JP6695652B2 - Non-aqueous photocurable inkjet composition container and recording method - Google Patents

Description

  The present invention relates to a non-aqueous photocurable inkjet composition container and a recording method.

  The inkjet recording method is capable of recording high-definition images with a relatively simple device, and is rapidly developing in various fields. Among them, various studies have been made on a container for storing the ink composition. For example, in Patent Document 1, storage that suppresses a curing reaction of a radically polymerizable compound during storage of an ink composition and suppresses an increase in viscosity, and does not inhibit a curing reaction during use of the ink composition. A storage container containing a photocurable ink composition containing no free thermal polymerization inhibitor for the purpose of providing a container and a storage method, wherein a curing reaction of a radically polymerizable compound is suppressed inside. A storage container for a photocurable ink composition, in which a solid containing a substance is arranged, is disclosed.

JP, 2007-131330, A

  However, an ink composition having excellent curability and adhesiveness often contains a relatively hydrophilic component, and tends to absorb moisture when stored in a conventional container. Moisture absorption of the ink composition during storage causes a decrease in curability. On the other hand, in order to suppress moisture absorption, it is also possible to form a metal vapor deposition layer on the surface of the container, but in that case, the visibility of the contents of the container decreases, and the occurrence of foreign matter cannot be specified. The problem arises.

  The present invention has been made to solve at least a part of the above-mentioned problems, and can suppress deterioration of curability and ensure visibility of contents, and a non-aqueous photocurable inkjet composition container and the container. It is an object of the present invention to provide a recording method using a container.

  The present inventors diligently studied to solve the above problems. As a result, they have found that the above problems can be solved by using a container having a predetermined configuration, and have completed the present invention.

That is, the present invention is as follows.
[1]
A non-aqueous photocurable inkjet composition containing a polymerizable compound having a moisture absorption rate of 10.71% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90%;
Housing the nonaqueous light curable ink jet composition, Ri Do a member having a metal oxide layer, a cartridge case for accommodating the container and container that have a visible light-transmissive, or at least the non-aqueous photocurable accommodating the container having a visible light-transmissive housing the ink jet composition, Ri Do a member having a metal oxide layer, and a cartridge case for accommodating the package and the package that have a visible light transmission properties, the Prepare,
As the polymerizable compound, one or more of acryloylmorpholine and 4-hydroxybutyl acrylate are included,
The content of the polymerizable compound is 2 to 30 mass% with respect to the total amount of the non-aqueous photocurable inkjet composition,
A non-aqueous photocurable inkjet composition container.
[2]
The non-aqueous photocurable inkjet composition container according to item [1], wherein the polymerizable compound has a moisture absorption rate at a temperature of 60 ° C. and a relative humidity of 90% of 10.71 to 11% by mass / 24 hours or more. ..
[3]
The content of the polymerizable compound is 20 to 30% by mass with respect to the total amount of the non-aqueous photo-curable inkjet composition, according to the item [1] or [2]. Containment body.
[4]
The non-aqueous system according to any one of the above items [1] to [3], wherein the metal oxide layer contains one or more oxides selected from the group consisting of silica, alumina, titania, zirconia, and ceria. A photocurable inkjet composition container.
[5]
The non-aqueous photo-curable inkjet composition container according to any one of [1] to [4], wherein the non-aqueous photo-curable inkjet composition further contains an acylphosphine oxide compound.
[6]
The non-aqueous photocurable inkjet composition container according to any one of items [1] to [5], wherein the polymerizable compound contains a radically polymerizable compound.
[7]
The non-aqueous photo-curable inkjet composition container according to any one of [1] to [6] above, wherein the non-aqueous photo-curable inkjet composition further contains a pigment and a pigment dispersant.
[8]
The accommodating the non-aqueous light-curable ink jet composition, Ri Do from the member having the metal oxide layer comprises a cartridge case for accommodating the container and the container that have a visible light-transmissive, items [1 ] The nonaqueous photocurable inkjet composition container of any one of [7] to [7].
[9]
The non-aqueous photocurable inkjet composition container according to any one of items [1] to [8], wherein the container or the package has a water permeability of 20 g / m ² · 24 hours or less.
[10]
The non-aqueous photocurable inkjet composition according to any one of items [1] to [9], wherein the ratio of the number of hydrophilic groups to the molecular weight of the polymerizable compound (molecular weight / number of hydrophilic groups) is 222 or less. body.
[11]
The nonaqueous photocurable inkjet composition container according to item [10], wherein the ratio of the number of hydrophilic groups to the molecular weight (molecular weight / number of hydrophilic groups) is 156 or less.
[12]
The non-aqueous photocurable inkjet according to any one of the above items [1] to [11], wherein the ratio of the number of carbon atoms to the number of hydrophilic groups of the polymerizable compound (carbon number / hydrophilic group number) is 10 or less. Composition container.
[13]
The nonaqueous photocurable inkjet composition container according to item [12], wherein the ratio of the number of carbon atoms to the number of hydrophilic groups (number of carbons / number of hydrophilic groups) is 8 or less.
[14]
The non-aqueous photocurable inkjet composition container according to any one of the above items [1] to [13], wherein the metal oxide layer has a thickness of 20 to 500 nm.
[15]
The non-aqueous photocurable inkjet composition container according to any one of the above items [1] to [14], wherein the polymerizable compound contains an HLB of 10 or more.
[16]
The non-aqueous photocurable inkjet composition container according to any one of items [1] to [15], which contains acryloylmorpholine as the polymerizable compound.
[17]
The non-aqueous photocurable inkjet composition container according to any one of items [1] to [16], which contains 4-hydroxybutyl acrylate as the polymerizable compound.
[18]
The non-aqueous photo-curable composition according to any one of [1] to [17], wherein the non-aqueous photo-curable inkjet composition further contains an acylphosphine oxide compound and a thioxanthone compound as photopolymerization initiators. Type inkjet composition container.
[19]
The non-aqueous photo-curable inkjet composition is sent from the non-aqueous photo-curable inkjet composition container according to any one of the above [1] to [18] to an ejection nozzle via an ink flow path. A liquid feeding step for liquidizing,
A discharging step of discharging the non-aqueous photocurable inkjet composition from the discharging nozzle onto the recording medium.
[20]
The non-water-based photo-curable inkjet composition having a peak emission wavelength of 350 to 420 nm is irradiated to the non-aqueous photo-curable inkjet composition adhered to the recording medium by using a light emitting diode. The recording method according to item [19], which includes a curing step of curing the material.

