JP5287398B2 - Active energy ray-curable inkjet ink storage pouch - Google Patents

Description

  The present invention relates to an active energy ray-curable inkjet ink storage pouch excellent in storage stability of an active energy ray-curable inkjet ink as a content, and a printing apparatus using the pouch.

 Conventionally, active energy ray-curable inks have been used for offset printing and silk screen printing, but the cost per color can be reduced by ejecting the required amount of ink droplets when needed during printing. In recent years, demand for active energy ray-curable inks for ink jet printing has been increasing from the point that on-demand printing is possible without requiring a plate. Active energy ray curable inks for inkjet printing include ultraviolet curable ink jet inks that are cured with ultraviolet rays. Compared to conventional water-based or solvent-based non-curable inkjet inks, environmentally friendly by reducing volatile solvents. In recent years, a patent has been disclosed (see Patent Documents 1 and 2) in that it can be printed on a substrate having quick drying properties, odor reduction, and no ink absorbability, and has high substrate selectivity.

 In recent years, in printing apparatuses using these active energy ray-curable inkjet inks, there is an increasing demand for ink supply in a pouch form instead of a bottle form in terms of a plastic-saving material. The performance required for ink packaging is to suppress the deterioration of the ink content and retain its function and properties. Conventionally, as a packaging material used for pouches, aluminum has excellent barrier properties. A packaging material using a metal foil made of a metal such as a barrier layer has been used. However, since the packaging material using an aluminum layer is excellent not only in light but also in gas barrier properties, active species that are naturally generated in response to some energy such as temperature and impact are not easily inactivated, and the viscosity of the ink is easily changed. Especially in inkjet ink, it is very important not to cause viscosity change because viscosity has a great influence on printing stability and resulting image quality compared to other printing method inks such as gravure and offset. It is. In addition, packaging materials that use aluminum layers have many disadvantages, such as being treated as non-combustible materials when discarded after use, and that metal detectors cannot be used for various inspections of packages. There was a problem.

JP-A-6-200204 Special Table 2000-504778

  An object of the present invention is to provide an active energy ray-curable inkjet ink storage pouch having excellent storage stability of the active energy ray-curable inkjet ink as a content, a storage method using the pouch, and printing using the pouch. Providing a device.

In order to suppress the change in viscosity of the active energy ray-curable inkjet ink that is the content of the pouch, it is important to inactivate the naturally occurring active species in response to some energy such as temperature and impact. For example, the main cause of viscosity change in radical ultraviolet curable ink, which is a typical active energy ray curable ink, is due to polymerization reaction of ink by radicals. Can be stopped.
In general, radical scavengers such as polymerization inhibitors and antioxidants are often used as methods for inactivating active species. Typical examples include quinone-based and phenol-based scavengers, and the addition of a small amount of these can suppress changes in the viscosity of the ink. However, when the scavenger is contained, the curability of the ink may be reduced, or the pigment component contained in the ink may be aggregated.

On the other hand, oxygen is also known to have an effect of inactivating active species. However, in a method of filling oxygen in the ink packaging container, it is impossible to fill the container volume with 100% of the ink. There is a problem in that the inside of the container is depressurized by the oxygen that is generated and a dent is generated in the container, or when all the oxygen is lost, the viscosity may eventually change. Also, in the method of making the ink packaging container itself oxygen permeable, a bottle having a thickness that requires a molding process is limited in material and thickness, and it is difficult to control the oxygen permeability.
As a result of diligent research, the present inventors have found that a pouch comprising a laminated film not including a gas barrier layer is easy to control the oxygen permeability, and causes problems such as deformation of the container and a low filling rate. In other words, the present inventors have found that the viscosity of the active energy ray-curable inkjet ink that is the content is suppressed and the storage stability is improved.

That is, the present invention relates to an active energy ray-curable inkjet ink storage pouch comprising a laminated film not including a gas barrier layer.
The active energy ray curable type according to the invention is characterized in that the oxygen permeability measured under conditions of 25 ° C. and 80% relative humidity in a surface area per liter of ink is 0.5 cc / 24 h · atm or more. The present invention relates to an inkjet ink storage pouch.
The present invention also relates to the active energy ray-curable inkjet ink storage pouch, wherein the active energy ray-curable inkjet ink comprises a polymerizable monomer and a radical photopolymerization initiator.

Furthermore, the present invention is such that the heat-sealable plastic layers of the laminated film (Y) obtained by sequentially laminating one or more stretched plastic films and heat-sealable plastic layers are opposed to each other and heat-sealed. The active energy ray-curable inkjet ink storage pouch characterized by the above.
Furthermore, the present invention relates to the active energy ray-curable inkjet ink storage pouch, wherein the stretched plastic film is a polyester film or a polyamide film.
Furthermore, the present invention relates to the above active energy ray-curable inkjet ink storage pouch, wherein the polyamide film is a nylon film.

Furthermore, the present invention relates to the active energy ray-curable inkjet ink storage pouch, wherein the heat-sealable plastic layer is a heat-sealable plastic film formed from polypropylene resin or polyethylene resin.
Furthermore, the present invention relates to the above active energy ray-curable inkjet ink storage pouch further comprising a printing layer.
Furthermore, the present invention relates to the active energy ray-curable inkjet ink storage pouch, wherein the printed layer has light shielding properties.

Furthermore, the present invention relates to the active energy ray-curable inkjet ink storage pouch, wherein the active energy ray-curable inkjet ink contains a pigment and a pigment dispersant.
Furthermore, the present invention relates to an ink storage method using the active energy ray-curable inkjet ink storage pouch.
The present invention further relates to an ink stored in the active energy ray-curable inkjet ink storage pouch.
Furthermore, the present invention relates to an inkjet printing apparatus using the active energy ray-curable inkjet ink storage pouch.

