じて認識されるものには限定されず、例えば無色の硬化膜であっても単色又は複数の色を有する硬化膜であっても、凹凸を有する形状であれば含まれる。 Further, when the overcoat layer is formed, the design property is imparted to the overcoat layer by adjusting the discharge amount of the ink composition and the conditions such as the time from the discharge of the ink composition to the irradiation of the active energy ray. You can also. For example, it is also possible to form a three-dimensional and highly designed overcoat layer with irregularities by making the surface matt or glossy, or by making the surface film thickness non-uniform. Specifically, after discharging the ink composition, the surface can be made glossy by irradiating active energy rays after a predetermined time has elapsed, and the surface can be quickly irradiated by irradiating active energy rays after discharging. It can be matte. In addition, unevenness can be imparted by increasing / decreasing the discharge amount per time depending on the discharge location, and unevenness difference from other locations can be achieved by repeating the ejection of the ink composition and the irradiation of active energy rays at the same location. It can also be granted. An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an uneven image are also within the scope of the present invention. Such an overcoat layer is desirably formed by an ink jet method from the viewpoint of easy condition adjustment. The concavo-convex image is not necessarily limited to what is visually recognized, and includes, for example, a colorless cured film or a cured film having a single color or a plurality of colors, as long as it has a concavo-convex shape. .
　以下、実施例により、本発明を更に詳細に説明するが、本発明はこれらの記載に何ら制限を受けるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these descriptions.
　＜インク組成物の調製（実施例１～３、比較例１～３、参考例）＞
　実施例、比較例、及び参考例における、インク組成物全量中におけるインク組成物の活性エネルギー線重合性モノマー、非反応性樹脂、重合禁止剤、重合開始剤、界面活性剤、顔料分散液の質量部を表１に示す。 <Preparation of ink composition (Examples 1 to 3, Comparative Examples 1 to 3, Reference Example)>
In Examples, Comparative Examples, and Reference Examples, the mass of the active energy ray polymerizable monomer, non-reactive resin, polymerization inhibitor, polymerization initiator, surfactant, and pigment dispersion of the ink composition in the total amount of the ink composition The parts are shown in Table 1.
　〔インク組成物の調製〕
　各材料を表１に示す割合になるように混合し、室温（２０～２５℃）にて１時間撹拌した。その後、溶け残りがないことを確認した。その後、メンブレンフィルターを用いて濾過を行い、実施例、比較例、及び参考例の活性エネルギー線硬化型インク組成物を調製した。 [Preparation of ink composition]
Each material was mixed so as to have a ratio shown in Table 1, and stirred at room temperature (20 to 25 ° C.) for 1 hour. Thereafter, it was confirmed that there was no undissolved residue. Then, it filtered using a membrane filter and prepared the active energy ray hardening-type ink composition of an Example, a comparative example, and a reference example.
　表１中、「イソボルニルアクリレート」は、大阪有機化学工業社製のＩＢＸＡ（イソボルニルアクリレート）を用いた。表１中、「フェノキシエチルアクリレート」は、サートマー社製のＳＲ３３９Ａを用いた。表１中、「Ｎ－ビニルカプロラクタム」は、ＡＳＨＬＡＮＤ社製のＶ－ＣＡＰ／ＲＣ（Ｍ）を用いた。表１中、「脂肪族ウレタンアクリレート」は、サートマー社製のＣＮ９９６を用いた。 In Table 1, as “isobornyl acrylate”, IBXA (isobornyl acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd. was used. In Table 1, SR339A manufactured by Sartomer was used as the “phenoxyethyl acrylate”. In Table 1, “N-vinylcaprolactam” used was V-CAP / RC (M) manufactured by ASHLAND. In Table 1, as the “aliphatic urethane acrylate”, CN996 manufactured by Sartomer was used.