FIG. 3 is an exploded perspective view showing an example of a non-aqueous photocurable inkjet composition container of the present embodiment.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary, but the present invention is not limited thereto. Various modifications are possible without departing from the spirit of the invention. In the drawings, the same elements will be denoted by the same reference symbols, without redundant description. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Non-aqueous photocurable inkjet composition container]
The non-aqueous photocurable inkjet composition container of the present embodiment (hereinafter, also referred to as “accommodator”) has a moisture absorption rate of 1.5% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90%. A non-aqueous photo-curable inkjet composition containing a polymerizable compound (hereinafter, also referred to as "ink composition"), and a container made of a member containing the non-aqueous photo-curable inkjet composition and having a metal oxide layer, Alternatively, a packaging body that contains at least a container that contains the non-aqueous photocurable inkjet composition and that includes a member having a metal oxide layer is provided.

In the present specification, the “container” refers to a container for directly containing the ink composition. In addition, the "packaging body" means at least a container that directly stores the ink composition, that is, a package that indirectly stores the ink composition. The package may contain at least the container, and may contain the entire container . The “container” is a concept that includes a container and a case that protects the container used as necessary, and refers to a container that directly or indirectly stores the ink composition. The container is used to store and transport the ink composition before the ink composition is used in the recording device, and when used, supplies the ink composition contained in the container to the recording device. Is. The container may be a container formed of only the container, that is, the container may be the container as it is.

  Examples of the form of the container include, but are not limited to, ink cartridges, packs, bottles, tanks, bottles, and cans. Among these, ink cartridges, packs, bottles, and tanks are preferable, and packs are more preferable, from the viewpoints of being widely used and easily controlling the water permeability and oxygen permeability described below to desired values.

  FIG. 1 is an exploded perspective view showing an example of the nonaqueous photocurable inkjet composition container of the present embodiment. The ink cartridge 40 includes an ink pack 70 filled with ink, and a cartridge case 72 including a main body case 76 for protecting the ink pack 70 by containing the ink pack 70 inside and a lid 78. The ink pack 70 has an ink supply port 74. The main body case 76 includes a cutout portion 80 and a groove portion 86, and the lid portion 78 includes a holding portion 82 and a hook portion 84. In the ink cartridge 40, the ink pack 70 is housed in the main body case 76 and the lid portion 84. At this time, the ink supply port 74 is fitted into the cutout portion 80, and then the pressing portion 82 and the cutout portion 80 are formed. It is fixed by being sandwiched. Further, the main body case 76 and the lid portion 84 are sealed by fitting the hook portion 84 into the groove portion 86. The ink pack 70 corresponds to the “container” of this embodiment, and the entire cartridge including the cartridge case 72 corresponds to the container. Although not shown, the “packaging body” may be a bag that accommodates the entire cartridge or a bag that accommodates the ink pack 70 in the cartridge and is accommodated in the cartridge case 72. Alternatively, the cartridge case 72 may also serve as the packaging body. The entire cartridge including the packaging body may be defined as a "container".

  The mode of use of the container is not particularly limited. For example, the container that is separate from the recording device is mounted on the recording device, and the ink composition is supplied from the container to the recording device in the mounted state. Aspect (A) of a cartridge or the like and an aspect (B) of a bottle or the like for supplying an ink composition to an ink tank or the like of a recording apparatus from an accommodation body which is a separate body from the recording apparatus, and the accommodation body of which is a recording apparatus in advance. The aspect (C) provided as a part thereof. In the case of the modes (A) and (C), the ink composition is supplied to the head of the recording apparatus from a mounted container or an installed container through a connecting portion such as an ink tube. , Can be recorded. In the mode (B), after transferring the ink composition from the container to the ink tank or the like of the recording apparatus, the ink composition is supplied from the ink tank to the head of the recording apparatus through the connecting portion such as the ink tube. , Can be recorded.

[Metal oxide layer]
The container containing the non-aqueous photocurable inkjet composition, or at least the container containing the non-aqueous photocurable inkjet composition, comprises a member having a metal oxide layer. The metal oxide layer is provided on at least one of the outer surface, the inner surface, and the inside of the member constituting the container or the package. It is preferable that the entire surface of the member containing the composition is provided. By having the metal oxide layer, the container or the package of the present embodiment has a lower moisture permeability and an excellent visibility. Furthermore, since the water permeability is low, it is possible to suppress the generation of foreign matter resulting from the moisture absorption of the ink composition. Further, since the visibility is excellent, it becomes easy to find a foreign substance generated in the container or the package.

  The metal oxide contained in the metal oxide layer is not particularly limited, but for example, an oxide of one or more metals selected from the group consisting of silica, alumina, titania, zirconia, and ceria is preferable. By containing such a metal oxide, the water permeability of the container or the package is further lowered, and the curability and adhesion of the ink composition to be contained tend to be maintained. The metal oxides contained in the metal oxide layer may be used alone or in combination of two or more. Further, the metal oxide layer may be a single layer or two or more layers.

  The thickness of the metal oxide layer is preferably 10 to 500 nm, more preferably 10 to 100 nm, and further preferably 20 to 80 nm. When the thickness of the metal oxide layer is 10 nm or more, the water permeability of the container or the package is further reduced, and the curability and adhesion of the ink composition to be contained tend to be maintained. Further, when the thickness of the metal oxide layer is 500 nm or less, visibility and flexibility tend to be further improved.

  The method for forming the metal oxide layer is not particularly limited, but for example, a method for depositing a metal oxide on the surface of a resin molded body or an inorganic molded body forming a container or a package, a resin forming a container or a package. A method of applying and drying a liquid composition containing a metal oxide on the surface of a molded body or an inorganic molded body is mentioned. Further, the container or the package of the present embodiment may be a layer in which the metal oxide layer mainly constitutes the container or the package.

