Ink composition, ink set, ink pack, and inkjet recording method

Abstract

To provide an ink pack excellent in storage stability of a filled ink composition.SOLUTION: In the ink pack, the liquid contact portion which comes into contact with the ink composition contains polyolefin, the ink composition contains a polymerizable compound, polyolefin derived from the liquid contact portion of the ink pack, and an anti-blocking agent of polyolefin, and in a case where the ink composition further contains a colorant, the anti-blocking agent of polyolefin contains 0.1% to 10% by mass of nanoparticles which are inorganic particles having a mean particle size of 5 to 1 000nm and a specific surface area of 10 600m2 / g based on the mass of the ink composition, and at least a part of the polyolefin derived from the liquid contact portion of the ink pack is adsorbed to the nanoparticles, when the ink composition does not contain a colorant, the aggregation inhibitor of polyolefin contains 0.1 to 10 mass% of a polymer dispersant having a weight average molecular weight of 1,000 or more and 70,000 or less based on the mass of the ink composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This patent application claims priority under the Paris Convention to Japanese Patent Application No. 2023-058772 (filing date: March 31, 2023), the entire contents of which are incorporated herein by reference. The present invention relates to an ink composition, an ink set, an ink pack, and an inkjet recording method. [Background technology]

[0002] Inkjet printers, which eject ink droplets from an ink nozzle head, are used in many printers because they are small and inexpensive, and can form images without contacting the surface of a recording medium. In recent years, from the perspective of environmental issues and to reduce the risk of coming into contact with ink when replacing the ink, ink has increasingly been provided in pouches rather than bottles, and pouches equipped with a plastic film are being used (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-214868 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when an ink composition is filled into a pouch with a plastic film as described in Patent Document 1, the storage stability of the ink is not necessarily sufficient, and there is a possibility that clogging of the ink head may occur, particularly when used under high-speed, high-resolution printing conditions.

[0005] Therefore, an object of the present invention is to provide an ink composition having excellent storage stability. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention. That is, the present invention includes the following preferred embodiments.

[0007] [1] An ink composition comprising a polymerizable compound, a polyolefin, and an agent for inhibiting aggregation of the polyolefin. [2] The composition according to [1], wherein the aggregation inhibitor comprises nanoparticles and / or a polymeric dispersant. [3] The composition according to [2], wherein at least a portion of the polyolefin is adsorbed onto nanoparticles. [4] The composition according to [2], wherein at least a portion of the polyolefin is dispersed in the composition. [5] The composition according to any one of [1] to [4], wherein the polyolefin is at least partially dissolved in the composition. [6] The polymerizable compound has an SP value of 7.8 (cal / cm 3 ) 1 / 2 More than 9.6(cal / cm 3 ) 1 / 2 The composition according to any one of [1] to [5], which contains the following monofunctional monomer (A): [7] The polymerizable compound has an SP value of 7.8 (cal / cm 3 ) 1 / 2 Less than or equal to 9.6 (cal / cm 3 ) 1 / 2 The composition according to [6], further comprising more than one monofunctional monomer (B). [8] The composition according to [7], wherein the mass ratio of the monofunctional monomers (A) and (B) is 1:1 to 10:1. [9] The composition according to any one of [1] to [8], wherein the mass ratio of the polymerizable compound to the aggregation inhibitor is 10:1 to 200:1.

[10] The composition according to any one of [1] to [9], wherein the polyolefin comprises polyethylene.

[11] The composition according to any one of [2] to

[10] , wherein the nanoparticles comprise at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, strontium titanate, lithopone, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silicon dioxide, tin oxide, phosphorus-containing tin oxide (PTO), antimony oxide, antimony-containing tin oxide (ATO), aluminum-containing zinc oxide (AZO), gallium-containing zinc oxide (GZO), indium oxide, and tin-containing indium oxide (ITO).

[12] The composition according to any one of [2] to

[11] , wherein the polymer dispersant contains a polyester polyamide having a weight-average molecular weight of 1,000 or more and 70,000 or less.

[13] The composition according to any one of [1] to

[12] , which does not contain a colorant.

[14] The composition according to any one of [1] to

[12] , further comprising a colorant.

[15] The composition according to

[14] , wherein the colorant comprises a white pigment.

[16] The composition according to any one of [1] to

[15] , which is filled in a container.

[17] The composition according to

[16] , wherein a liquid-contacting part in the container that comes into contact with the ink composition contains polyolefin.

[18] The composition according to

[17] , wherein the polyolefin comprises polyethylene having a crystallinity of 35% or more and 55% or less.

[19] The composition according to any one of [1] to

[18] , which is an inkjet ink composition.

[20] An ink set comprising the composition according to

[13] and / or the composition according to

[14] .

[21] An ink pack filled with an ink composition, In the ink pack, a liquid-contacting portion that comes into contact with the ink composition contains polyolefin, The ink composition includes a polymerizable compound, a polyolefin derived from a liquid-contacting portion of the ink pack, and an aggregation inhibitor for the polyolefin.

[22] The ink pack according to

[21] , wherein the polyolefin includes polyethylene having a crystallinity of 35% or more and 55% or less.

[23] The ink pack according to

[21] or

[22] , wherein the ink pack is a laminate including at least one layer selected from the group consisting of a gas barrier layer, an adhesive layer, and a heat seal layer.

[24] The ink pack according to

[23] , wherein the heat seal layer contains the polyolefin according to

[22] .

[25] An inkjet recording method comprising the steps of: discharging the composition according to any one of [1] to

[19] from an inkjet head onto a substrate; and photocuring the composition discharged onto the substrate. [Effects of the Invention]

[0008] According to the present invention, an ink composition having excellent storage stability can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention. Furthermore, even if the estimated mechanism of action differs from the actual mode, it is still included within the scope of the present invention.

[0010] <Ink composition> The ink composition of the present invention comprises a polymerizable compound, a polyolefin, and an aggregation inhibitor for the polyolefin.

[0011] The present inventors have discovered that when an ink composition is filled into a container with a plastic film and stored for a long period of time, there is a problem in that foreign matter is generated in the ink composition, which can cause clogging of the ink head. Further investigation into the foreign matter revealed that when the material of the innermost layer of the container is plastic, particularly polyolefin, the polyolefin dissolves and aggregates in the ink composition, resulting in the composition being present as foreign matter. Based on this, the present inventors have further investigated the matter and concluded that the dissolution of polyolefin into the ink composition itself is rarely a problem, but that it is important to prevent the aggregation of the dissolved polyolefin. Based on this, they have discovered a polyolefin aggregation inhibitor and have completed the present invention, which incorporates this into an ink composition.

[0012] <Polyolefin agglomeration inhibitor> The ink composition of the present invention contains an aggregation inhibitor for polyolefins (hereinafter, sometimes simply referred to as "aggregation inhibitor"). The aggregation inhibitor is not particularly limited as long as it is a compound that can inhibit aggregation of polyolefins dissolved in the ink composition as described above, but specifically, the aggregation inhibitor preferably contains nanoparticles and / or a polymer dispersant. When the aggregation inhibitor contains nanoparticles and / or a polymer dispersant, aggregation of polyolefins dissolved in the ink composition can be further inhibited.