　表１中、「ＣＡＢ５５１－０．０１」とは、イーストマン　ケミカル　ジャパン社製のＣＡＢ５５１－０．０１（セルロースアセテートブチレート樹脂）である。表１中、「Ｄｅｇａｌａｎ６６／０２Ｎ」とは、ＥＶＯＮＩＫ　ＩＮＤＵＳＴＲＩＥＳ社製のＤｅｇａｌａｎ６６／０２Ｎ（アクリル樹脂）である。表１中、「ＴＥＧＯ　ＶａｒｉＰｌｕｓ　ＳＫ」とは、エボニックデグサジャパン社製のＴＥＧＯ　ＶａｒｉＰｌｕｓ　ＳＫ（ポリオール樹脂）である。表１中、「ＣＡＢ５５１－０．０１」とは、イーストマン　ケミカル　ジャパン社製のＣＡＢ５５１－０．０１（セルロースアセテートブチレート樹脂）である。表１中、「ダイヤナール　ＢＲ１１３」とは、三菱レイヨン社製のダイヤナール　ＢＲ１１３（アクリル樹脂）である。表１中、「Ｄｅｇａｌａｎ６４／１２Ｎ」とは、ＥＶＯＮＩＫ　ＩＮＤＵＳＴＲＩＥＳ社製のＤｅｇａｌａｎ６４／１２Ｎ（アクリル樹脂）である。表１中、「ＴＥＧＯ　ＡｄｄＢｏｎｄ　ＬＴＨ」とは、エボニックデグサジャパン社製のＴＥＧＯ　ＡｄｄＢｏｎｄ　ＬＴＨ（変性特殊ポリエステル）である。 In Table 1, “CAB551-0.01” is CAB551-0.01 (cellulose acetate butyrate resin) manufactured by Eastman Chemical Japan. In Table 1, “Degalan 66 / 02N” is EVALIK INDUSTRIES's Degalan 66 / 02N (acrylic resin). In Table 1, “TEGO VariPlus SK” is TEGO VariPlus SK (polyol resin) manufactured by Evonik Degussa Japan. In Table 1, “CAB551-0.01” is CAB551-0.01 (cellulose acetate butyrate resin) manufactured by Eastman Chemical Japan. In Table 1, “Dianar BR113” is a dialal BR113 (acrylic resin) manufactured by Mitsubishi Rayon Co., Ltd. In Table 1, “Degalan 64 / 12N” refers to Degalan 64 / 12N (acrylic resin) manufactured by EVONIK INDUSTRIES. In Table 1, “TEGO AddBond LTH” is TEGO AddBond LTH (modified special polyester) manufactured by Evonik Degussa Japan.
　　表１中、「Ｇｅｎｏｒａｄ２２」とは、Ｒａｈｎ社製のＧｅｎｏｒａｄ２２（Ｎーニトロソ－Ｎ－フェニルヒドロキシルアミンアルミニウム塩溶液（有効成分約０．００５％））であって重合禁止剤である。表１中、「アンテージＴＤＰ」とは、川口化学工業社製のアンテージＴＤＰ（フェノチアジン）であって重合禁止剤である。 In Table 1, “Genorad22” is Genorad22 (N-nitroso-N-phenylhydroxylamine aluminum salt solution (active ingredient: about 0.005%)) manufactured by Rahn and is a polymerization inhibitor. In Table 1, “ANTAGE TDP” is ANTAGE TDP (phenothiazine) manufactured by Kawaguchi Chemical Industry Co., Ltd. and is a polymerization inhibitor.
　表１中、「ＤＡＩＤＯ　ＵＶ－ＣＵＲＥ　ＡＰＯ」とは、大同化成工業社製のＤＡＩＤＯ　ＵＶ－ＣＵＲＥ　ＡＰＯ（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）であって重合開始剤である。表１中、「ＤＥＴＸ」とは、三菱商事ケミカル社製、ＤＯＵＢＬＥＣＵＲＥ　ＤＥＴＸ（２，４－ジエチルチオキサンテン－９－オン）であって重合開始剤を意味する。表１中、「Ｓｐｅｅｄｃｕｒｅ　ＢＭＳ」とは、Ｌａｍｂｓｏｎ社製のＳｐｅｅｄｃｕｒｅ　ＢＭＳ（４－ベンゾイル　４’－メチルジフェニル　スルフィド）であって重合開始剤である。 In Table 1, “DAIDO UV-CURE APO” is DAIDO UV-CURE APO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by Daido Kasei Kogyo Co., Ltd. and is a polymerization initiator. In Table 1, “DETX” means DOUBLECURE DETX (2,4-diethylthioxanthen-9-one) manufactured by Mitsubishi Corporation Chemical Co., and means a polymerization initiator. In Table 1, “Speedcure BMS” is Speedcure BMS (4-benzoyl 4′-methyldiphenyl sulfide) manufactured by Lambson and is a polymerization initiator.
　表１中、「ＢＹＫＵＶ３５７０」とは、ビックケミー・ジャパン社製のＢＹＫＵＶ３５７０（ポリエステル変性ポリジメチルシロキサン溶液（有効成分７０％））であって界面活性剤である。 In Table 1, “BYKUV3570” is BYKUV3570 (polyester-modified polydimethylsiloxane solution (active ingredient 70%)) manufactured by Big Chemie Japan, and is a surfactant.