  According to the present invention, it is possible to provide an active energy ray-curable inkjet ink storage pouch capable of suppressing a change in viscosity of the active energy ray-curable inkjet ink as a content and improving storage stability.

Hereinafter, the present invention will be described in detail.
[Pouches, laminated films]
The pouch of the present invention can be formed from various laminated films that do not include a gas barrier layer. Generally, the heat-sealable plastic layer on one side of the laminated film is disposed so as to face the inside of the pouch, the heat-sealable plastic layers are brought into contact with each other, heated, and fused. Often, this is not a limitation.
There is no limitation on the shape of the pouch, and any shape can be used as long as it can be suitably used for packaging ink-jet ink.

  The laminated film constituting the pouch of the present invention has an oxygen permeability of 0.5 cc / 24 h · measured under the conditions of 25 ° C. and 80% relative humidity in the surface area per liter of ink which is the contents when the pouch is made. It has a performance of atm or higher. If the oxygen permeability is too small, the viscosity of the ink is liable to change and the storage stability is impaired.

The laminated film is formed from one or more plastic films, and the oxygen permeability of the entire laminated film can be controlled by selecting the material and film thickness of the film. From the viewpoint of productivity and strength of the pouch, it is preferable to use a structure in which one or more stretched plastic films and a heat-sealable plastic layer are laminated.
Hereinafter, embodiments of the pouch of the present invention will be described in detail with reference to the drawings. 1 to 4 are schematic views showing a cross-sectional configuration of the pouch of the present invention and a laminated film constituting the pouch.

FIG. 1 shows one of the pouch embodiments. That is, the heat-sealable plastic layer of the laminated film in which the stretched plastic film (C) and the heat-sealable plastic layer (D) are sequentially laminated is shown.
FIG. 2 shows an aspect of the laminated film constituting the pouch. That is, the aspect which laminated | stacked the stretched plastic film (C) and the heat-sealable plastic layer (D) sequentially is shown.

FIG. 3 shows another embodiment of the laminated film. That is, it has two layers of stretched plastic films (C1) and (C2), two adhesive layers (E1) and (E2), and a heat-sealable plastic layer (D). In this case, the stretched plastic films (C1) and (C2) and the adhesive layers (E1) and (E2) can be independently the same or different stretched plastic films and adhesive layers.
FIG. 4 shows another embodiment of the laminated film. That is, it has two stretched plastic films (C1) and (C2), two adhesive layers (E1) and (E2), a printing layer (F), and a heat-sealable plastic layer (D). . Also in this case, as in FIG. 3, the stretched plastic films (C1) and (C2) and the adhesive layers (E1) and (E2) are independently the same or different stretched plastic films and adhesive layers. be able to.

Hereinafter, each layer will be described in detail.
[Gas barrier layer]
The gas barrier layer of the present invention is a layer having oxygen barrier properties, and has an oxygen permeability measured under conditions of 25 ° C. and 80% relative humidity of 10 cc · 20 μm / m ² · 24 h · atm or less. Say. Specific examples of such a property include an aluminum layer, an ethylene-vinyl alcohol copolymer film, a polyvinyl alcohol film, or a film on which an inorganic compound such as silicon oxide or aluminum oxide is deposited. As long as the gas barrier property is satisfied, there is no particular limitation.

[Stretched plastic film]
The stretched plastic film used in the present invention is preferably a material excellent in dimensional stability, heat resistance, and mechanical strength. For example, polyolefins such as polyethylene, polypropylene, and polybutene, ethylene-vinyl alcohol copolymers, polyvinyl alcohol, Formalized polyvinyl alcohol (vinylon), polyester such as polymethyl acrylate, polystyrene, polyethylene terephthalate, polyethylene 2,6 naphthalate, polyethylene butyrate, nylon 6, nylon 6-6, nylon 6-10, nylon 6-12 , Polyamides such as nylon 11 and nylon 12, polymethylpentene, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether imide, polyimide, polycarbonate , Stretched films of polyketone, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polyfuccavinyl, polyfuccavinylidene, polytrifucaethylene chloride, polytetrafluoroethylene, cellulose, methylcellulose, carboxymethylcellulose, etc., especially polyolefins, Polyester and polyamide are preferable, and polyester and polyamide are particularly preferable. Nylon is preferable as the polyamide, and biaxial stretching is preferable for stretching.
Of course, the present invention is not limited to these films, and it is possible to use a film obtained by bonding two or more of the above films by a known method as required.

When a plurality of stretched plastic films are used, the same kind of plastic film or a different kind of plastic film can be used. In the case of using a different plastic film, it is preferable to combine biaxially stretched polyethylene terephthalate (hereinafter also referred to as PET) and biaxially stretched nylon (hereinafter also referred to as ON).
Note that, unlike a heat-sealable plastic layer, which will be described later, the stretched plastic film has a property that it does not soften or melt under heat-sealing conditions (temperature, time, pressure, etc.) when forming the packaging material.

  The stretched plastic film or the like has a total amount of one or more additives such as pigments, antioxidants, antistatic agents, ultraviolet absorbers, lubricants, etc. as the total amount per 100 parts by weight of the resin. It can also be added within the range of 0.001 part to 5.0 parts.