[Other constituent materials of members]
The container or package comprises a member having a metal oxide layer. As the structure other than the metal oxide layer of the member, a molded body made of a resin material (resin molded body) or a molded body made of an inorganic material (inorganic molded body) can be used. It may have a physical layer. The constituent material forming the resin molded body or the inorganic molded body is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polypropylene, polyethylene, polyamide fibers, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer ( EVOH), resins such as polystyrene; or inorganic substances such as glass. In addition, the above-mentioned constituent materials may be blended at an appropriate ratio or used in combination of plural kinds.

  The member can be configured as a film, a member having a three-dimensional shape such as a box or a bottle, and the film is preferable in terms of the weight of the container. Of the above-mentioned constituent materials, the film material having good durability when used as a film is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polyethylene, polypropylene, polyamide fiber, ethylene vinyl acetate copolymer, ethylene. Examples thereof include plastic films such as vinyl alcohol copolymer and polystyrene. Among these, high density, low density or linear low density polyethylene, polypropylene, polyamide fiber, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, and polystyrene are preferable. The film material may be a laminated film or a stretched film. Examples of the inorganic molded body include glass and metal. The member may be any member as long as it has at least a metal oxide layer, and may be a member having a metal oxide layer as a main constituent element, for example, a member including only a metal oxide layer.

The oxygen permeability of the member having the metal oxide layer of the container or the package is preferably 5.0 cc · 20 μm / (m ² · day · atm) or less, more preferably 2.0 cc · 20 μm / (m ^2). · Day · atm) or less, and even more preferably 1.0 cc · 20 μm / (m ² · day · atm) or less. When the oxygen permeability is within the above range, the dissolved oxygen amount of the ink composition during storage tends to be less likely to change. The oxygen permeability can be measured by the method defined in JIS K 7126 (ISO 15105).

  In order to improve the oxygen permeability, the container or package may have a gas barrier layer. The gas barrier layer is not particularly limited, but examples thereof include a metal layer such as an aluminum layer, an ethylene vinyl alcohol copolymer layer, and an organic layer such as a polyvinyl alcohol layer.

  The total thickness of the container or the member of the package is preferably 50 μm or more, more preferably 70 μm or more, and further preferably 100 μm or more. When the total thickness of the container or the package is 100 μm or more, the water content and the amount of dissolved oxygen of the contained ink composition are less likely to change, and the strength of the container or the package tends to be obtained. The total thickness of the container or package is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less. When the total thickness of the container or package is 200 μm or less, flexibility tends to be further improved.

  The volume of the ink composition that can be contained in the container or the package is preferably 100 to 5,000 mL, more preferably 100 to 4,000 mL, further preferably 300 to 3,000 mL, and even more preferably Is 500-2500 mL. When the capacity of the container or the package is within the above range, the ink composition can be used up after the use of the container or the package is started and while the dissolved oxygen amount of the ink in the container or the package hardly changes. Also, there are advantageous effects such as the fact that the amount of dissolved oxygen of the ink composition during storage does not easily change.

  The container or package preferably has a visible light transmittance. "Visible light" refers to light having a wavelength of 400 to 800 nm. The visible light transmittance is preferably 40% or more, more preferably 50% or more, still more preferably 60% or more as an average transmittance in the above wavelength range. When the visible light transmittance is 40% or more, the visibility tends to be further improved. The upper limit of the visible light transmittance is not particularly limited, but it is preferably 100% or less. The visible light transmittance is decreased by increasing the thickness of the molded body (member) made of the metal oxide layer and other constituent materials, and the visible light transmittance of the molded body (member) made of the metal oxide layer and other constituent materials is reduced. Increased by reducing the thickness. The visible light transmittance can be measured by the method described in Examples.

The water permeability of the container or package is preferably 20 g / m ² · 24 hours or less, more preferably 10 g / m ² · 24 hours or less, and further preferably 5.0 g / m ² · 24 hours or less. Is. When the water permeability is 20 g / m ² · 24 hours or less, the curability and adhesiveness of the ink composition contained can be maintained, and the generation of foreign matter tends to be suppressed. The water permeability of the container or package is preferably 0.10 g / m ² · 24 hours or more, more preferably 0.20 g / m ² · 24 hours or more, and further preferably 1.0 g / m ^2. m ² · 24 hours or more, more preferably 2.0 g / m ² · 24 hours or more. When the water permeability is 0.10 g / m ² · 24 hours or less, the storage stability of the composition tends to be further improved. The moisture permeability increases, for example, by decreasing the thickness of the member, and decreases by increasing the thickness. The water permeability can be measured by the method described in the examples.

[Non-aqueous photocurable inkjet composition]
The non-aqueous photocurable inkjet composition contains a polymerizable compound having a moisture absorption rate of 1.5% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90%. In the present embodiment, such a polymerizable compound is also referred to as a hydrophilic polymerizable compound.

[Hydrophilic polymerizable compound]
Among the polymerizable compounds, those having a moisture absorption rate of 1.5% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90% are included. It is preferably 1.75 to 11% by mass / 24 hours, and more preferably 1.90 to 10% by mass / 24 hours. When the moisture absorption rate of the above compound is 1.5% by mass / 24 hours or more, it is excellent in curability and advantageous. In addition, when the moisture absorption rate of the above compound is 11% by mass / 24 hours or less, the generation of foreign matters and the like due to moisture absorption tends to be more suppressed. The moisture absorption rate can be measured by the method described in the examples.

  The polymerizable compound having a moisture absorption rate of 1.5% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90% is not particularly limited, and examples thereof include acryloylmorpholine, 4-hydroxybutyl acrylate, and tetrahydrofurfuryl acrylate. , 2-hydroxy-3-phenoxypropyl acrylate, and monofunctional monomers such as 2- (2-vinyloxyethoxy) ethyl acrylate and dipropylene glycol diacrylate.