[0013] In the present invention, the nanoparticles are preferably particles having an average particle diameter of 1 μm or less (1000 nm or less), and more preferably inorganic particles having an average particle diameter of 1 μm (1000 nm) or less. Furthermore, the nanoparticles are preferably white or highly transparent nanoparticles having hiding power so as not to affect the hue and transparency of the color ink composition, clear ink composition, or primer ink composition. Specifically, the nanoparticles preferably contain at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, strontium titanate, lithopone, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silicon dioxide, tin oxide, phosphorus-containing tin oxide (PTO), antimony oxide, antimony-containing tin oxide (ATO), aluminum-containing zinc oxide (AZO), gallium-containing zinc oxide (GZO), indium oxide, and tin-containing indium oxide (ITO), more preferably contain at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, silicon dioxide, tin oxide, and zinc oxide, and even more preferably contain at least one of titanium oxide, silicon dioxide, and aluminum oxide. In the present invention, the average particle size may refer to a particle size obtained by observing and measuring the particle sizes of individual primary particles separated by grain boundaries using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) or the like, determining the average major axis diameter and the average minor axis diameter of at least 100 particles, and then averaging the average major axis diameter and the average minor axis diameter.

[0014] The average particle size of the nanoparticles is preferably 800 nm or less, more preferably 500 nm or less, and even more preferably 100 nm or less. When the average particle size of the nanoparticles is below the upper limit, the specific surface area is sufficiently large, and as described below, the eluted polyolefin can be sufficiently adsorbed, thereby suppressing polyolefin aggregation. Furthermore, the smaller the average particle size, the larger the specific surface area, and accordingly the number of polyolefin adsorption sites described below also increases. Therefore, the lower limit of the average particle size is not particularly limited, but if the particle size is too small, particles may aggregate together. Therefore, the average particle size of the nanoparticles is usually 5 nm or more, preferably 10 nm or more. That is, the average particle size of the nanoparticles is usually 5 to 1,000 nm, preferably 5 to 800 nm, more preferably 10 to 500 nm, and even more preferably 10 to 100 nm. Furthermore, the specific surface area of ​​the nanoparticles is preferably 10 to 600 m 2 / g, more preferably 20 to 400m 2 The specific surface area of ​​the nanoparticles can be determined, for example, by the multipoint nitrogen adsorption method (BET method).

[0015] In the ink composition of the present invention, it is preferable that at least a portion of the eluted polyolefin is adsorbed to the nanoparticles. Without being limited by theory, it is believed that the nanoparticles described above have adsorption sites on their surfaces, which can adsorb the eluted polyolefin and thereby inhibit polyolefin aggregation. In other words, the nanoparticles that can have adsorption sites on their surfaces can be suitably used as the aggregation inhibitor of the present invention. The adsorption of polyolefin to nanoparticles in the ink composition can be confirmed, for example, by centrifuging the ink composition and analyzing the fraction corresponding to the pigment and nanoparticles separated from the settled solid component using IR (infrared absorption spectroscopy) or NMR (nuclear magnetic resonance spectroscopy), for example, by the method described in the Examples below.

[0016] When the ink composition of the present invention contains nanoparticles as an aggregation inhibitor, the content of the nanoparticles is preferably 0.1 to 10 mass %, more preferably 0.2 to 7 mass %, and even more preferably 0.3 to 4 mass %, based on the mass of the ink composition. When the content of the nanoparticles is within this range, the storage stability of the ink composition can be improved.

[0017] In the present invention, the polymer dispersant has a weight average molecular weight (M w) is preferably 1,000 or more. Specifically, for example, DisperBYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-164, DisperBYK-166, DisperBYK-167, DisperBYK-168, DisperBYK-169, DisperBYK-200, DisperBYK-201, DisperBYK-202, DisperBYK-203, DisperBYK-204, DisperBYK-205, DisperBYK-206, DisperBYK-207, DisperBYK-208, DisperBYK-209, DisperBYK-210, DisperBYK-211, DisperBYK-212, DisperBYK-213, DisperBYK-214, DisperBYK-215, DisperBYK-216, DisperBYK-217, DisperBYK-218, DisperBYK-219, DisperBYK-220, DisperBYK-221, DisperBYK-222, DisperBYK-223, DisperBYK-224, DisperBYK-225, DisperBYK-226, DisperBYK-227, DisperBYK-228, DisperBYK-229, DisperBYK-230, DisperBYK-231, DisperBYK-232, DisperBYK-233, DisperBYK-234, DisperBYK-235, DisperBYK-236, DisperBYK-237, DisperBYK-238, DisperBYK-239, DisperBYK-240, DisperBYK-24 BYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (all manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA4080, EFKA5010, EFKA5207, EFKA5244, EFKA6745, EFKA6750, EFKA7414, EFKA7462, EFKA7500, EFKA7570, EFKA7575, EFKA7 580 (all manufactured by Efka Additives), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco), Solsperse 3000, 9000, 13240, 13940, 17000, 24000, 26000, 28000, 32000, 32500, 32600, 33000, 33500, 34750, 35100, 3 Examples of suitable dispersants include various Solsperse dispersants such as 6000, 37500, 39000, 41000, and 71000 (all manufactured by Lubrizol Japan Corporation), Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, and P-123 (all manufactured by ADEKA Corporation), Isonet S-20 (manufactured by Sanyo Chemical Industry Co., Ltd.), Disparlon KS-860, 873SN, and 874 (polymer dispersants), #2150 (aliphatic polycarboxylic acid), and #7004 (polyether ester type) (all manufactured by Kusumoto Chemical Industry Co., Ltd.), and Uniqjet 9520 (manufactured by UNIQCHEM). The polymer dispersant may be used alone or in combination of two or more. w ) may refer to the weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

[0018] Among the polymer dispersants mentioned above, the weight average molecular weight (M w The polymer dispersant preferably contains a polyester polyamide having a molecular weight (Mw) of 1,000 or more and 70,000 or less, more preferably 1,500 or more and 60,000 or less. When the polymer dispersant contains such a polyester polyamide, aggregation of polyolefins dissolved in the ink composition can be further suppressed. Polyester polyamides can be produced by reacting acid-terminated polyesters such as polycaprolactone, poly(12-hydroxystearic acid), and polyricinoleic acid with polyamines such as polyethyleneimine and polyallylamine. Specific examples of such polyester polyamides include Solsperse 32000, Solsperse 32500, Solsperse 32600, Solsperse 33000, Solsperse 33500, Solsperse 34750, Solsperse 35100, Solsperse 37500, and Uniqjet 9520.

[0019] In the ink composition of the present invention, it is preferable that at least a portion of the dissolved polyolefin is dispersed in the ink composition. Without being limited by theory, it is believed that the polymer dispersant solubilizes, emulsifies, and suspends the polyolefin through hydrophobic interactions and molecular chain entanglement, thereby dispersing the polyolefin in the ink composition and suppressing its aggregation. The dispersion of the polyolefin in the ink composition can be confirmed by analyzing the supernatant after centrifuging the ink composition with a dynamic light scattering particle size distribution analyzer, IR, NMR, etc., and can be confirmed, for example, by the method described in the Examples below.

[0020] When the ink composition of the present invention contains a polymer dispersant as an aggregation inhibitor, the content of the polymer dispersant is preferably 0.1 to 10 mass %, more preferably 0.5 to 9 mass %, and even more preferably 0.7 to 8 mass %, based on the mass of the ink composition. When the content of the polymer dispersant is within this range, the storage stability of the ink composition can be improved.