Moreover, in order to ensure the strength as a pouch, those containing various reinforcing materials can be used as the plastic substrate constituting the laminated film. That is, one of fiber reinforcing materials such as glass fiber, aromatic polyamide fiber, carbon fiber, pulp, cotton and linter, powder reinforcing material such as carbon black and white carbon, or flaky reinforcing material such as glass flake and aluminum flake. Two or more types can be blended in a total amount of 2 to 150 parts by weight per 100 parts by weight of the stretched plastic film, and for the purpose of increasing the amount, heavy or soft calcium carbonate, mica, talc, kaolin, gypsum , Clay, barium sulfate, alumina powder, silica powder, magnesium carbonate, etc. may be blended according to a formulation known per se in an amount of 5 to 100 parts by weight as a total amount per 100 parts by weight of the film. There is no problem.
Moreover, in order to improve adhesiveness, it may be subjected to a corona treatment or an ion bombardment treatment as a pretreatment, or may be subjected to a chemical treatment, a solvent treatment or the like.

  Although there is no restriction | limiting in particular about the thickness of a film, The thing of the range of 3-500 micrometers can be utilized from the point of intensity | strength or handling. Preferably it is a thing of the range of 5-100 micrometers, More preferably, it is a thing of the range of 10-50 micrometers.

[Heat-sealable plastic layer]
The heat-sealable plastic layer used in the present invention has a role as a sealant layer when forming a pouch. That is, the heat-sealable plastic layers are brought into contact with each other and heated to be fused to form a packaging material. Therefore, the heat sealability in the present invention is the temperature at the time of heat sealing, specifically, the heat seal device is set to about 80 to 200 ° C., and softens or melts at such a set temperature, and the heat sealable plastic layers , Which adhere to each other.

  Specific examples of the heat-sealable plastic layer include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene- (meth) acrylic acid copolymer Examples thereof include a layer made of a resin such as a cross-linked product (ionomer) of a polymer and a metal ion such as sodium or zinc, an ethylene-acrylonitrile copolymer, an ethylene-vinyl acetate copolymer.

The heat-sealable plastic layer is preferably a heat-sealable plastic film formed from polyethylene resin, polypropylene resin or the like, and is a linear low density polyethylene film (hereinafter also referred to as LLDPE) or an unstretched polypropylene film (hereinafter also referred to as CPP). Is particularly preferred.
The optimum thickness of the heat-sealable plastic layer varies depending on the type, but is generally in the range of 1 to 200 μm.

  As a forming method, the above-mentioned resin is laminated by extrusion laminating, or a dry laminating method in which a film made of the above-mentioned resin is laminated using an adhesive layer, but it may be laminated by other known methods. good.

[Adhesive layer]
The adhesive layer bears the function of adhering both layers between the laminated films, and various types of adhesives such as urethane and imine can be used as the adhesive forming the adhesive layer. As for the coating method, an adhesive layer or the like can be provided by using a known method such as gravure coating, reverse coating, roll coating or the like.

[Print layer]
The printing layer of the present invention includes various pigments, extender pigments and plasticizers, desiccants, stabilizers, and the like in conventionally used ink binder resins such as urethane, acrylic, nitrocellulose, rubber, and vinyl chloride. These are characters, designs and the like formed by inks to which the additives are added. The printed layer may be contained anywhere in the laminated film, and preferably has light shielding properties in order to improve the light stability of the active energy ray-curable inkjet ink. Having light-shielding properties means that the light transmittance is low, and it is particularly preferable that the ultraviolet transmittance is low.

The printing layer having a light shielding property is a white ink containing a white pigment, a black ink containing a black pigment, an ink containing inorganic pigment fine particles having an ultraviolet blocking property, etc. on the film surface constituting the laminated film, One layer or two or more layers are stacked to form a solid print. When printing two or more layers, different colors or different inks may be combined.
Titanium oxide is suitably used as the white pigment, carbon black is suitably used as the black pigment, and zinc oxide is suitably used as the inorganic pigment fine particles having ultraviolet blocking properties.
As the light shielding property, the light transmittance in the ultraviolet wavelength region of 200 to 400 nm is preferably 5% or less, preferably 1% or less, and particularly preferably 0.1% or less. As the thickness of the printing layer having light-shielding property increases, the light-shielding property improves, but the film strength decreases. Therefore, it is preferably 10 g / m 2 or less, preferably 7 g / m 2 or less, and most preferably 5 g / m 2 or less. In order to improve the film strength, a curing agent may be used in combination.

  As a method for forming a printing layer, for a film constituting a laminated film, for example, a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, a roll coating, a knife edge coating, a gravure A known coating method such as coating can be used.

[Active energy ray-curable inkjet ink]
The active energy ray-curable ink jet ink of the present invention refers to an ink jet ink that causes an electron orbit of an ink composition to be affected by irradiation of active energy rays to be described later and causes a polymerization reaction of radicals, cations, anions, and the like.
Below, an active energy ray and an ink composition are demonstrated in detail.

[Active energy rays, photo radical polymerization initiator]
The active energy ray described in the present invention affects an electron orbit of an irradiated object such as an electron beam, an ultraviolet ray, and an infrared ray, and indicates an energy ray that can trigger a polymerization reaction such as a radical, a cation, and an anion. The energy ray is not limited to this as long as it induces a polymerization reaction.

  In the present invention, when ultraviolet rays are used as active energy rays, a radical photopolymerization initiator is blended in the ink. As the radical photopolymerization initiator, those of molecular cleavage type or hydrogen abstraction type are suitable for the present invention. Specific examples include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one, bis (2,4,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1,2-octanedione, 1- (4- (phenylthio) -2,2- (O-benzoyloxime)) and the like are preferably used, and other molecular cleavage types include 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2 -Methyl-1-phenylpropane-1-o 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one Moreover, benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide, etc., which are hydrogen abstraction type photopolymerization initiators, can also be used in combination.

For the photo radical polymerization initiator, as sensitizers, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, An amine that does not cause an addition reaction with the polymerizable component, such as N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone, can also be used in combination. Of course, it is preferable to select and use the radical photopolymerization initiator and the sensitizer, which are excellent in solubility in the ultraviolet curable compound and do not inhibit the ultraviolet transmittance.
The radical photopolymerization initiator and the sensitizer are used in the range of 1 to 25% by weight, preferably 5 to 23% by weight, more preferably 10 to 20% by weight, based on the total amount of the ultraviolet curable composition.

