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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