[0021] In a preferred embodiment of the present invention, when the ink composition of the present invention is a clear ink composition that does not contain a colorant, which will be described later, the aggregation inhibitor preferably contains at least one of nanoparticles or a polymer dispersant, and from an economical viewpoint, it is more preferable that the aggregation inhibitor consists of a polymer dispersant. In another preferred embodiment of the present invention, the ink composition of the present invention may further contain a colorant (color ink composition). In this case, the dispersant for dispersing the colorant may constitute part of the aggregation inhibitor of the present invention. Furthermore, when the ink composition of the present invention further contains a colorant, the aggregation inhibitor preferably contains both nanoparticles and a polymer dispersant. Without being limited by theory, it is believed that when only the polymer dispersant is present in the color ink composition, the polymer dispersant can preferentially disperse the colorant and therefore does not function as an aggregation inhibitor, making it difficult to disperse the polyolefin.

[0022] In a preferred embodiment of the present invention, when the ink composition of the present invention is a color ink composition described below, the mass ratio of nanoparticles to polymeric dispersant in the composition (mass of nanoparticles:mass of polymeric dispersant) can be appropriately changed depending on the type and / or amount of other components in the composition, but is preferably 0.5:1 to 5:1, more preferably 1:1 to 4:1. When the mass ratio of nanoparticles to polymeric dispersant in the color ink composition is within this range, the storage stability of the ink composition can be improved. If the amount of polymeric dispersant is too high relative to the nanoparticles, the number of adsorption sites for the nanoparticles decreases, weakening the adsorption effect of eluted polyolefin and potentially reducing storage stability. Furthermore, the mass ratio of colorant (e.g., pigment) to nanoparticles in the color ink composition (mass of colorant:mass of nanoparticles) can be appropriately changed depending on the type and / or amount of colorant, but is preferably 1:1 to 10:1, more preferably 1.5:1 to 8:1. When the mass ratio of colorant to nanoparticles in the color ink composition is within the above range, the storage stability of the ink composition can be improved.

[0023] In a preferred embodiment of the present invention, when the ink composition is a color ink composition containing a colorant and uses only a polymeric dispersant as an aggregation inhibitor, the content of the polymeric dispersant is preferably 10 to 300 parts by mass, more preferably 20 to 250 parts by mass, and even more preferably 30 to 200 parts by mass, relative to 100 parts by mass of the colorant. Within the above upper and lower limits, the polymeric dispersant is present in the color ink composition in a state where it is not adsorbed to the colorant, and the polymeric dispersant can function as an aggregation inhibitor. Additionally, the viscosity of the ink composition is not too high, making it suitable for inkjet printing.

[0024] In the present invention, it is preferred that at least a portion of the eluted polyolefin is dissolved in the ink composition. As described above, elution of the polyolefin itself is acceptable, and therefore all of the eluted polyolefin may be dissolved in the ink composition. The dissolution of the polyolefin in the ink composition can be confirmed, for example, by centrifuging the ink composition, sedimenting the solid components, and analyzing the supernatant solution with a dynamic light scattering particle size distribution analyzer, IR, NMR, etc., or by centrifuging the ink composition and analyzing fractions corresponding to the pigment and nanoparticles separated from the sedimented solid components with IR, NMR, etc., and can be confirmed, for example, by the method described in the Examples below. In this specification, the term "dissolved" may also include a state in which the eluted polyolefin is solvated with monomers and the like without agglomerating, and is present as polyolefin aggregates of, for example, several nm in size, without being adsorbed onto the nanoparticles or dispersed in the dispersant.

[0025] <Polymerizable compound> The ink composition of the present invention contains a polymerizable compound. The polymerizable compound in the present invention is preferably a compound that undergoes a polymerization reaction upon irradiation with light and has the function of curing a composition containing the polymerizable compound. Specifically, a compound having at least one ethylenic double bond selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a vinyl ether group is preferred, and a compound having at least one ethylenic double bond selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinyl ether group is more preferred. In this specification, "(meth)acrylate" is a general term for "acrylate" and "methacrylate." Terms such as "(meth)acrylamide" and "(meth)acryloyloxy" have the same meaning. When the ink composition of the present invention contains a polymerizable compound that undergoes a polymerization reaction upon irradiation with ultraviolet light, it becomes an ultraviolet-curable ink composition. Furthermore, the polymerizable compound is preferably a radically polymerizable compound that undergoes a polymerization reaction by radical polymerization.

[0026] The ink composition of the present invention contains a polymerizable compound having an SP value of 7.8 (cal / cm 3 ) 1 / 2 More than 9.6(cal / cm 3 ) 1 / 2 It is preferable to contain the following monofunctional monomer (A) (hereinafter, sometimes simply referred to as "monomer (A)"). In the present invention, the monofunctional monomer may have one ethylenic double bond in one molecule. The SP value of the monomer (A) is preferably 8.0 (cal / cm 3 ) 1 / 2 More preferably, 8.2 (cal / cm 3 ) 1 / 2 More preferably, 8.4 (cal / cm 3 ) 1 / 2 More preferably, 8.6 (cal / cm 3 ) 1 / 2 More preferably, 8.8 (cal / cm 3 ) 1 / 2 It is preferably 9.5 (cal / cm 3 ) 1 / 2Less than or equal to 9.3 (cal / cm 3 ) 1 / 2 That is, the SP value of the monomer (A) is preferably 7.8 to 9.6 (cal / cm 3 ) 1 / 2 , more preferably 8.0 to 9.6 (cal / cm 3 ) 1 / 2 , and more preferably 8.2 to 9.6 (cal / cm 3 ) 1 / 2 , and even more preferably 8.4 to 9.5 (cal / cm 3 ) 1 / 2 , and particularly preferably 8.6 to 9.5 (cal / cm 3 ) 1 / 2 , or 8.8 to 9.3 (cal / cm 3 ) 1 / 2 When the SP value of the monomer (A) is within the above range, the storage stability of the ink composition can be improved. In addition, the affinity with plastics that can be used as substrates can be improved, and therefore the adhesion of the ink composition to substrates can be improved.

[0027] Here, it is known that the SP value of each monomer can be calculated from the molecular structure. The solubility parameter in this specification may mean the value at 25°C obtained by the Fedors method (Yuji Harasaki, "Basic Science of Coatings," Chapter 3, page 35, 1977, Maki Shoten Publishing).

[0028] Examples of such monomer (A) include (meth)acrylates such as 2-ethylhexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, isobutyl (meth)acrylate, ethyl (meth)acrylate, stearyl (meth)acrylate, and lauryl (meth)acrylate; and monomers having a vinyl ether group such as hexyl vinyl ether, phenyl vinyl ether, and cyclohexyl vinyl ether. These may be used alone or in combination of two or more. Among the monomers (A), from the viewpoint of improving adhesion to the substrate, it is preferable to include at least one selected from the group consisting of 2-ethylhexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0029] The content of monomer (A), based on the mass of the entire ink composition, is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less. That is, the content of monomer (A), based on the mass of the entire ink composition, is preferably 20 to 80% by mass, more preferably 30 to 80% by mass, even more preferably 40 to 80% by mass, still more preferably 50 to 75% by mass, and particularly preferably 55 to 75% by mass. When the content of monomer (A) is within the above range, the storage stability of the ink composition can be further improved, and adhesion to substrates can also be further improved.