[Polymerizable monomer]
The polymerizable monomer in the present invention is an active energy ray curing reaction component, and specifically represents a molecule having an ethylenically unsaturated double bond.

  Specific examples of the monofunctional polymerizable monomer used in the present invention include cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, methylphenoxyethyl (meth) acrylate, and 4-t-butyl. Cyclohexyl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, tribromophenyl (meth) acrylate, ethoxylated tribromophenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate (or ethylene oxide array / Or propylene oxide addition monomer), acryloylmorpholine, isobornyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, N-vinyl capro Cutam, N-vinylpyrrolidone, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 4-hydroxybutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, 2 -Methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxyethoxyethyl ( Acrylate), butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, dipropylene glycol (meth) acrylate, β-carboxylethyl (meth) acrylate, ethyl diglycol (meth) Acrylate, trimethylolpropane formal mono (meth) acrylate, imide (meth) acrylate, isoamyl (meth) acrylate, ethoxylated succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate, ω-carboxypolycaprolactone mono (meth) Examples thereof include, but are not limited to, acrylate and N-vinylformamide.

  Further, among these polymerizable monomers having high ink jet suitability, cyclohexyl acrylate, methylphenoxyethyl acrylate, 2-phenoxyethyl acrylate (or its ethylene oxide / or propylene oxide addition monomer), acryloylmorpholine, isobornyl acrylate, N- Vinyl caprolactam, N-vinyl pyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, isooctyl acrylate, and lauryl acrylate can be more preferably used.

  Ink jet aptitude is aptitude as an active energy ray-curable ink jet ink, and specifically means discharge stability in an ink jet discharge device and curability when irradiated with active energy rays. Rheological properties such as the viscosity and surface tension of the monomer affect the ejection stability, and structural properties such as the number of functional groups and molecular weight of the monomer affect the curability.

  Furthermore, from the viewpoint of safety and coating film performance, methylphenoxyethyl acrylate, 2-phenoxyethyl acrylate (or its ethylene oxide / or propylene oxide addition monomer), acryloylmorpholine, isobornyl acrylate, N-vinylcaprolactam 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, and lauryl acrylate can be more preferably used.

  Specific examples of the polyfunctional polymerizable monomer include dimethylol-tricyclodecane di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, and cyclohexanedimethanol. Di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, tri (2-hydroxyethyl isocyanurate) tri (meth) acrylate, tri (meth) allyl isocyanurate , Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylated 1,6-hex Diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, hydroxypivalate trimethylolpropane tri (meth) acrylate , Ethoxylated phosphate tri (meth) acrylate, ethoxylated tripropylene glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, tetramethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, propoxylate glyceryl tri (meth) acrylate, Tetramethylol methane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, neopentyl glycol oligo (Meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, ethoxylated neopentyl Glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Ethoxylated trimethylolpropane tri (meth) acrylate, there may be mentioned propoxylated trimethylolpropane tri (meth) acrylate, but is not limited thereto.

  Among these, dimethylol-tricyclodecane diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meta) ) Acrylate can be used more suitably. These monofunctional and polyfunctional monomers may be used alone or in combination of two or more as required.

  The composition ratio of the polymerizable monomer is not particularly limited, and can be set as necessary.

  In addition to the above, what is called an oligomer or a prepolymer may be used for the inkjet ink of the present invention. Specifically, “Ebecryl 230, 244, 245, 270, 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 294 / 35HD, manufactured by Daicel UCB, 1259, 1264, 4866, 9260, 8210, 1290.1290K, 5129, 2000, 2001, 2002, 2100, KRM7222, KRM7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20T, 204, 205, 6602, 220, 4450, 770, IRR567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR302, 450, 670, 830, 835, 870, 1 30, 1870, 2870, IRR267, 813, IRR483, 811, 436, 438, 446, 505, 524, 525, 554W, 584, 586, 745, 767, 1701, 1755, 740 / 40TP, 600, 601, 604, 605, 607, 608, 609, 600 / 25TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2958, 2959, 3200, 3201, 3404, 3411, 3412, 3415, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3703, 3702, RDX63182, 6040, IRR419 ", manufactured by Sartomer CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9873, CN991, "Laromar EA81L, F87" manufactured by BASF LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8981, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D, UA19T, LR9005, PO83F, PO33F, L8489, L9489 LR8996, LR9013 LR9019, PO9026V, PE9027V "manufactured by Cognis" Photomer 3005, 3015, 3016, 3072, 3982, 3215, 5010, 5429, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660 "," Art Resin UN-9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, manufactured by Negami Kogyo Co., Ltd. 1200TPK, 6060PTM, 6060P "," Nippon Gosei Chemical Co., Ltd. "" purple light UV-6630B, 7000B, 7510B, 7461TE, 3000B, 320 " 0B, 3210EA, 3310B, 3500BA, 3520TL, 3700B, 6100B, 6640B, 1400B, 1700B, 6300B, 7550B, 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B, “Kayarad” R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C-0011, TCR-1234, ZFR-1122, UX-2201, UX-2301, UX3204, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX-4101 "and the like.