　表１中、「シアンミルベース」は、東洋インキ製造社製の顔料「リオノールブルーＦＧ－７４００」と、ビックケミー・ジャパン社製の分散剤「ＢＹＫＪＥＴ－９１５０」（有効成分７０％）とを、Ｄ（分散有効成分重量分）／Ｐ（顔料重量分）＝０．４　の比率とし、更に、大阪有機化学工業社製のＩＢＸＡにて、ミルベース中の顔料分を１２重量％となるように混合して製造した顔料分散液である。 In Table 1, “Cyan Mill Base” is a pigment “Rionol Blue FG-7400” manufactured by Toyo Ink Manufacturing Co., Ltd. and a dispersant “BYKJET-9150” (active ingredient 70%) manufactured by Big Chemie Japan Co., Ltd. The ratio of (dispersed active ingredient weight) / P (pigment weight) = 0.4, and further mixed with IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd. so that the pigment content in the mill base is 12% by weight. Pigment dispersion prepared in
　＜初期粘度（Ｖａ）測定試験＞
　実施例、比較例、及び参考例の活性エネルギー線硬化型インク組成物について後述する保管試験前の粘度（初期粘度）（Ｖａ）を測定した。具体的には、ＤＩＮ　ＥＮ　ＩＳＯ　１２０５８－１に基づいて、落球粘度計を用いて４０℃で粘度を測定した。測定結果を表１に示す（表１中「初期粘度（Ｖａ）」と表記）。 <Initial viscosity (Va) measurement test>
The viscosity (initial viscosity) (Va) before the storage test described below was measured for the active energy ray-curable ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, the viscosity was measured at 40 ° C. using a falling ball viscometer based on DIN EN ISO 12058-1. The measurement results are shown in Table 1 (indicated as “initial viscosity (Va)” in Table 1).
　＜６０℃２８日保管後粘度（Ｖｂ）測定試験＞
　実施例、比較例、及び参考例の活性エネルギー線硬化型インク組成物について保管試験を行い、保管試験後の粘度（Ｖｂ）を測定した。具体的には、実施例、比較例、及び参考例の活性エネルギー線硬化型インク組成物について、およそ２５ｍｌを容量３０ｍｌの褐色ガラスびんへ入れ密栓した試料を、温度を６０℃、保管期間を２８日とし、保管試験を行った。そして、保管試験後の実施例、比較例、及び参考例の活性エネルギー線硬化型インク組成物について、上記の初期粘度（Ｖａ）測定試験と同様の方法で粘度を測定した。測定結果を表１に示す（表１中「６０℃２８日保管後粘度（Ｖｂ）」と表記）。尚、表１中において、活性エネルギー線硬化型インク組成物がゲル化してしまい、粘度が測定できなかった活性エネルギー線硬化型インク組成物については、「ゲル化」と記載した。 <Viscosity (Vb) measurement test after storage at 60 ° C. for 28 days>
The storage test was performed about the active energy ray hardening-type ink composition of an Example, a comparative example, and a reference example, and the viscosity (Vb) after a storage test was measured. Specifically, with respect to the active energy ray-curable ink compositions of Examples, Comparative Examples, and Reference Examples, approximately 25 ml of a sample sealed in a brown glass bottle with a capacity of 30 ml was sealed at a temperature of 60 ° C. and a storage period of 28. The storage test was conducted. And about the active energy ray hardening-type ink composition of the Example after a storage test, a comparative example, and a reference example, the viscosity was measured by the method similar to said initial viscosity (Va) measurement test. The measurement results are shown in Table 1 (expressed as “viscosity after storage at 60 ° C. for 28 days (Vb)” in Table 1). In Table 1, the active energy ray-curable ink composition in which the active energy ray-curable ink composition gelled and the viscosity could not be measured was described as “gelation”.