[0030] The ink composition of the present invention contains a polymerizable compound having an SP value of 7.8 (cal / cm 3 ) 1 / 2Less than or equal to 9.6 (cal / cm 3 ) 1 / 2 It is preferable that the copolymer further contains a monofunctional monomer (B) (hereinafter, sometimes simply referred to as "monomer (B)"). The SP value of the monomer (B) is preferably 7.6 (cal / cm 3 ) 1 / 2 Less than or equal to 7.5 (cal / cm 3 ) 1 / 2 or less, more preferably 7.4 (cal / cm 3 ) 1 / 2 More preferably, 7.3 (cal / cm 3 ) 1 / 2 or less, or preferably 9.8 (cal / cm 3 ) 1 / 2 More preferably, 10.0 (cal / cm 3 ) 1 / 2 More preferably, 10.2 (cal / cm 3 ) 1 / 2 More preferably, 10.5 (cal / cm 3 ) 1 / 2 More preferably, 11.0 (cal / cm 3 ) 1 / 2 When the SP value of the monomer (B) is within the above range, the affinity with plastics that may be contained in the innermost layer of the container can be reduced, and therefore the storage stability of the ink composition can be improved.

[0031] SP value is 7.8 (cal / cm 3 ) 1 / 2 Examples of monomers with an SP value of less than 9.6 (cal / cm) include isobutyl vinyl ether and n-butyl vinyl ether. 3 ) 1 / 2Examples of monomers with a viscosity of more than 1000 MPa include dicyclopentanyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, N-vinyl-2-caprolactam, acryloylmorpholine, ω-carboxy-polycaprolactone mono(meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. These may be used alone or in combination of two or more. When two or more types are combined, the SP value of the two or more types must be 7.8 (cal / cm 3 ) 1 / 2 Monomers having an SP value of less than 9.6 (cal / cm 3 ) 1 / 2 Monomers having an SP value of 7.8 (cal / cm 3 ) 1 / 2 Monomers with an SP value of less than 9.6 (cal / cm 3 ) 1 / 2 More than one monomer may be combined.

[0032] Among the monomers (B), from the viewpoint of improving the storage stability of the ink composition, it is preferable to include at least one selected from the group consisting of 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and benzyl (meth)acrylate.

[0033] The content of monomer (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, based on the mass of the entire ink composition. That is, the content of monomer (B) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the mass of the entire ink composition. When the content of monomer (B) is within this range, the storage stability of the ink composition can be further improved.

[0034] In the ink composition of the present invention, the ratio of the mass of monomer (A) to the mass of monomer (B) (mass of monomer (A) : mass of monomer (B)) is preferably 1:1 to 10:1, more preferably 4:1 to 10:1, even more preferably 4.8:1 to 10:1, and still more preferably 6:1 to 10:1. When the ratio of the mass of monomer (A) to the mass of monomer (B) is within the above range, the storage stability and adhesion to substrates of the ink composition can be improved.

[0035] The ink composition of the present invention may contain a polyfunctional monomer as a polymerizable compound in addition to the monofunctional monomers (A) and (B). In the present invention, the polyfunctional monomer may refer to a compound having two or more ethylenic double bonds in one molecule. The polyfunctional monomer is not particularly limited, but preferred examples include 1,6-hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, bisphenol A diol, and the like. Bifunctional (meth)acrylate monomers such as Nol A PO adduct di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate; trifunctional or higher polyfunctional (meth)acrylate monomers such as pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin propoxy tri(meth)acrylate, and pentaerythritol ethoxy tetra(meth)acrylate;Examples of suitable vinyl monomers include polyfunctional monomers having a vinyl group, such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol vinyl ether, butylene divinyl ether, dibutylene glycol divinyl ether, neopentyl glycol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, norbornyl dimethanol divinyl ether, isovinyl divinyl ether, divinylresorcinol, divinylhydroquinone, glycerin trivinyl ether, glycerin ethylene oxide adduct trivinyl ether (6 moles of ethylene oxide added), trimethylolpropane trivinyl ether, trivinyl ether ethylene oxide adduct trivinyl ether (3 moles of ethylene oxide added), pentaerythritol trivinyl ether, and ditrimethylolpropane hexavinyl ether. These may be used alone or in combination of two or more. The inclusion of a polyfunctional monomer in the ink composition of the present invention can improve the storage stability of the composition and the strength of printed matter. The content of the polyfunctional monomer is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the mass of the entire ink composition, and is preferably 40% by mass or less, and more preferably 30% by mass or less. That is, the content of the polyfunctional monomer is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 30% by mass, and even more preferably 20 to 30% by mass, based on the mass of the entire ink composition. When the content of the polyfunctional monomer is within the above range, the storage stability of the composition is further improved, and the strength of the printed matter can be further improved.

[0036] The SP value of the polyfunctional monomer is preferably 7.5 (cal / cm 3 ) 1 / 2 More preferably, 7.7 (cal / cm 3 ) 1 / 2 More preferably, 7.8 (cal / cm3 ) 1 / 2 It is preferably 12.0 (cal / cm 3 ) 1 / 2 Less than 11.0 (cal / cm 3 ) 1 / 2 More preferably, 10.0 (cal / cm 3 ) 1 / 2 That is, the SP value of the polyfunctional monomer is preferably 7.5 to 12.0 (cal / cm 3 ) 1 / 2 , more preferably 7.7 to 11.0 (cal / cm 3 ) 1 / 2 , and more preferably 7.8 to 10.0 (cal / cm 3 ) 1 / 2 When the SP value of the polyfunctional monomer is within the above range, the storage stability of the ink composition can be improved.

[0037] The ink composition of the present invention may contain a polymerizable compound other than the monofunctional monomer (A), monofunctional monomer (B), and polyfunctional monomer described above. Examples of such polymerizable compounds include oligomers. The oligomer is a component that has the property of being polymerized and cured when irradiated with actinic energy rays. Here, in this specification, the term "oligomer" may refer to one having a weight-average molecular weight of 500 to 10,000. The weight-average molecular weight of the oligomer is preferably 800 or more, and more preferably more than 1,000. The weight-average molecular weight can be measured in terms of polystyrene using GPC (gel permeation chromatography). One type of oligomer may be used alone, or two or more types may be used in combination.

[0038] Examples of the oligomer include epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, urethane (meth)acrylate oligomer, and polyether (meth)acrylate oligomer.

[0039] When the ink composition of the present invention contains an oligomer, the content thereof is preferably 0.1 to 30 mass %, and more preferably 0.5 to 20 mass %, based on the total mass of the ink composition. When the content of the oligomer is within this range, the storage stability of the ink composition can be improved.

[0040] In the ink composition of the present invention, the ratio of the mass of the polymerizable compound to the mass of the aggregation inhibitor (mass of polymerizable compound:mass of aggregation inhibitor) is preferably 10:1 to 200:1, more preferably 30:1 to 200:1, even more preferably 50:1 to 200:1, still more preferably 80:1 to 200:1, and particularly preferably 100:1 to 200:1. When the ratio of the mass of the polymerizable compound to the mass of the aggregation inhibitor is within the above range, the storage stability of the ink composition can be improved.

[0041] The content of the polymerizable compound in the ink composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, based on the total mass of the ink composition, and is preferably 90% by mass or less, more preferably 89% by mass or less, even more preferably 85% by mass or less. That is, the content of the polymerizable compound in the ink composition of the present invention is preferably 30 to 90% by mass, more preferably 40 to 89% by mass, even more preferably 45 to 85% by mass, based on the total mass of the ink.

[0042] <Polyolefin> The ink composition of the present invention contains a polyolefin. In the present invention, the polyolefin preferably contains at least one selected from the group consisting of polyethylene, polypropylene, and polybutylene, and more preferably contains polyethylene. The polyolefin may be contained alone or in combination of two or more types.