[Pigment]
The ink shown by this invention shows the liquid printed or applied to the base-material surface. This ink can be used as a coating application when it does not contain a coloring component, and can be used as a material for displaying graphics, characters, photographs, etc. when it contains a coloring component. Conventionally, dyes and pigments are widely used as the coloring component, but pigments are often used particularly from the viewpoint of weather resistance. As a pigment component,
Specific examples of carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, manufactured by Degussa. 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", Cabot's" REGAL 400R, 660R, 330R, 250R "," MOGUL E, L ", Mitsubishi Chemical “MA7, 8, 11, 77, 100, 100R, 100S, 220, 230” “# 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 "
And so on. Further, in the present invention, yellow, magenta, cyan ink, or other colors such as white can be used, and pigments used in inks generally used in printing applications and paint applications can be used, such as color developability and light resistance. Can be selected according to the required use.

The ratio of the pigment to the total ink is 1 to 15 parts by weight for organic pigments such as yellow, magenta, cyan and black with respect to 100 parts by weight of ink. It is preferable to mix | blend in arbitrary ratios of 5 weight part-40 weight part.
When a pigment is contained, it is preferable to add a pigment dispersant in order to improve the dispersibility of the pigment and the storage stability of the ink. There are various types of pigment dispersants such as a high molecular type dispersant and a low molecular type dispersant. These can be selected according to dispersibility, for example, hydroxyl group-containing carboxylic acid ester, salt of long chain polyaminoamide and high molecular weight acid ester, salt of high molecular weight polycarboxylic acid, long chain polyaminoamide and polar acid ester. Salt, high molecular weight unsaturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxy Ethylene alkyl phosphate ester, polyoxyethylene nonylphenyl ether, stearylamine acetate and the like can be used.

Specific examples of the pigment dispersant include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylate)" manufactured by BYK Chemie, "Disperbyk-101 ( (Polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 ( Polymer copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated) Saturated acid polycarboxylic acid and silicon system "," Lactimon (long chain amine and unsaturated acid poly) Recarboxylic acid and silicon) ”.
Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) "," Floren TG-710 (urethane oligomer) "," Flownon "manufactured by Kyoeisha Chemical Co., Ltd. “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (manufactured by Enomoto Kasei Co., Ltd.) Aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ” That.

  Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (poly) Carboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, “Abisia” Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000, “Nikkor T106 (polyoxy) manufactured by Nikko Chemical Co., Ltd. Ethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), “Ajisper PB821, 822, 824” manufactured by Ajinomoto Fine Techno Co., etc.

  The pigment dispersant is preferably contained in the composition in an amount of 0.1 to 10% by weight. Further, in order to further improve the dispersibility of the pigment and the storage stability of the ink, it is preferable to add an acidic derivative of an organic pigment to the composition of the present invention when the pigment is dispersed.

[Additive]
In the ink-jet ink of the present invention, various additives such as a plasticizer, a surface tension adjuster, an ultraviolet ray inhibitor, a slipping agent, an antiblocking agent, a light stabilizer, and an antioxidant can be used.
As a surface tension adjusting agent for improving the wettability to the substrate, the slipperiness of the printed film, and the blocking property, “BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 370, 375, 377, 350, 352, 354, 355, 356, 358N, 361N, 357, 390, 392, UV3500, UV3510, UV3570 “Tegorad-2100, 2200, 2250, 2500, 2700” and the like manufactured by the company are listed. These surface conditioners are preferably contained in the composition in an amount of 0.001 to 1% by weight, and may be used alone or in combination of two or more as required.

[ink]
The ink-jet ink of the present invention is preferably an ink-jet ink comprising a polymerizable monomer. In this case, the pigment is well dispersed together with the polymerizable monomer and the pigment dispersant using a normal disperser such as a sand mill. Manufactured by. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with a monomer. Sufficient dispersion is possible even with dispersion by a normal disperser. Therefore, excessive dispersion energy is not required, and a large amount of dispersion time is not required. An ink having excellent properties is prepared. The ink is preferably filtered through a filter having a pore size of 3 μm or less, and more preferably 1 μm or less.

The inkjet ink of the present invention is preferably adjusted to have a high viscosity at 25 ° C. of 5 to 50 mPa · s. An ink having a viscosity of 5 to 50 mPa · s at 25 ° C. exhibits stable ejection characteristics, particularly from a head having a normal frequency of 4 to 10 KHz to a head having a high frequency of 10 to 50 KHz.
When the viscosity is less than 5 mPa · s, a decrease in the follow-up property of the discharge is recognized in the high-frequency head. When the viscosity exceeds 50 mPa · s, even if a mechanism for reducing the viscosity by heating is incorporated in the head, the discharge itself A drop occurs, the ejection stability becomes poor, and the ejection cannot be performed at all.

  The ink-jet ink of the present invention preferably has an electric conductivity of 10 μS / cm or less in the piezo head and does not cause electrical corrosion inside the head. Further, in the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.

  In order to form an image with the inkjet ink of the present invention, a method is preferred in which the ink is ejected and drawn on a substrate by an inkjet recording method and then the ink is cured by irradiation with an active energy ray such as ultraviolet rays. It is not limited to.

  When irradiating ultraviolet rays as a light source for active energy rays, for example, high-pressure mercury lamps, metal halide lamps, low-pressure mercury lamps, ultra-high pressure mercury lamps, UV-LEDs that are monochromatic light, ultraviolet lasers, and sunlight are also used. can do. When cured with an electron beam, it is usually cured with an electron beam having an energy of 300 eV or less, but it can also be cured instantaneously with an irradiation dose of 1 to 5 Mrad.

[Preservation method]
The ink of the present invention is stored using the inkjet storage pouch of the present invention. The storage temperature is preferably −10 to 50 ° C., more preferably 0 to 40 ° C., and particularly preferably 5 to 35 ° C. In addition, the storage environment is preferably a light-shielding environment, and particularly when the laminated film does not include a light-shielding printing layer, the light-shielding environment is more preferable.