  Among the above, from the group consisting of an oxygen atom bonded to two acyclic hydrocarbon groups (hereinafter, also referred to as "acyclic hydrocarbon group containing an oxygen atom"), a heterocyclic group containing an oxygen atom, and a hydroxyl group. Polymerizable compounds having one or more selected are preferred. These are also called hydrophilic groups. Since such a polymerizable compound has a hydrophilic group having relatively high water absorption, the present invention is particularly advantageous. The acyclic hydrocarbon group containing an oxygen atom is one in which an acyclic hydrocarbon group is bonded to each of the two bonds of the oxygen atom. The two acyclic hydrocarbon groups, which may be the same or different, are monovalent or divalent or higher saturated or unsaturated acyclic hydrocarbon groups, respectively, and the number of carbon atoms per acyclic hydrocarbon group. Is preferably 1 to 8. The heterocyclic group containing an oxygen atom has an oxygen atom as an atom constituting the heterocycle. The heterocycle is preferably a 3- to 8-membered ring. The hydroxyl group is a hydroxyl group contained in the molecule of the polymerizable compound. Examples of the polymerizable compound having an acyclic hydrocarbon group containing an oxygen atom include 2- (2-vinyloxyethoxy) ethyl acrylate and dipropylene glycol diacrylate, and a heterocyclic group containing an oxygen atom may be used. Examples of the polymerizable compound having include acryloylmorpholine and tetrahydrofurfuryl acrylate, and examples of the polymerizable compound having a hydroxyl group include 4-hydroxybutyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate. .. An ether bond is mentioned as an acyclic hydrocarbon group containing an oxygen atom. The above-mentioned polymerizable compound having a hydrophilic group tends to have a moisture absorption rate of 1.5% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90%, but the moisture absorption rate is different from that of hydrophilic groups in the molecule. The moisture absorption rate may be confirmed by the method described in Examples, for example, by preparing the above-mentioned polymerizable compound having a hydrophilic group and determining the balance with the portion.

  The above-mentioned polymerizable compound preferably contains a radical polymerizable compound, more preferably a hydrophilic radical polymerizable compound. When the polymerizable compound contains a radically polymerizable compound, curability tends to be further improved.

  The HLB (Hydrophile-Lipophile Balance) value of the above-mentioned polymerizable compound is preferably 8 or more, preferably 9 or more, and preferably 10 or more. Since the polymerizable compound having an HLB value of 8 or more has a relatively high water absorption, the present invention is particularly advantageous. The upper limit of the HLB value of the polymerizable compound is not particularly limited, but it is preferably 13 or less. The HLB value in this specification is defined by the Griffin method.

  The ratio of the number of hydrophilic groups to the molecular weight (molecular weight / number of hydrophilic groups) per molecule of the above-mentioned polymerizable compound is preferably 30 or more, more preferably 50 or more, and further preferably 100 or more. When the molecular weight / hydrophilic group number of the polymerizable compound is 30 or more, the adhesion to the substrate tends to be further improved. The molecular weight / number of hydrophilic groups of the polymerizable compound is preferably 250 or less, more preferably 200 or less, and further preferably 100 or less. A polymerizable compound having a molecular weight / number of hydrophilic groups of 250 or less has relatively high water absorption, and thus the present invention is particularly advantageous. The hydrophilic group is not particularly limited, and examples thereof include an oxygen atom bonded to two acyclic hydrocarbon groups, a heterocyclic group containing an oxygen atom, and a hydroxyl group.

  The ratio of the number of carbon atoms to the number of hydrophilic groups (number of carbons / number of hydrophilic groups) per molecule of the above-mentioned polymerizable compound is preferably 3 or more, more preferably 4 or more, and further preferably 7 or more. is there. When the number of carbon atoms / hydrophilic group of the polymerizable compound is 3 or more, the adhesiveness to the substrate tends to be further improved. The number of carbon atoms / hydrophilic groups of the polymerizable compound is preferably 13 or less, more preferably 12 or less, still more preferably 10 or less, still more preferably 8 or less. The polymerizable compound having 13 or less carbon atoms / hydrophilic groups has relatively high water absorption, and thus the present invention is particularly advantageous.

  The content of the above-mentioned polymerizable compound is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 45% by mass or more, and even more preferably the total amount of the ink composition. Is 50% by mass or more, and particularly preferably 60% by mass or more. When the content of the polymerizable compound is 20% by mass or more, curability and adhesion tend to be further improved. Further, the content of the polymerizable compound is preferably 98% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and further more preferably based on the total amount of the ink composition. Is 80% by mass or less, and particularly preferably 70% by mass or less. When the content of the polymerizable compound is 98% by mass or less, foreign matter tends to be less likely to occur.

  The non-aqueous photocurable inkjet composition may include a monofunctional, difunctional, trifunctional or higher functional polymerizable compound other than the hydrophilic polymerizable compound. Other polymerizable compounds are not particularly limited, and examples thereof include monofunctional monomers such as phenoxyethyl acrylate and isobornyl acrylate; and 2 such as 1,6-hexanediol diacrylate and dimethylol-tricyclodecane diacrylate. Functional monomers: trifunctional monomers such as pentaerythritol triacrylate can be mentioned.

  The polymerizable compounds may be used alone or in combination of two or more. The content of all the polymerizable compounds contained in the ink composition is preferably 70% by mass or more based on the total amount of the ink composition.

[Photopolymerization initiator]
The ink composition may further include a photopolymerization initiator. The photopolymerization initiator is not particularly limited, but examples thereof include acylphosphine oxide compounds and thioxanthone compounds. Of these, acylphosphine oxide compounds are preferable. By containing the acylphosphine oxide compound, the curability tends to be further improved.

(Acylphosphine oxide compound)
The acylphosphine oxide-based compound is susceptible to oxygen inhibition, but on the other hand, the use of the acylphosphine oxide-based compound tends to further improve the curability when an LED is used. The combination of the acylphosphine oxide compound and the thioxanthone compound tends to be more excellent in the curing process by UV-LED, and the curability and adhesion of the ink composition tend to be further excellent.

  The acylphosphine oxide compound is not particularly limited, and examples thereof include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

  Commercially available products of the acylphosphine oxide compounds are not particularly limited, and examples thereof include IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) and DAROCUR TPO (2,4,6-trimethylbenzoyl-). Diphenyl-phosphine oxide).