[0043] The polyolefin forming the container (described below) generally has a weight-average molecular weight of about 20,000 to about 300,000, while the weight-average molecular weight of the polyolefin contained in the ink composition is usually about 10,000 to about 50,000. The weight-average molecular weight of the polyolefin can be measured, for example, by gel permeation chromatography (GPC) in terms of polystyrene.

[0044] The ink composition of the present invention is preferably filled in a container. The shape of the container is not particularly limited, and may be, for example, a cartridge, a bottle, a tank, a pouch, etc. The configuration of the container is also not particularly limited.

[0045] In the present invention, the polyolefin contained in the ink composition is preferably derived from a polyolefin contained in the liquid-contacting portion that comes into contact with the ink composition in a container filled with the ink composition. In other words, the ink composition of the present invention is preferably filled in a container containing a polyolefin in the liquid-contacting portion. The polyolefin contained in the ink composition of the present invention can be contained in the ink composition by, for example, storing the ink composition under normal usage conditions after production, such as one year at room temperature, 60 to 240 days at 30°C to 50°C, 30 days at 60°C, or 4 days at 70°C. Furthermore, the ink composition may be free of polyolefin immediately after production and before being filled into a container. Therefore, one aspect of the present invention may also include an ink composition containing a polymerizable compound and a polyolefin aggregation inhibitor.

[0046] In a container filled with the ink composition of the present invention, the polyolefin contained in the liquid-contacting portion of the container is preferably selected from the group consisting of polyethylene, polypropylene, and polybutylene, more preferably polyethylene, from the viewpoint of the heat-sealing properties of the container. One type of polyolefin may be contained alone, or two or more types may be contained.

[0047] In the present invention, the crystallinity of the polyethylene is preferably 35% or more, more preferably 40% or more, and preferably 55% or less, more preferably 50% or less. That is, the crystallinity of the polyethylene is preferably 35 to 55%, more preferably 40 to 50%. When the crystallinity of the polyethylene is within the above range, heat sealing is facilitated, improving the sealability of the container and the storage stability of the ink composition. The crystallinity of the polyethylene can be adjusted within the above range by, for example, appropriately adjusting the type of monomer used during polymerization, the type of polymerization catalyst, and polymerization conditions (e.g., pressure during polymerization). The crystallinity of the polyethylene can be determined, for example, using X-ray diffraction (XRD). In the present invention, the polyethylene is preferably linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), high-density polyethylene (HDPE), or ultra-high molecular weight polyethylene (UHMW-PE), with linear low-density polyethylene (LLDPE) being more preferred. The melting point of the polyethylene is preferably 120°C or more and 140°C or less. When the melting point of the polyethylene is within the above range, the storage stability of the ink composition is improved and the sealing properties of the container can be improved. The melting point of the polyethylene can be determined, for example, using a DSC (differential scanning calorimeter).

[0048] In one embodiment where the container filled with the ink composition of the present invention is a pouch, the layer configuration is not particularly limited as long as the innermost layer is a polyolefin layer. For example, the layer configuration may be, from the outermost layer, a resin layer such as PET, a metal layer such as aluminum, a resin layer such as nylon, and a polyolefin layer. The thickness of each layer can be adjusted appropriately depending on the application, but layers other than polyolefin are usually 5 to 30 μm, preferably 10 to 20 μm, and polyolefin layers are usually 20 to 70 μm, preferably 30 to 60 μm. The thickness of each layer can be measured, for example, using a contact thickness meter. Additionally, the layers may be bonded together using an adhesive or pressure-sensitive adhesive, the type and thickness of which can be selected appropriately depending on the application.

[0049] <Other additives> The ink composition of the present invention may contain other additives as needed, provided that the effects of the present invention are not impaired. Examples of other additives include polymerization initiators, surface conditioners, polymerization inhibitors, photosensitizers, cosensitizers, storage stabilizers, preservation stabilizers, antioxidants, colorants, ultraviolet absorbers, light stabilizers, chain transfer agents, conductive salts, fillers, organic solvents, diluent solvents, and thickeners.

[0050] The polymerization initiator is a compound that generates reactive species under the influence of heat or light and can initiate the polymerization reaction of the polymerizable compound contained in the ink composition. Examples of reactive species include active species such as radicals, cations, and anions. Among these, a photopolymerization initiator that generates radicals upon irradiation with light is preferred from the viewpoint of ease of reaction control.

[0051] Examples of the photopolymerization initiator include benzoin compounds having 14 to 18 carbon atoms (e.g., benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.), acetophenone compounds having 8 to 18 carbon atoms (e.g., acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc.), anthraquinone compounds having 14 to 19 carbon atoms (e.g., 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.), and Examples of suitable thioxanthone compounds include, but are not limited to, thioxanthone compounds having 13 to 17 carbon atoms (e.g., 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.), ketal compounds having 16 to 17 carbon atoms (e.g., acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenone compounds having 13 to 21 carbon atoms (e.g., benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, etc.), acylphosphine oxide compounds having 22 to 28 carbon atoms (e.g., 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), and mixtures of these compounds. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint of curability, it is preferable to contain at least one selected from acetophenone compounds and acylphosphine oxide compounds, and 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc. are preferred.Furthermore, commercially available products may be used as the photopolymerization initiator, and examples thereof include DAROCUR TPO manufactured by BASF, and Omnirad 184 and Omnirad 907 manufactured by IGM Resins.

[0052] The content of the photopolymerization initiator in the ink composition of the present invention is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, based on the mass of the entire ink composition, and is preferably 20% by mass or less, and more preferably 15% by mass or less. That is, the content of the photopolymerization initiator in the ink composition of the present invention is preferably 5 to 20% by mass, more preferably 8 to 20% by mass, and even more preferably 10 to 15% by mass, based on the mass of the entire ink composition. When the content of the photopolymerization initiator is within the above range, the amount of unreacted monomer components and the amount of photopolymerization initiator remaining undissolved can be reduced, and the storage stability of the ink composition can be improved.

[0053] The photosensitizer is a compound that can absorb specific active energy rays to promote the decomposition of the polymerization initiator and further promote the polymerization reaction of the polymerizable compound. Examples of photosensitizers include polynuclear aromatics (e.g., pyrene, perylene, triphenylene, 2-ethyl-9,10-dimethoxyanthracene, etc.), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal, etc.), cyanines (e.g., thiacarbocyanine, oxacarbocyanine, etc.), merocyanines (e.g., merocyanine, carbomerocyanine, etc.), thiazines (e.g., thionine, methylene blue, toluidine blue, etc.), acridines (e.g., acridine orange, chloroflavin, acriflavine, etc.), anthraquinones (e.g., anthraquinone, etc.), squaryliums (e.g., squalium, etc.), coumarins (e.g., 7-diethylamino-4-methylcoumarin, etc.), thioxanthones (e.g., isopropylthioxanthone, etc.), and thiochromanones (e.g., thiochromanone, etc.). Among them, thioxanthones are preferred as the photosensitizer, and isopropylthioxanthone is more preferred. The sensitizers may be used alone or in combination of two or more.

[0054] When the ink composition contains a photosensitizer, the content thereof is preferably 0.1 to 5 mass %, and more preferably 0.5 to 4 mass %, relative to the total mass of the ink composition. When the content of the photosensitizer is within this range, the curability and curing speed of the ink composition can be improved.

[0055] The polymerization inhibitor is used to suppress excessive polymerization at the temperature at which the ink composition is ejected, and can improve the storage stability of the ink composition and the ejection stability from an inkjet head. Specific examples of the polymerization inhibitor include nitroso-based polymerization inhibitors, hydroquinone, methoxyhydroquinone, benzoquinone, p-methoxyphenol, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl [TEMPOL (HO-TEMPO)], cupferron Al, and hindered amines.