　［評価基準］
　初期粘度（Ｖａ）及び６０℃２８日保管後粘度（Ｖｂ）から、（Ｖｂ－Ｖａ）／Ｖａ×１００（単位は％）を計算し、表１中「保存安定性評価」に、（Ｖｂ－Ｖａ）／Ｖａ×１００が１０％以上若しくは－１０％以下の活性エネルギー線硬化型インク組成物、又は保管試験後にゲル化した活性エネルギー線硬化型インク組成物、については「ＮＧ」と記載し、（Ｖｂ－Ｖａ）／Ｖａ×１００が－１０％超１０％未満及び保管試験後にゲル化しなかった活性エネルギー線硬化型インク組成物については「ＧＯＯＤ」と記載した。 [Evaluation criteria]
From the initial viscosity (Va) and the viscosity after storage at 60 ° C. for 28 days (Vb), (Vb−Va) / Va × 100 (unit:%) is calculated. Va) / Va × 100 is 10% or more or −10% or less of the active energy ray-curable ink composition, or the active energy ray-curable ink composition gelled after the storage test is described as “NG”. An active energy ray-curable ink composition having (Vb−Va) / Va × 100 of more than −10% and less than 10% and which did not gel after the storage test was described as “GOOD”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より酸価が３．０ｍｇＫＯＨ／ｇ以下の非反応性樹脂を含有する実施例１～３の活性エネルギー線硬化型インク組成物は、酸価が３．０ｍｇＫＯＨ／ｇを超える非反応性樹脂を含有する比較例１～３の活性エネルギー線硬化型インク組成物に比べ、粘度安定性の高い活性エネルギー線硬化型インク組成物であることが分かる。 From Table 1, the active energy ray-curable ink compositions of Examples 1 to 3 containing a non-reactive resin having an acid value of 3.0 mgKOH / g or less are non-reactive resins having an acid value of more than 3.0 mgKOH / g. It can be seen that this is an active energy ray-curable ink composition having higher viscosity stability than the active energy ray-curable ink compositions of Comparative Examples 1 to 3 containing
　一方、酸価が３．５ｍｇＫＯＨ／ｇの非反応性樹脂を含有する比較例１の活性エネルギー線硬化型インク組成物は、保管試験前における活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖａと保管試験後における活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖｂの比である（Ｖｂ－Ｖａ）／Ｖａ×１００（単位は％）が１０％を大幅に超えており、粘度安定性の低い活性エネルギー線硬化型インク組成物であることが確認された。 On the other hand, the active energy ray-curable ink composition of Comparative Example 1 containing a non-reactive resin having an acid value of 3.5 mgKOH / g is a viscosity Va at 40 ° C. of the active energy ray-curable ink composition before the storage test. The ratio of viscosity Vb at 40 ° C. of the active energy ray-curable ink composition after storage test and (Vb−Va) / Va × 100 (unit:%) greatly exceeds 10%, and viscosity stability It was confirmed that it was an active energy ray-curable ink composition having a low viscosity.
　又、比較例２及び比較例３の活性エネルギー線硬化型インク組成物は、保管試験後に活性エネルギー線硬化型インク組成物がゲル化してしまい、同様に粘度安定性の低い活性エネルギー線硬化型インク組成物であることが確認された。 Moreover, the active energy ray-curable ink compositions of Comparative Examples 2 and 3 gelled after the storage test, and similarly, the active energy ray-curable inks having low viscosity stability. It was confirmed to be a composition.
　尚、参考例の非反応性樹脂自体を含有していない活性エネルギー線硬化型インク組成物は、実施例１～３の活性エネルギー線硬化型インク組成物と同様に粘度安定性の低い活性エネルギー線硬化型インク組成物ではある。しかしながら、初期粘度（Ｖａ）自体が実施例１～３の活性エネルギー線硬化型インク組成物と比べて低い。すなわち、実施例１～３の活性エネルギー線硬化型インク組成物が、非反応性樹脂を含有することにより、印刷装置やその装置の仕様（例えば、印刷装置のノズル等）に応じて最適となるように粘度の厳密に調整が可能であることが確認された。 The active energy ray-curable ink composition not containing the non-reactive resin itself of the reference example is an active energy ray having low viscosity stability as in the active energy ray-curable ink compositions of Examples 1 to 3. It is a curable ink composition. However, the initial viscosity (Va) itself is lower than that of the active energy ray-curable ink compositions of Examples 1 to 3. That is, the active energy ray-curable ink compositions of Examples 1 to 3 are optimized according to the printing apparatus and the specifications of the apparatus (for example, the nozzle of the printing apparatus) by containing the non-reactive resin. Thus, it was confirmed that the viscosity can be adjusted strictly.