  The content of the acylphosphine oxide-based compound is preferably 5.0 to 15.0% by mass, more preferably 6.0 to 14.0% by mass, and further preferably to the total mass of the ink composition. Is 7.0-10.0 mass%. When the content of the acylphosphine oxide compound is 5.0% by mass or more, the curability tends to be more excellent. Further, since the content of the acylphosphine oxide compound is 15.0% by mass or less, the undissolved residue or the precipitation of the photopolymerization initiator is less likely to occur, and the coloration of the ink or the coating film by the photopolymerization initiator itself is less likely to occur. Yellowing tends to decrease.

(Thioxanthone compound)
By including the thioxanthone compound, the surface tackiness can be reduced, and in particular, in the case of a thin film that is easily affected by oxygen inhibition, the ink surface can be cured to prevent color mixing and bleeding between dots.

  The thioxanthone compound is not particularly limited, but it is preferable to include, for example, one or more selected from the group consisting of thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. In addition, although not particularly limited, 2,4-diethylthioxanthone is preferable as diethylthioxanthone, 2-isopropylthioxanthone is preferable as isopropylthioxanthone, and 2chlorothioxanthone is preferable as chlorothioxanthone. An ink composition containing such a thioxanthone compound tends to be more excellent in curability, storage stability, and ejection stability. Among these, thioxanthone compounds including diethylthioxanthone are preferable. By including diethylthioxanthone, ultraviolet light (UV light) in a wide range tends to be more efficiently converted into active species.

  Commercially available thioxanthone compounds are not particularly limited, but include, for example, Speedcure DETX (2,4-diethylthioxanthone), Speedcure ITX (2-isopropylthioxanthone) (above, manufactured by Lambson), KAYACURE DETX-S (2. 4-diethyl thioxanthone) (manufactured by Nippon Kayaku Co., Ltd. (Nippon Kayaku Co., Ltd.)).

  The total content of the photopolymerization initiator is preferably 5.0 to 20% by mass, more preferably 5.0 to 15% by mass, and further preferably 7 to 13% based on the total mass of the ink composition. It is% by mass. When the total content of the polymerization initiators is 5.0% by mass or more, the surface tackiness can be further reduced, and the ink surface is hardened to prevent color mixing and bleeding between dots when the thin film is susceptible to oxygen inhibition. Tend to be able to. Further, when the total content of the polymerization initiator is 20% by mass or less, the coloring of the ink by the initiator itself is small, the yellowing of the hue is small, and the undissolved or precipitated initiator tends to be small.

[Pigment and pigment dispersant]
The ink composition may include a pigment, and may further include a pigment dispersant together with the pigment. Since the pigment and the pigment dispersant are likely to cause the generation of foreign matter due to moisture absorption, the present invention is particularly advantageous when the ink composition contains them.

(Pigment)
The pigment used for the black ink is not particularly limited, but, for example, No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 52. 2200B, etc. (above, manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (above, Colombia Carbon, CarbonRabular 400R). Regal1 330R, Regal1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 1400, etc. (Cabot Co., Inc., CABOK C. APBK. , Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ac Spl, Color Black S160, Color Black U160, Color Black FW2, Color Black FW2, Color Black FW2, Color Black FW200, Color Black S160, Color Black S160, Color Black S160, Color Black S60, Color Black Black 4A and Special Black 4 (these are manufactured by Degussa).

  The pigment used in the white ink is not particularly limited, but examples thereof include C.I. I. Pigment White 6, 18, 21, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, white hollow resin particles and polymer particles.

  The pigment used in the yellow ink is not particularly limited, but examples thereof include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180.

  The pigment used in the magenta ink is not particularly limited, and examples thereof include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168. , 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment Violet 19, 23, 32, 33, 36, 38, 43, 50.

  The pigment used in the cyan ink is not particularly limited, but examples thereof include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Butt Blue 4, 60 may be mentioned.

  The pigments other than the above are not particularly limited, and examples thereof include C.I. I. Pigment Green 7, 10, C.I. I. Pigment Brown 3, 5, 25, 26, C.I. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63.

(Pigment dispersant)
The above pigment may be a dispersible pigment. Examples of the method of dispersing the pigment include a method of dispersing using a pigment dispersant.

  The pigment dispersant is not particularly limited, and examples thereof include polyvinyl alcohols; polyvinylpyrrolidones; polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic acid ester. Acrylic resins such as copolymers, acrylic acid-acrylic acid alkyl ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid alkyl ester copolymers, styrene Styrene-acrylic resins such as -α-methylstyrene-acrylic acid copolymer and styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer; styrene-maleic acid copolymer; styrene-maleic anhydride copolymer Polymers; vinyl naphthalene-acrylic acid copolymers; vinyl naphthalene-maleic acid copolymers; vinyl acetate-ethylene copolymers, vinyl acetate-fatty acid vinyl ethylene copolymers, vinyl acetate-maleic acid ester copolymers, acetic acid Vinyl acetate-based copolymers such as vinyl-crotonic acid copolymer and vinyl acetate-acrylic acid copolymer, or salts thereof; proteins such as glue, gelatin, casein, albumin; natural gums such as gum arabic and tragacanth Rubbers; glucosides such as sabonine; alginic acid and alginic acid derivatives such as propylene glycol alginate, triethanolamine alginate, ammonium alginate; and cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose and the like. The pigment dispersants may be used alone or in combination of two or more.

[Polymerization inhibitor]
The ink composition of this embodiment may include a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, hydroquinone monomethyl ether (MEHQ), 1-o-2,3,5-trimethylhydroquinone, and hydroquinones represented by 2-tert-butylhydroquinone; catechol, Catechols represented by 4-methylcatechol and 4-tert-butylcatechol; phenol, butylhydroxytoluene, butylhydroxyanisole, p-methoxyphenol, cresol, pyrogallol, 3,5-di-t-butyl-4-hydroxy Toluene, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-butylphenol), and 4,4'-thiobis (3-methyl-6-). phenols typified by t-butylphenol); 2,2,6,6-tetramethylpiperidine-N-typified by 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl Compounds having oxyl skeleton, compounds having 2,2,6,6-tetramethylpiperidine skeleton, compounds having 2,2,6,6-tetramethylpiperidine-N-alkyl skeleton, and 2,2,6,6 -Hindered amines represented by compounds having a tetramethylpiperidine-N-acyl skeleton are included. The polymerization inhibitors may be used alone or in combination of two or more.