[0056] The content of the polymerization inhibitor is generally preferably 0.001 to 1.5% by mass, and more preferably 0.01 to 1.0% by mass, relative to the total mass of the ink composition. When the content of the polymerization inhibitor is within this range, the storage stability of the ink composition can be further improved, and the ejection stability from the inkjet head can be further improved.

[0057] The surface conditioner is used to improve the wettability of the recording medium and to prevent cissing. Specific examples of surface conditioners include anionic surface conditioners such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts; nonionic surface conditioners such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene-polyoxypropylene block copolymers; cationic surface conditioners such as alkylamine salts and quaternary ammonium salts; silicone-based surface conditioners; and fluorine-based surface conditioners.

[0058] The content of the surface conditioner is selected appropriately depending on the purpose of use, but is generally preferably 0.0001 to 1 mass %, and more preferably 0.001 to 0.5 mass %, relative to the total mass of the ink composition. By adjusting the amount of surface conditioner added within this range as needed, the surface tension of the ink composition can be adjusted.

[0059] In one embodiment of the present invention, the ink composition of the present invention preferably contains a colorant (color ink composition). In another embodiment, the ink composition of the present invention preferably does not contain a colorant (clear ink composition). In the present invention, the clear ink composition may contain no colorant or may contain only a small amount of a pigment and / or dye, such as a bluing agent. When the ink composition of the present invention is a clear ink composition, the content of the colorant is typically 0.1% by mass or less, more preferably 0.05% by mass or less, based on the total mass of the ink composition, with the lower limit being 0% by mass. In other words, the content of the colorant in the clear ink composition is typically 0 to 0.1% by mass, more preferably 0 to 0.05% by mass, based on the total mass of the ink composition.

[0060] When the ink composition is a color ink composition containing a colorant, the composition is not particularly limited, but it is preferable that the colorant contains at least one selected from the group consisting of cyan, magenta, yellow, white, and black. In some cases, violet, blue, green, orange, red, etc. can also be used. In a preferred embodiment of the present invention, the colorant preferably contains a white pigment, from the viewpoint of being able to further suppress the aggregation of polyolefins by combining it with an aggregation inhibitor.

[0061] The colorant is not particularly limited, and can be appropriately selected from known water-soluble dyes, oil-soluble dyes, pigments, and the like. However, since the ink composition of the present invention is non-aqueous, the colorant is preferably an oil-soluble dye or pigment that is easily dispersed and dissolved uniformly in a non-aqueous medium, and it is particularly preferable to use a pigment.

[0062] As the pigment, either an organic pigment or an inorganic pigment can be used. Preferred examples of black pigments include carbon black pigments, etc. Generally, pigments of black and the three primary colors of cyan, magenta, and yellow are used, but other hues, such as metallic luster pigments of gold or silver, and colorless or pale-colored extender pigments, can also be used depending on the purpose.

[0063] Examples of pigments that exhibit magenta include monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.), disazo pigments such as CI Pigment Red 38 (Pyrazolone Red B, etc.), azo lake pigments such as CI Pigment Red 53:1 (Lake Red C, etc.) and CI Pigment Red 57:1 (Brilliant Carmine 6B), condensed azo pigments such as CI Pigment Red 144 (Condensed Azo Red BR, etc.), perinone pigments such as CI Pigment Red 194 (Perinone Red, etc.), perylene pigments such as CI Pigment Red 149 (Perylene Scarlet, etc.), and CI Pigment Violet 19 (unsubstituted quinacridone, CINQUASIA Magenta). quinacridone pigments such as CI Pigment Red 122 (dimethylquinacridone) and CI Pigment Red 202 (dichloroquinacridone), isoindolinone pigments such as CI Pigment Red 180 (isoindolinone red 2BLT, etc.), and alizarin lake pigments such as CI Pigment Red 83 (madder lake, etc.).

[0064] Examples of cyan pigments include disazo pigments such as CI Pigment Blue 25 (dianisidine blue, etc.), phthalocyanine pigments such as CI Pigment Blue 15, CI Pigment Blue 15:3 (IRGALITE BLUE GLO; manufactured by Ciba Specialty Chemicals), and CI Pigment Blue 15:4, acid dye lake pigments such as CI Pigment Blue 24 (peacock blue lake, etc.), and alkali blue pigments such as CI Pigment Blue 18 (alkali blue V-5:1).

[0065] Examples of pigments that exhibit yellow color include monoazo pigments such as CI Pigment Yellow 1 (Fast Yellow G, etc.) and CI Pigment Yellow 74, disazo pigments such as CI Pigment Yellow 12 (Disazo Yellow AAA, etc.) and CI Pigment Yellow 17, non-benzidine azo pigments such as CI Pigment Yellow 180 and CI Pigment Yellow 200 (Novoperm Yellow 2HG), azo lake pigments such as CI Pigment Yellow 100 (Tartrazine Yellow Lake, etc.), condensed azo pigments such as CI Pigment Yellow 95 (Condensed Azo Yellow GR, etc.), acid dye lake pigments such as CI Pigment Yellow 115 (Quinoline Yellow Lake, etc.), basic dye lake pigments such as CI Pigment Yellow 18 (Thioflavin Lake, etc.), anthraquinone pigments such as Flavanthrone Yellow (Y-24), and isoindoli. Examples of pigments include isoindolinone pigments such as Non Yellow 3RLT (Y-110), quinophthalone pigments such as Quinophthalone Yellow (Y-138), isoindoline pigments such as Isoindoline Yellow (Y-139), nitroso pigments such as CI Pigment Yellow 153 (nickel nitroso yellow, etc.), metal complex azo pigments such as CI Pigment Yellow 150 (nickel complex salt), and metal complex azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow, etc.).

[0066] Examples of black pigments include carbon black, titanium black, and aniline black. An example of carbon black is SPECIAL BLACK 250 (manufactured by Degussa).

[0067] Examples of white pigments include CI Pigment White 6, 18, and 21. Specific examples of white pigments that can be used include basic lead carbonate (2PbCO3Pb(OH)2, also known as silver white), zinc oxide (ZnO, also known as zinc white), titanium oxide (TiO2, also known as titanium white), and strontium titanate (SrTiO3, also known as titanium strontium white). Compared to other white pigments, titanium oxide has a lower specific gravity, a higher refractive index, and is chemically and physically stable. As a result, it has high hiding power and coloring power as a pigment, and also has excellent durability against acids, alkalis, and other environments. Therefore, it is preferable to use titanium oxide as the white pigment. Other white pigments (other than the white pigments listed above) may also be used if necessary. The average particle size of the white pigment is preferably 100 to 500 nm in terms of the effect of improving hiding power, and the average particle size of the nanoparticles serving as the aggregation inhibitor of polyolefin is preferably 5 to 100 nm. In a preferred embodiment of the present invention, nanoparticles are used as an agent for inhibiting polyolefin aggregation in an ink composition containing a white pigment. The presence of nanoparticles having an average particle size and / or specific surface area different from that of the white pigment in the ink composition can further inhibit polyolefin aggregation.

[0068] Among these known pigments, the cyan pigment is preferably Pigment Blue 15:3 or Pigment Blue 15:4, the magenta pigment is preferably Pigment Red 122, Pigment Red 202 or Pigment Violet 19, and the yellow pigment is more preferably Pigment Yellow 150, Pigment Yellow 180 or Pigment Yellow 155. Furthermore, the white pigment is preferably titanium oxide.