Claims (10)

  1. 　活性エネルギー線重合性モノマーと、非反応性樹脂と、を含有するインクジェット用インクとして用いられる活性エネルギー線硬化型インク組成物であって、
    　ＪＩＳ　Ｋ　００７０：１９９２に基づいて測定された前記非反応性樹脂の酸価が３．０ｍｇＫＯＨ／ｇ以下である、活性エネルギー線硬化型インク組成物。     An active energy ray-curable ink composition used as an ink jet ink containing an active energy ray polymerizable monomer and a non-reactive resin,
    An active energy ray-curable ink composition, wherein the acid value of the non-reactive resin measured based on JIS K 0070: 1992 is 3.0 mgKOH / g or less.
  2. 　前記非反応性樹脂の含有量が前記活性エネルギー線硬化型インク組成物の全量中０．１質量％以上５質量％以下である、請求項１に記載の活性エネルギー線硬化型インク組成物。 The active energy ray-curable ink composition according to claim 1, wherein the content of the non-reactive resin is 0.1% by mass or more and 5% by mass or less in the total amount of the active energy ray-curable ink composition.
  3. 　前記非反応性樹脂の数平均分子量が１０万以下である、請求項１又は２に記載の活性エネルギー線硬化型インク組成物。 The active energy ray-curable ink composition according to claim 1 or 2, wherein the non-reactive resin has a number average molecular weight of 100,000 or less.
  4. 　前記非反応性樹脂がセルロース系樹脂、（メタ）アクリル系樹脂、及びポリオール系樹脂からなる群より選択される少なくとも１種の樹脂である、請求項１から３のいずれかに記載の活性エネルギー線硬化型インク組成物。 The active energy ray according to any one of claims 1 to 3, wherein the non-reactive resin is at least one resin selected from the group consisting of a cellulose resin, a (meth) acrylic resin, and a polyol resin. A curable ink composition.
  5. 　前記活性エネルギー線重合性モノマーの少なくとも１種は（メタ）アクリル酸エステルである、請求項１から４のいずれかに記載の活性エネルギー線硬化型インク組成物。 The active energy ray-curable ink composition according to any one of claims 1 to 4, wherein at least one of the active energy ray polymerizable monomers is a (meth) acrylic acid ester.
  6. 　ＪＩＳ　Ｋ　００７０：１９９２に基づいて測定された前記活性エネルギー線重合性モノマーの酸価が、１．０ｍｇＫＯＨ／ｇ以下である、請求項１から５のいずれかに記載の活性エネルギー線硬化型インク組成物。 The active energy ray-curable ink composition according to claim 1, wherein an acid value of the active energy ray-polymerizable monomer measured based on JIS K 0070: 1992 is 1.0 mgKOH / g or less. object.
  7. 　請求項１から６のいずれかに記載の活性エネルギー線硬化型インク組成物を６０℃２８日放置し、保管試験前の前記活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖａ（単位はｍＰａ・ｓ）と保管試験後の前記活性エネルギー線硬化型インク組成物の４０℃における粘度Ｖｂ（単位はｍＰａ・ｓ）の比である（Ｖｂ－Ｖａ）／Ｖａ×１００（単位は％）が－１０％超１０％未満である、活性エネルギー線硬化型インク組成物。 The active energy ray-curable ink composition according to any one of claims 1 to 6 is left at 60 ° C for 28 days, and the viscosity Va of the active energy ray-curable ink composition before storage test at 40 ° C (unit: mPa). (Vb−Va) / Va × 100 (unit:%) is a ratio of viscosity Vb (unit: mPa · s) at 40 ° C. of the active energy ray-curable ink composition after storage test An active energy ray-curable ink composition that is more than 10% and less than 10%.
  8. 　基材上に、請求項１から７のいずれかに記載の活性エネルギー線硬化型インク組成物の硬化膜であるインク硬化膜層が形成された積層体。 A laminate in which an ink cured film layer that is a cured film of the active energy ray-curable ink composition according to any one of claims 1 to 7 is formed on a substrate.
  9. 　請求項１から７のいずれかに記載の活性エネルギー線硬化型インク組成物を使用して基材上に画像及び／又は凹凸像を形成する像形成方法。 An image forming method for forming an image and / or a concavo-convex image on a substrate using the active energy ray-curable ink composition according to any one of claims 1 to 7.
  10. 　請求項１から７のいずれかに記載の活性エネルギー線硬化型インク組成物を使用して基材上に画像及び／又は凹凸像を形成する印刷物の製造方法。 A method for producing a printed material, wherein an image and / or a concavo-convex image is formed on a substrate using the active energy ray-curable ink composition according to any one of claims 1 to 7.
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