[Printer]
The ink of the present invention is printed by the ink jet printing apparatus of the present invention. In general, an inkjet printing apparatus is a printing apparatus that performs printing by ejecting ink from a discharge port to a print medium. The inkjet head discharges ink from the discharge port and supplies ink to the inkjet head. And supply system. Since the ink in the present invention is an active energy ray curable ink, it is preferable that an active energy ray irradiation device is attached to the printing apparatus, and the irradiation device preferably operates alone or in conjunction with an inkjet head. However, it is not limited to these.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”.

<Oxygen permeability>
The oxygen permeability of the laminated film was determined by measuring oxygen permeability at 25 ° C. and 80% RH using an oxygen permeation tester OX-TRAN TWIN manufactured by Modern Control. Specifically, oxygen gas and nitrogen gas (carrier gas) humidified at 25 ° C. and 80% RH were used.
<Viscosity change rate evaluation>
The ink was sealed in a pouch at a filling rate of 100% and then stored for 30 days in a light-shielded oven maintained at 50 ° C. The ink viscosity before and after storage was measured using an E-type viscometer VISCOMETER TV-22 manufactured by Toki Sangyo Co., Ltd., and the viscosity change rate was determined.
<Curability evaluation>
On the hard polyvinyl chloride plate, the ink before and after storage used in the above viscosity evaluation was replaced with a bar coater No. 8 was applied, and immediately after that, ultraviolet rays were irradiated with a metal halide lamp 120 W / cm manufactured by Integration Technology Co., and the conveyor speeds when the ink before and after storage was cured were compared. The evaluation criteria are as follows.
○: The curing conveyor speed is the same. Δ: The curing conveyor speed has a difference of less than 10 m / min. X: The curing conveyor speed has a difference of 10 m / min or more.

<ΔE>
For the cured film of the ink before and after storage used for the curable evaluation, Lab was measured at three arbitrary locations using 530 manufactured by X-rite, and the average value was determined. From the cured film Lab values before and after storage, the color difference ΔE with respect to before storage was determined.

First, Pigment Dispersion A was prepared with the following composition. Hereinafter, a dispersion was prepared by adding a pigment and a dispersant to a monomer, stirring the mixture with a high-speed mixer or the like until uniform, and then dispersing the obtained mill base with a horizontal sand mill for about 1 hour.
<Pigment dispersion A>
Solsperse 32000 (pigment dispersant manufactured by Avicia) 9.0 parts 2-phenoxyethyl acrylate 61.0 parts Further, Pigment Dispersion B was prepared with the following composition. This dispersion was prepared by adding a pigment and a dispersant into an organic solvent, stirring the mixture with a high speed mixer or the like until uniform, and then dispersing the resulting mill base with a horizontal sand mill for about 2 hours.
<Pigment dispersion B>
・ Hostaperm Red E5B02 (Clariant quinacridone pigment) 20.0 parts ・ Solspers 24000 (Avisia pigment dispersion) 6.0 parts ・ 2-phenoxyethyl acrylate 74.0 parts

Further, Pigment Dispersion C was prepared with the following composition. This dispersion was prepared by adding a pigment and a dispersant to an organic solvent, stirring the mixture with a high speed mixer or the like until uniform, and then dispersing the obtained mill base with a horizontal sand mill for about 1.5 hours.
<Pigment dispersion C>
・ YELLOW PIGMENT E4GN
(Nickel complex azo pigment manufactured by LANXESS) 20.0 parts · Solsperse 33000 (pigment dispersant manufactured by Avicia) 15.0 parts · 25.0 parts of 2-phenoxyethyl acrylate

An ink-jet ink was obtained by using the pigment dispersion to make an ink with the following formulation.
<Inkjet ink A>
-Pigment dispersion A 11.5 parts-2-phenoxyethyl acrylate 40.0 parts-N-vinylcaprolactam 15.0 parts-Ethoxylated trimethylolpropane triacrylate 20.0 parts-Ebecryl 8402 (manufactured by Daicel UCB) 5 .5 parts, Irgacure 907 (Ciba Specialty Chemicals) 4.0 parts, Irgacure 819 (Ciba Specialty Chemicals) 4.0 parts <Inkjet ink B>
-Pigment dispersion B 18.0 parts-33.5 parts 2-phenoxyethyl acrylate-15.0 parts N-vinylcaprolactam-20.0 parts ethoxylated trimethylolpropane triacrylate-5.5 parts Ebecryl 8402-Irgacure 907 4.0 parts ・ Irgacure 819 4.0 parts

<Inkjet ink C>
Pigment dispersion C 17.0 parts 2-phenoxyethyl acrylate 34.5 parts N-vinylcaprolactam 15.0 parts Ethoxylated trimethylolpropane triacrylate 20.0 parts Ebecryl 8402 5.5 parts Irgacure 907 4.0 parts Irgacure 819 4.0 parts <Inkjet ink D>
Pigment Dispersion A 11.5 parts 2-phenoxyethyl acrylate 44.0 parts N-vinylcaprolactam 20.0 parts 2- (1,2-cyclohexanedicarboximide) ethyl acrylate 9.5 parts Ebecryl 8402 7 .0 part ・ Irgacure 907 4.0 parts ・ Irgacure 819 4.0 parts

<Inkjet ink E>
Pigment dispersion A 11.5 parts Isoboronyl acrylate 10.0 parts Lauryl acrylate 5.0 parts N-vinylcaprolactam 32.5 parts Tripropylene glycol diacrylate 18.0 parts Ethoxylated trimethylolpropane Triacrylate 23.0 parts, Irgacure 907 4.0 parts, Irgacure 819 4.0 parts <Inkjet ink F>
-Pigment dispersion A 11.5 parts-2-phenoxyethyl acrylate 5.0 parts-Isooctyl acrylate 10.5 parts-N-vinylcaprolactam 20.0 parts-Tripropylene glycol diacrylate 20.0 parts-Hydroxypivalic acid Neopentyl glycol diacrylate 25.0 parts · Irgacure 907 4.0 parts · Irgacure 819 4.0 parts