[0069] In order to form an image with excellent color reproducibility, the following pigments may be used as pigments of particular colors such as violet, blue, green, orange, and red, if necessary. Violet pigments include CI Pigment Violet 1 (Rhodamine B), CI Pigment Violet 2 (Rhodamine 3B), CI Pigment Violet 3 (Methyl Violet Lake), CI Pigment Violet 3:1 (Methyl Violet Lake), CI Pigment Violet 3:3 (Methyl Violet Lake), CI Pigment Violet 5:1 (Alizarin Maroon), CI Pigment Violet 13 (Ultramarine Pink), CI Pigment Violet 17 (Naphthol AS), and CI Pigment Violet 23 (Dimethyl Violet). Commercially available pigments include CI Pigment Violet 25 (Naphthol AS), CI Pigment Violet 29 (Perylene Violet), CI Pigment Violet 31 (Violanthrone Violet), CI Pigment Violet 32 ​​(Benzimidazolone Bordeaux HF3R), CI Pigment Violet 36 (Thioindigo), CI Pigment Violet 37 (Dioxazine Violet), CI Pigment Violet 42 (Quinacridone Maroon B), and CI Pigment Violet 50 (Naphthol AS).

[0070] As blue pigments, CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66, and the like are commercially available.

[0071] Commercially available green pigments include CI Pigment Green 1 (Brilliant Green Lake), CI Pigment Green 4 (Malachite Green Lake), CI Pigment Green 7 (Phthalocyanine Green), CI Pigment Green 8 (Pigment Green B), CI Pigment Green 10 (Nickel Azo Yellow), and CI Pigment Green 36 (Brominated Phthalocyanine Green).

[0072] Orange pigments include CI Pigment Orange 1 (Hansa Yellow 3R), CI Pigment Orange 2 (Orthonitro Orange), CI Pigment Orange 3 (β-naphthol), CI Pigment Orange 4 (Naphthol AS), CI Pigment Orange 5 (β-naphthol), CI Pigment Orange 13 (Pyrazolone Orange G), CI Pigment Orange 15 (Disazo Orange), CI Pigment Orange 16 (Anisidine Orange), and CI Pigment Orange 17 (Persian Orange Le). CI Pigment Orange 19 (Naphthalene Yellow Lake), CI Pigment Orange 24 (Naphthol Orange Y), CI Pigment Orange 31 (Condensed Azo Orange), CI Pigment Orange 34 (Disazopyrazolone Orange), CI Pigment Orange 36 (Benzimidazolone Orange HL), CI Pigment Orange 38 (Naphthol Orange), CI Pigment Orange 40 (Pyranthrone Orange), CI Pigment Orange 43 (Perinone Orange), CI Pigment Orange 46 (Ethyl Red Lake C), CI Pigment Orange 48 (Quinacridone Gold), CI Pigment Orange 49 (Quinacridone Gold), CI Pigment Orange 51 (Pyranthrone Orange), CI Pigment Orange 60 (Imidazolone Orange HGL), CI Pigment Orange 61 (Isoindolinone Orange), CI Pigment Orange 62 (Benzimidazolone Orange H5G), CI Pigment Orange 64 (Benzimidazolone), CI Pigment Orange 65 (Azomethine Orange) , CI Pigment Orange 66 (Isoindolin Orange), CI Pigment Orange 67 (Pyrazoloquinazolone Orange), CI Pigment Orange 68 (Azomethine Orange), CI Pigment Orange 69 (Isoindolinone Orange), CI Pigment Orange 71 (Diketopyrrolopyrrole Orange), CI Pigment Orange 72 (Imidazolone Orange H4GL), CI Pigment Orange 73 (Diketopyrrolopyrrole Orange), CI Pigment Orange 74 (Naphthol Orange 2RLD), CIPigment Orange 81 (Diketopyrrolopyrrole Orange) and other pigments are commercially available.

[0073] Commercially available red pigments include CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, and CI Pigment Red 270.

[0074] Of these, from the viewpoints of color reproducibility, lightfastness, and stability of pigment dispersions, CI Pigment Violet 23 is preferred as a pigment that exhibits a violet color, CI Pigment Orange 36 and CI Pigment Orange 71 are preferred as pigments that exhibit an orange color, and CI Pigment Green 7 and CI Pigment Green 36 are preferred as pigments that exhibit a green color.

[0075] Since the finer the dispersed average particle diameter of the colorant used, the better the color development, the dispersed average particle diameter of the colorant is preferably 0.01 μm or more and 0.4 μm or less, and more preferably 0.02 μm or more and 0.2 μm or less. It is preferable to select the colorant, dispersant, and dispersion medium, and set the dispersion conditions, classification conditions, and filtration conditions so that the maximum dispersed particle diameter is preferably 3 μm or less, more preferably 1 μm or less. This dispersed particle diameter control can suppress clogging of the head nozzles and maintain the ejection stability of the ink composition. The dispersed particle size of the colorant can be measured by a known measurement method, specifically, for example, by a particle size distribution analyzer using a centrifugal sedimentation light transmission method, an X-ray transmission method, a laser diffraction / scattering method, or a dynamic light scattering method.

[0076] The content of the colorant in the ink composition is selected appropriately depending on the color and purpose of use, but from the viewpoints of image density and storage stability, it is preferably 0.2 to 30 mass % and more preferably 0.5 to 20 mass % relative to the total mass of the ink composition.

[0077] When a pigment is used as the colorant, a pigment dispersant other than the pigment derivative or polymer dispersant may be further used to improve the dispersibility of the pigment.

[0078] Specific examples of the pigment derivative include pigment derivatives having a dialkylaminoalkyl group and pigment derivatives having a dialkylaminoalkylsulfonic acid amide group.

[0079] Specific examples of pigment dispersants other than polymer dispersants include ionic or nonionic surfactants having a weight average molecular weight of 1,000 or less.

[0080] The content of the pigment derivative and the pigment dispersant other than the polymer dispersant in the ink composition is preferably 0.05 to 5% by mass, respectively, relative to the total amount of the ink composition.

[0081] The method for producing the ink composition of the present invention is not particularly limited, and the ink composition can be produced, for example, by uniformly mixing the components constituting the ink composition using a mixer / stirrer, a disperser, or the like.

[0082] In the present invention, from the viewpoint of the storage stability of the ink composition, it is preferable that the aggregation inhibitor be uniformly dispersed in the ink composition. Therefore, as a method for uniformly mixing the components constituting the ink composition, for example, a method is preferred in which a pigment particle dispersion and an aggregation inhibitor dispersion are separately prepared and then mixed, in order to suppress aggregation during the dispersion treatment of the pigment particles and the aggregation inhibitor. Furthermore, during the dispersion treatment, it is preferable to optimize the selection of a disperser and the dispersion conditions so as to minimize destruction of the primary particle crystals.

[0083] The ink composition of the present invention is preferably applied onto a recording medium by an inkjet system. That is, the ink composition of the present invention is preferably an inkjet ink composition. Therefore, it is preferable that the physical properties of the ink composition are suitable for the inkjet system. Specifically, the viscosity of the ink composition of the present invention at 25°C is preferably 50 mPa·s or less, more preferably 40 mPa·s or less, and even more preferably 30 mPa·s or less. When the viscosity is equal to or less than the upper limit, the ink composition can be appropriately ejected from the ink head even at high speeds. There is no particular lower limit for the viscosity of the ink composition, but it is typically about 3.0 mPa·s. That is, the viscosity of the ink composition of the present invention at 25°C is preferably 3 to 50 mPa·s, more preferably 3 to 40 mPa·s, and even more preferably 3 to 30 mPa·s. The viscosity can be adjusted within the above range by, for example, appropriately adjusting the type and / or amount of the polymerizable compound; the type and / or amount of the photopolymerization initiator; etc. The viscosity can be measured, for example, using a viscometer, by the method described in the Examples.