  The content of the polymerization inhibitor is preferably 0.05 to 1.0% by mass, more preferably 0.10 to 0.50% by mass, further preferably 0, based on the total mass of the ink composition. 10 to 0.30% by mass. When the content of the polymerization inhibitor is 0.05% by mass or more, storage stability tends to be further improved. Further, when the content of the polymerization inhibitor is 1.0% by mass or less, the curability tends to be further improved.

[Non-aqueous]
The ink composition of this embodiment is non-aqueous. Specifically, the content of water is preferably 0 to 1.0% by mass, more preferably 0 to 0.50% by mass, and further preferably 0 to 0.30% by mass. Alternatively, the ink composition contains substantially no water.

〔Recording method〕
The recording method of the present embodiment uses a non-aqueous photocurable inkjet composition containing a polymerizable compound having a moisture absorption rate of 1.5% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90%, the above-mentioned non-aqueous photocurable composition. A liquid feeding step of feeding a curable inkjet composition container to an ejection nozzle through an ink flow path, and ejecting the non-aqueous photocurable inkjet composition from the ejection nozzle to a recording medium. And a discharge step of performing.

[Liquid transfer process]
The liquid feeding step is a step of feeding the non-aqueous photo-curable inkjet composition from the non-aqueous photo-curable inkjet composition container to the ejection nozzle via the ink flow path. Here, the “ink flow path” refers to a flow path for flowing ink in the inkjet recording device. As the ink flow path, for example, an ink supply path for supplying the ink from the ink container that stores the ink to the inkjet recording head, or a flow path for circulating the ink to the nozzle opening in the inkjet recording head Is mentioned. Further, as a liquid feeding method, a conventionally known method can be used.

[Discharging process]
The discharging step is a step of discharging the non-aqueous photocurable inkjet composition from the discharging nozzle onto the recording medium.

[Curing process]
The recording method of the present embodiment may further include a curing step. In the curing step, the non-water-based photocurable inkjet composition attached to the recording medium is irradiated with ultraviolet light having an emission peak wavelength of 350 to 420 nm using a light emitting diode (LED), It is a step of curing the water-based photocurable inkjet composition. By using the LED, it is possible to reduce the size and the life of the inkjet recording apparatus and to increase the efficiency and cost of the inkjet recording method, as compared with the case of using a metal halide light source or a mercury lamp.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

[Material for Ink Composition]
The main materials for the ink compositions used in the following examples and comparative examples are as follows.
[Polymerizable compound]
(Trifunctional monomer)
SR444 (pentaerythritol triacrylate, manufactured by Sartomer)
(Bifunctional monomer)
VEEA (2- (2-vinyloxyethoxy) ethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.)
SR508 (dipropylene glycol diacrylate, manufactured by Sartomer)
V # 230 (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
KAYARAD R-684 (dimethylol-tricyclodecane diacrylate, manufactured by Nippon Kayaku Co., Ltd.)
(Monofunctional monomer)
ACMO (Acryloylmorpholine, manufactured by Kojin Film & Chemicals)
4HBA (4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
V # 150 (Tetrahydrofurfuryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
DA141 (2-hydroxy-3-phenoxypropyl acrylate, manufactured by Nagase Chemtex)
V # 192 (phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
IBXA (isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
[Surfactant]
BYK3500 (Silicone type surfactant, manufactured by BASF)
[Polymerization inhibitor]
MEHQ (p-methoxyphenol, manufactured by Kanto Chemical Co., Inc.)
LA7RD (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl, manufactured by ADEKA)
[Polymerization initiator]
Hostalux KCB (Clariant)
Irgacure 819 (manufactured by BASF)
Speedcure TPO (LAMBSON)
Speedcure DETX (LAMBSON)
[Pigment]
PR122 (C.I. Pigment Red 122)
Titanium oxide [pigment dispersant]
BYK180 (manufactured by BYK) for white pigments Solsperse 36000 (manufactured by Lubrizol) for magenta pigments

[Preparation of ink composition]
Each material was mixed with the composition shown in Table 1 below, and sufficiently stirred to obtain each ink composition 1-9. In Table 1 below, the unit of numerical values is mass%, and the total is 100.0 mass%.

[Method of measuring moisture absorption rate of polymerizable compound]
A sample bottle (13.5 mL) containing 7 mL of a polymerizable compound was left undisclosed in a disposable cup (200 mL) containing 50 cc of water, and the upper portion of the disposable cup was covered with Saran wrap (registered trademark). Sealed. This disposable cup was allowed to stand in a constant temperature bath at 60 ° C. for 24 hours to prepare a moisture absorption sample. After absorbing moisture, the sample bottle was closed and the amount of water contained in the polymerizable compound was measured using a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd., trace moisture analyzer, AQ-2200). The amount of increase in water content before and after the moisture absorption test was calculated by the following formula to obtain the moisture absorption rate.
Moisture absorption rate = (water content after moisture absorption−water content before moisture absorption) / mass of polymerizable compound before moisture absorption × 100

[Production of container]
As the base material, a low-density polyethylene film having a thickness of 80 μm was used. One side of this PET film was pretreated by reactive ion etching using a plasma treatment device. At this time, a high-frequency power source was used for the electrodes and the atmosphere was a mixed gas of argon / oxygen. Then, a film in which silica having a thickness of 50 nm was vapor-deposited in-line on a pretreatment surface by reactive ion etching was obtained by a vacuum vapor deposition apparatus by an electron beam heating system. Then, using the obtained film, a container 1 for containing the ink composition was prepared.