<Inkjet ink G>
-Pigment dispersion A 11.5 parts-2-phenoxyethyl acrylate 5.0 parts-Isooctyl acrylate 10.5 parts-N-vinylcaprolactam 20.0 parts-Tripropylene glycol diacrylate 20.0 parts-Hydroxypivalic acid Neopentylglycol diacrylate 25.0 parts, Irgacure 369 (manufactured by Ciba Specialty Chemicals) 4.0 parts, DAIDO UV-CURE APO (manufactured by Daido Kasei Kogyo Co., Ltd.) 2.0 parts 0 copies

<Adhesive>
A two-component curable urethane adhesive (manufactured by Toyo Morton Co., Ltd., TM250HVR, AT-RT86L-60) is prepared using ethyl acetate, and a mixed liquid (= adhesive layer forming coating) having a solid content of 30% by weight. )

[Example 1]
On the biaxially stretched polypropylene film (hereinafter also referred to as OPP, thickness 20 μm), the above-mentioned mixed solution for adhesive was applied to a bar coater no. 10 is applied and dried in an electric oven at 80 ° C. for 30 seconds, and then a linear low-density polyethylene film (hereinafter also referred to as LLDPE, thickness 60 μm) is applied while applying pressure under heating (dry lamination method). The laminated film was obtained. Table 1 shows the results of measuring the oxygen transmission rate of the obtained laminated film.
Next, the heat-sealable plastic layers (LLDPE) of the laminated film were bonded together while applying pressure under heating to obtain a pouch having the surface area shown in Table 1.

  Ink-jet ink A (1.5 L) was sealed in the pouch under conditions where air did not enter, and heat-sealed to obtain a pouch for storing ink-jet ink of the present invention. The obtained inkjet ink storage pouch was stored for 30 days in a light-shielded oven maintained at 50 ° C., and the ink viscosity change rate, curability, and ΔE before and after storage were evaluated. The obtained results are shown in Table 1.

[Example 2]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 1 except that the OPP was changed to a biaxially stretched polyester film (hereinafter also referred to as PET, thickness 12 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 3]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 2 except that LLDPE was changed to an unstretched polypropylene film (hereinafter also referred to as CPP, thickness 60 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Example 4]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 1 except that the OPP was changed to a biaxially stretched nylon film (hereinafter also referred to as ON, thickness 15 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 5]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 4 except that LLDPE was changed to an ethylene vinyl acetate copolymer film (hereinafter also referred to as EVA, thickness 60 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Example 6]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 4 except that LLDPE was changed to CPP (thickness 60 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 7]
On the PET film (thickness: 12 μm), the adhesive mixture was mixed with a bar coater No. 10 was applied and dried in an electric oven at 80 ° C. for 30 seconds, and then ON (thickness: 15 μm) was bonded by a dry laminating method to obtain a laminated film precursor. In the same manner, CPP (thickness 60 μm) was bonded onto the obtained laminated film precursor to obtain a laminated film.
An inkjet ink storage pouch was obtained in the same manner as in Example 1 except that the obtained laminated film was used. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Example 8]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 7 except that CPP was changed to LLDPE (thickness 60 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 9]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Example 8 except that the inkjet ink A was changed to the inkjet ink B. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 10]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Example 8 except that the inkjet ink A was changed to the inkjet ink C. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Example 11]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Example 8 except that the inkjet ink A was changed to the inkjet ink D. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 12]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Example 8 except that the inkjet ink A was changed to the inkjet ink E. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 13]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Example 8 except that the inkjet ink A was changed to the inkjet ink F. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 14]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Example 8 except that the inkjet ink A was changed to the inkjet ink G. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 15]
A white ink (manufactured by Toyo Ink Mfg. Co., Ltd., Fine Star R631 White) was applied to a bar coater No. 1 on PET (thickness 12 μm). 8 and dried in an electric oven at 80 ° C. for 30 seconds to obtain PET having a printed layer.
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 8 except that PET was changed to PET having the printed layer. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Example 16]
A white ink (manufactured by Toyo Ink Mfg. Co., Ltd., Fine Star R631 White) was applied to a bar coater No. 4 was dried in an electric oven at 80 ° C. for 30 seconds, and then black ink (Toyo Ink Mfg. Co., Ltd., Finestar R92 Black) was applied onto the ink layer with a bar coater No. 4 4 and dried in an electric oven at 80 ° C. for 30 seconds to obtain PET having a printed layer.
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 8 except that PET was changed to PET having the printed layer. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 17]
On PET (thickness: 12 μm), ultraviolet blocking ink (manufactured by Toyo Ink Manufacturing Co., Ltd., N532LP clear UVS) was applied to bar coater No. 8 and dried in an electric oven at 80 ° C. for 30 seconds to obtain PET having a printed layer.
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 8 except that PET was changed to PET having the printed layer. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 18]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 8 except that the surface area of the pouch was changed to the area shown in Table 1. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Example 19]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Example 8 except that ON (15 μm) was changed to ON (25 μm) and the surface area of the pouch was changed to the area shown in Table 1. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Example 20]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Example 8 except that PET (12 μm) was changed to PET (25 μm) and the surface area of the pouch was changed to the area shown in Table 1. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Comparative Example 1]
Adhesive liquid mixture was applied to the bar coater No. 1 on the vapor deposition layer side of silicon oxide vapor deposition PET (thickness 12 μm). 10 was applied and dried in an electric oven at 80 ° C. for 30 seconds, and then ON (thickness: 15 μm) was bonded by a dry laminating method to obtain a laminated film precursor. Similarly, LLDPE (thickness 60 μm) was bonded onto the obtained laminated film precursor to obtain a laminated film. Table 1 shows the results of measuring the oxygen transmission rate of the obtained laminated film.
Next, the heat-sealable plastic layers (LLDPE) of the laminated film were bonded together while applying pressure under heating to obtain a pouch having the surface area shown in Table 1.