  A container 2 for containing the ink composition was prepared in the same manner as the container 1 except that aluminum oxide having a thickness of 50 nm was deposited. Further, a container 3 for containing the ink composition is prepared in the same manner as the preparation of the container 1 described above except that a 12 μm-thick biaxially stretched polyethylene terephthalate (PET) film having no metal oxide layer is used as a substrate. Was produced. Further, a container 4 for containing the ink composition was prepared in the same manner as the preparation of the container 1 except that aluminum having a thickness of 50 nm was vapor-deposited.

(Water permeability)
The water vapor transmission rates of the containers 1 to 4 were measured by JIS K 7129 plastic-film and sheet method of determining water vapor transmission rate (gas chromatography method). First, the low humidity chamber and the high humidity chamber were separated by a test piece. In the gas chromatograph method, the low humidity chamber is evacuated by a vacuum pump, a gas controlled to a constant relative humidity is flowed through the high humidity chamber, the water vapor that has permeated the test piece is collected in a measuring tube for a certain time, and the collected water vapor amount is collected by a gas chromatograph. The water vapor permeability was calculated by measuring with a graph.

(Oxygen permeability)
The oxygen transmission rates of the containers 1 to 4 were measured by JIS K 7126 plastic-film and sheet gas permeability test method (gas chromatograph method). One side (low pressure side) separated by the test piece is kept in vacuum, the test gas is introduced to the other side (high pressure side), and the amount of gas passing through the test piece and permeating to the low pressure side is measured by gas chromatography to measure the gas permeation. The degree was calculated.

[Foreign material evaluation]
Each of the ink compositions was sealed in a container prepared as described above, and the container was stored at a temperature of 60 ° C. and a relative humidity of 90% for 7 days. The container after storage was housed in an ink cartridge as a package, and the cartridge was mounted on a printer (PX-G5000, manufactured by Seiko Epson Corporation). Then, the ink composition in the container was continuously ejected for 10 minutes from a head having 360 nozzles. At this time, the ink temperature was adjusted in the head so that the viscosity of the ink composition was 10 mPa · s. After ejection, the nozzles were inspected and the number of non-ejection nozzles was counted. Based on the number of non-ejection nozzles, the generation of foreign matter due to storage was evaluated according to the following evaluation criteria. In the case of evaluation B, when the ink composition in the container was filtered with a filter paper, a residue that was seen as a foreign substance was found.
A: The number of non-ejection nozzles was 1 or less.
B: Two or more non-ejection nozzles.

[Curability]
Each of the ink compositions was sealed in a container prepared as described above, and the container was stored at a temperature of 60 ° C. and a relative humidity of 90% for 7 days. The container after storage was housed in an ink cartridge as a package, and the cartridge was mounted on a printer (PX-G5000, manufactured by Seiko Epson Corporation). Then, the ink composition in the container was ejected from a head having 360 nozzles and attached to the recording medium. Then, the ink composition on the recording medium was irradiated with ultraviolet light at an integrated energy of 200 mJ / cm ² to obtain a coating film having a film thickness of 10 μm.

The coating film of the ink composition after the ultraviolet light irradiation was rubbed with a cotton swab to confirm the presence or absence of scratches or the presence of stains on the cotton swab. The curability was evaluated according to the following evaluation criteria based on the presence or absence of scratches or the presence or absence of stains on the swab.
AA: No scratches or stains on the swab were observed at an integrated energy of 150 mJ / cm ² .
A: Presence or absence of scratches or stains on the cotton swab was not observed by irradiation with an accumulated energy of 200 mJ / cm ² , but presence or absence of scratches or stains on the cotton swab was recognized at an accumulated energy of 150 mJ / cm ² .
B: Presence or absence of scratches or stains on the cotton swabs were observed even after irradiation with integrated energy of 200 mJ / cm ² .

[Adhesion]
Each of the ink compositions was sealed in a container prepared as described above, and the container was stored at a temperature of 60 ° C. and a relative humidity of 90% for 7 days. The container after storage was housed in an ink cartridge as a package, and the cartridge was mounted on a printer (PX-G5000, manufactured by Seiko Epson Corporation). Then, the ink composition in the container was ejected from a head having 360 nozzles and attached to the recording medium. Then, the ink composition on the recording medium was irradiated with ultraviolet light at an integrated energy of 200 mJ / cm ² to obtain a coating film having a film thickness of 10 μm.

As a cutting tool, a single-blade cutting tool (a generally commercially available cutter) and a guide for cutting at equal intervals using the single-blading cutting tool were prepared. First, the blade of a cutting tool was applied so as to be perpendicular to the coating film, and six parallel cuts were made in the recorded material. After making these 6 cuts, the direction was changed by 90 °, and 6 more cuts were made so as to be orthogonal to the cuts already made. In this way, a coating film having cuts in a grid pattern was obtained. Next, take out the transparent adhesive tape (width: 25 ± 1 mm) so that the length is about 75 mm, attach the tape to the grid-shaped notches in the coating film, and use your fingers enough to see through the coating film. I rubbed the tape. Next, within 5 minutes after the tape was attached, the tape was reliably peeled off from the coating film at an angle close to 60 ° in 0.5 to 1.0 seconds. Based on the presence or absence of peeling of the coating film from the recording medium at this time, the adhesion was evaluated according to the following evaluation criteria.
A: No peeling was observed.
B: Peeling was observed.

〔Visibility〕
The average transmittance in the visible light region of 400 to 800 nm of the container manufactured as described above was measured with a spectrophotometer (manufactured by Hitachi, Ltd., product name U-3300 spectrophotometer). The visibility was evaluated based on the obtained transmittance.
A: The transmittance was 40% or more.
B: The transmittance was less than 40%.

〔viscosity〕
The viscosity of each ink composition after preparation at 20 ° C. was measured with a viscometer (product name MCR-300 manufactured by Physica), and the viscosity was evaluated according to the following criteria. A cone (diameter 75 mm, angle 1 °) was used and the shear rate was 200 s ⁻¹ .
AA: The viscosity was 15 mPa · s or less.
A: The viscosity was higher than 15 mPa · s and lower than 20 mPa · s.
B: The viscosity was 20 mPa · s or more.