Ink-jet ink A (1.5 L) was sealed in the pouch under conditions where air did not enter, and heat-sealed to obtain a pouch for storing ink-jet ink. The obtained inkjet ink storage pouch was stored for 30 days in a light-shielded oven maintained at 50 ° C., and the ink viscosity change rate, curability, and ΔE before and after storage were evaluated. The obtained results are shown in Table 1.
Table 1 shows the ink viscosity change rate, curability, and ΔE before and after pouch storage.

[Comparative Example 2]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Comparative Example 1 except that inkjet ink A was changed to inkjet ink B. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Comparative Example 3]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Comparative Example 1 except that the inkjet ink A was changed to the inkjet ink C. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Comparative Example 4]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Comparative Example 1 except that the inkjet ink A was changed to the inkjet ink D. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Comparative Example 5]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Comparative Example 1 except that the inkjet ink A was changed to the inkjet ink E. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Comparative Example 6]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Comparative Example 1 except that the inkjet ink A was changed to the inkjet ink F. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

[Comparative Example 7]
A laminated film and an inkjet ink storage pouch were obtained in the same manner as in Comparative Example 1 except that the inkjet ink A was changed to the inkjet ink G. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Comparative Example 8]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Comparative Example 1 except that the silicon oxide vapor-deposited PET was changed to PET (thickness 12 μm) and the ON was changed to the AL vapor-deposited PET (thickness OO μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Comparative Example 9]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Comparative Example 8 except that the LLDPE was changed to CPP (thickness 60 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Comparative Example 10]
On the PET (thickness 12 μm), the mixed liquid for adhesive was applied to a bar coater No. 10 was applied and dried in an electric oven at 80 ° C. for 30 seconds, and then ON (thickness: 15 μm) was bonded by a dry laminating method to obtain a laminated film precursor. In the same manner, AL foil (thickness 7 μm) and LLDPE (thickness 60 μm) were bonded onto the obtained laminated film precursor to obtain a laminated film.

An inkjet ink storage pouch was obtained in the same manner as in Comparative Example 1 except that the laminated film was used. Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.
[Comparative Example 11]
A laminated film and a pouch for storing ink-jet ink were obtained in the same manner as in Comparative Example 10 except that the LLDPE was changed to CPP (thickness 60 μm). Table 1 shows the oxygen permeability, ink viscosity change rate before and after pouch storage, curability, and ΔE of the obtained laminated film.

It is sectional drawing of the pouch (A) for active energy ray hardening type inkjet ink preservation | save of this invention which consists of a stretched plastic film (C) / heat-sealable plastic layer (D). It is sectional drawing of the laminated | multilayer film (B) which comprises the active energy ray hardening-type inkjet ink storage pouch of this invention which consists of a stretched plastic film (C) / heat-sealable plastic layer (D). Active energy ray-curable inkjet ink storage of the present invention comprising stretched plastic film (C1) / adhesive layer (E1) / stretched plastic film (C2) / adhesive layer (E2) / heat-sealable plastic layer (D) It is sectional drawing of the laminated | multilayer film (B) which comprises a pouch. Active energy ray of the present invention comprising stretched plastic film (C1) / printing layer (F) / adhesive layer (E1) / stretched plastic film (C2) / adhesive layer (E2) / heat-sealable plastic layer (D) It is sectional drawing of the laminated | multilayer film (B) which comprises the pouch for curable inkjet ink preservation | save.

(A) ... Pouch (B) ... Laminated film (C) ... Stretched plastic film (D) ... Heat-sealable plastic layer (E) ... Adhesive layer (F) ... Print layer

Claims (11)

It consists of a laminated film that does not include a gas barrier layer (the gas barrier layer includes a metal layer), and further has an oxygen permeability of 0.5 cc / (24 h) measured under conditions of 25 ° C. and 80% relative humidity on the surface area per liter of ink. An active energy ray-curable inkjet ink storage pouch characterized by having atm) or more. The active energy ray-curable inkjet ink storage pouch according to claim 1, wherein the active energy ray-curable inkjet ink comprises a polymerizable monomer and a radical photopolymerization initiator. The heat-sealable plastic layers of a laminated film obtained by sequentially laminating one or more stretched plastic films and a heat-sealable plastic layer are opposed to each other and heat-sealed. Or an active energy ray-curable inkjet ink storage pouch according to 2; 4. The active energy ray-curable inkjet ink storage pouch according to claim 3, wherein the stretched plastic film is a polyester film or a polyamide film. The active energy ray-curable inkjet ink storage pouch according to claim 4, wherein the polyamide film is a nylon film. 4. The active energy ray-curable inkjet ink storage pouch according to claim 3, wherein the heat-sealable plastic layer is a heat-sealable plastic film formed from polypropylene resin or polyethylene resin. The active energy ray-curable inkjet ink storage pouch according to claim 1, further comprising a printing layer. 8. The active energy ray-curable inkjet ink storage pouch according to claim 7, wherein the printed layer has a light shielding property. The active energy ray-curable inkjet ink storage pouch according to claim 1, wherein the active energy ray-curable inkjet ink contains a pigment and a pigment dispersant. An ink storage method using the active energy ray-curable inkjet ink storage pouch according to claim 1. An ink jet printing apparatus using the active energy ray-curable ink jet ink storage pouch according to claim 1.

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