(Examples 1-9, Comparative Examples 1-6)
By accommodating any of the ink compositions 1 to 9 in any of the containers (packs) 1 to 4 and sealing the container, a container having the ink composition enclosed therein was obtained. The combinations of the ink composition and the container are as shown in Table 2.

  In Comparative Examples 1 to 3 and 6, since the container does not have a metal oxide layer, the curability deteriorates due to moisture absorption, and in Comparative Example 1, generation of foreign matter was further confirmed. Further, Comparative Example 2 was an ink composition having relatively low hygroscopicity, but the curability was deteriorated because the container did not have a metal oxide layer. Comparative Example 4 was inferior in visibility because the container had a metal layer instead of the metal oxide layer. Furthermore, in Comparative Example 5, the container had the metal oxide layer, but the curability was lowered because it was a relatively hydrophobic ink composition. In Comparative Example 6, the content of the acylphosphine oxide compound in the ink composition was larger than that of Comparative Example 1 and the curability was improved, but the residue was derived from the acylphosphine oxide compound. Foreign matter was also observed. From this, it was found that the present invention is also useful in that it is possible to reduce the generation of foreign substances derived from the acylphosphine oxide compound, while using the acylphosphine oxide compound to obtain a composition having more excellent curability.

  40 ... Ink cartridge, 70 ... Ink pack, 72 ... Cartridge case, 74 ... Ink supply port, 76 ... Main body case, 78 ... Lid part.

Claims (20)

A non-aqueous photocurable inkjet composition containing a polymerizable compound having a moisture absorption rate of 10.71% by mass / 24 hours or more at a temperature of 60 ° C. and a relative humidity of 90%;
Housing the nonaqueous light curable ink jet composition, Ri Do a member having a metal oxide layer, a cartridge case for accommodating the container and container that have a visible light-transmissive, or at least the non-aqueous photocurable accommodating the container having a visible light-transmissive housing the ink jet composition, Ri Do a member having a metal oxide layer, and a cartridge case for accommodating the package and the package that have a visible light transmission properties, the Prepare,
As the polymerizable compound, one or more of acryloylmorpholine and 4-hydroxybutyl acrylate are included,
The content of the polymerizable compound is 2 to 30 mass% with respect to the total amount of the non-aqueous photocurable inkjet composition,
A non-aqueous photocurable inkjet composition container.   The non-aqueous photocurable inkjet composition container according to claim 1, wherein a moisture absorption rate of the polymerizable compound at a temperature of 60 ° C. and a relative humidity of 90% is 10.71 to 11% by mass / 24 hours.   The non-aqueous photo-curable inkjet composition container according to claim 1, wherein the content of the polymerizable compound is 20 to 30 mass% with respect to the total amount of the non-aqueous photo-curable inkjet composition.   The non-aqueous photocurable type according to claim 1, wherein the metal oxide layer contains one or more oxides selected from the group consisting of silica, alumina, titania, zirconia, and ceria. Inkjet composition container.   The non-aqueous photo-curable inkjet composition container according to any one of claims 1 to 4, wherein the non-aqueous photo-curable inkjet composition further contains an acylphosphine oxide compound.   The non-aqueous photocurable inkjet composition container according to claim 1, wherein the polymerizable compound comprises a radically polymerizable compound.   The non-aqueous photo-curable inkjet composition container according to any one of claims 1 to 6, wherein the non-aqueous photo-curable inkjet composition further contains a pigment and a pigment dispersant. The accommodating the non-aqueous light-curable ink jet composition, Ri Do from the member having the metal oxide layer comprises a cartridge case for accommodating the container and the container that have a visible light transmission, according to claim 1 The non-aqueous photocurable inkjet composition container according to any one of items 1 to 7. The non-aqueous photocurable inkjet composition container according to any one of claims 1 to 8, wherein the container or the package has a water permeability of 20 g / m ² · 24 hours or less.   The non-aqueous photocurable inkjet composition container according to any one of claims 1 to 9, wherein the ratio of the number of hydrophilic groups to the molecular weight of the polymerizable compound (molecular weight / number of hydrophilic groups) is 222 or less.   The non-aqueous photocurable inkjet composition container according to claim 10, wherein the ratio of the number of hydrophilic groups to the molecular weight (molecular weight / number of hydrophilic groups) is 156 or less.   The non-aqueous photocurable inkjet composition according to any one of claims 1 to 11, wherein the ratio of the number of carbon atoms to the number of hydrophilic groups of the polymerizable compound (carbon number / hydrophilic group number) is 10 or less. body.   The non-aqueous photocurable inkjet composition container according to claim 12, wherein the ratio of the number of carbon atoms to the number of hydrophilic groups (number of carbons / number of hydrophilic groups) is 8 or less.   The nonaqueous photocurable inkjet composition container according to any one of claims 1 to 13, wherein the metal oxide layer has a thickness of 20 to 500 nm.   The non-aqueous photocurable inkjet composition container according to claim 1, wherein the polymerizable compound includes one having an HLB of 10 or more.   The non-aqueous photocurable inkjet composition container according to any one of claims 1 to 15, comprising acryloylmorpholine as the polymerizable compound.   The non-aqueous photocurable inkjet composition container according to any one of claims 1 to 16, comprising 4-hydroxybutyl acrylate as the polymerizable compound.   The non-aqueous photo-curable inkjet composition according to any one of claims 1 to 17, wherein the non-aqueous photo-curable inkjet composition further contains, as a photopolymerization initiator, an acylphosphine oxide-based compound and a thioxanthone-based compound. A container for things. A delivery for delivering the non-aqueous photo-curable inkjet composition from the non-aqueous photo-curable inkjet composition container according to any one of claims 1 to 18 to an ejection nozzle through an ink flow path. Liquid process,
A discharging step of discharging the non-aqueous photocurable inkjet composition from the discharging nozzle onto the recording medium.   The non-water-based photo-curable inkjet composition having a peak emission wavelength of 350 to 420 nm is irradiated to the non-aqueous photo-curable inkjet composition adhered to the recording medium by using a light emitting diode. The recording method according to claim 19, further comprising a curing step of curing the object.

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