[0084] The surface tension of the ink composition of the present invention is preferably 20 mN / m or more, more preferably 25 mN / m or more, and preferably 35 mN / m or less, more preferably 32 mN / m or less. That is, the surface tension of the ink composition of the present invention is preferably 20 to 35 mN / m, more preferably 25 to 32 mN / m. When the surface tension of the ink composition is equal to or greater than the above-mentioned lower limit and equal to or less than the above-mentioned upper limit, droplets can be ejected normally from the nozzle even during high-speed ejection, allowing images to be properly drawn. The surface tension can be adjusted within the above-mentioned range by, for example, appropriately adjusting the type and / or amount of the polymerizable compound; the type and / or amount of the surface conditioner; etc. The surface tension can be measured, for example, using a surface tensiometer.

[0085] <Ink set> The present invention encompasses ink sets containing ink compositions containing a colorant (color ink compositions) and / or ink compositions not containing a colorant (clear ink compositions). In one embodiment of the present invention, the ink set preferably contains color ink compositions of multiple colors (e.g., cyan, magenta, yellow, black, and white), or contains color ink compositions of multiple colors and a clear ink composition. Furthermore, the ink set of the present invention may optionally contain a primer ink composition in addition to the color ink composition and / or the clear ink composition.

[0086] The primer ink is placed between the recording medium and the image recorded with the ink composition, and can improve the adhesion and durability of the image recorded with the ink composition of the present invention.

[0087] The primer ink composition used with the ink set of the present invention is not particularly limited, and known primer ink compositions used in conventional inkjet systems can be used. Specifically, the primer ink composition contains at least one polymerizable compound, and optionally also contains a polymerization initiator, a polymerization inhibitor, a surface conditioner, and other additives. From the viewpoint of adhesion, the polymerizable compound used in the primer ink composition is preferably a (meth)acrylate, and it is more preferable to mainly use a monofunctional (meth)acrylate.

[0088] <Ink pack> The present invention encompasses an ink pack filled with an ink composition, wherein a liquid-contacting portion of the ink pack that comes into contact with the composition contains a polyolefin, and the ink composition contains a polymerizable compound, a polyolefin derived from the liquid-contacting portion of the ink pack, and an aggregation inhibitor for the polyolefin.

[0089] In this embodiment, the ink pack of the present invention contains an ink composition containing a polyolefin aggregation inhibitor, and therefore can suppress aggregation of the polyolefin even if the polyolefin elutes into the ink composition from the liquid-contacting part of the ink pack. Note that the ink composition and polyolefin contained in the ink pack of the present invention are preferably the same as the ink composition and polyolefin described in the above sections <Ink composition> and <Polyolefin>.

[0090] Therefore, in the ink pack of the present invention, the crystallinity of the polyethylene is preferably 35 to 55%, more preferably 40 to 50%. When the crystallinity of the polyethylene is within this range, heat fusion is facilitated, improving the sealing properties of the ink pack and the storage stability of the ink composition in the ink pack.

[0091] The ink pack that can be used in the present invention is not particularly limited, but is preferably a laminate having multiple layers, such as a laminate including a base film and at least one of a gas barrier layer, an adhesive layer, and a heat seal layer.

[0092] In a preferred embodiment of the present invention, the ink pack preferably includes a heat seal layer, and the heat seal layer preferably includes polyethylene having a crystallinity of 35 to 55%. When the heat seal layer includes the polyethylene, heat sealing is facilitated, improving the sealability of the ink pack and the storage stability of the ink composition in the ink pack. Furthermore, the moldability of the ink pack can be improved.

[0093] In one embodiment of the present invention, the ink pack includes a container such as a cartridge, bottle, tank, or pouch, an ink inlet, an ink outlet, and an ink composition filled in the pack.

[0094] The pouch may be an aluminum pouch, which may have a layer structure in which, from the outer layer, a PET layer, an aluminum layer, a nylon layer, an adhesive layer, and an LLDPE layer are laminated.

[0095] The ink pack of the present invention can be used, for example, by housing the ink pack in an ink cartridge and then mounting the ink cartridge in an inkjet recording apparatus.

[0096] <Inkjet recording method> In the inkjet recording method using the ink composition of the present invention, an image is formed on a substrate using the ink composition described above. More specifically, the ink composition described above is ejected onto a substrate from an inkjet head, and the composition ejected onto the substrate is photocured.

[0097] Photocuring of the ink composition of the present invention may be carried out simultaneously with or immediately after ejection. The reactivity of the polymerizable compound in the ink composition (monomer double bond reactivity) may be adjusted depending on the process and application. For example, when the ink composition is partially cured (monomer double bond reactivity is approximately 50%), curing shrinkage of the monomer is suppressed, which may suppress curling caused by the difference in shrinkage between the substrate and the ink composition coating, thereby improving adhesion to the substrate. Ultimately, from the viewpoint of strength and low tack of the printed material, it is preferable that the ink composition is fully cured (monomer double bond reactivity is 90 to 100%). The reactivity can be determined, for example, by measuring the infrared absorption spectrum (IR) of the coating film. Examples of light for photocuring include far infrared rays, infrared rays, visible light, near ultraviolet rays, and ultraviolet rays. Among these, near ultraviolet rays or ultraviolet rays are preferred from the viewpoint of ease and efficiency of the curing process.

[0098] The amount of energy required for the photocuring reaction varies depending on the type and content of the polymerization initiator, but generally, the cumulative light dose is 100 mJ / cm 2 More than 10,000mJ / cm 2 The following is preferable.

[0099] In the recording method of the present invention, the ink composition is ejected from the inkjet head (preferably by an inkjet nozzle) in a droplet size of preferably 1 pL to 25 pL, more preferably 1 pL to 15 pL. A droplet size within this range is effective in that it enables depiction of an image with high sharpness and density.

[0100] The ink composition of the present invention is preferably ejected from the inkjet head so that the thickness of the coating film on the substrate is preferably 1 to 20 μm.

[0101] As the substrate, both absorbent and non-absorbent substrates can be used. Examples of absorbent substrates include paper, cloth, fiber, leather, and wood. Examples of non-absorbent substrates include plastic films, substrates such as paper coated with plastic, and substrates with plastic films attached thereto. Examples of plastics include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, polypropylene, acrylic resin, and polyacetal. Other non-absorbent substrates that can be used include metals such as aluminum, iron, gold, silver, copper, nickel, titanium, chromium, molybdenum, silicon, lead, zinc, and stainless steel, as well as glass and ceramics.

[0102] The substrate may be subjected to a surface modification treatment depending on the purpose and use. Examples of the surface modification treatment include corona treatment, plasma treatment, flame treatment, and chemical cleaning treatment. The surface modification treatment can be carried out by a method known in the art. [Example]

[0103] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. In the examples, "%" and "parts" mean "% by mass" and "parts by mass" unless otherwise specified.

[0104] The components of the ink compositions used in each of the examples and comparative examples are shown in Table 1 below.

[0105] [Table 1]

[0106] (SP value of monomer) The SP values ​​of the monomers in Table 1 are values ​​at 25°C obtained by the Fedors method (Harasaki Yuji, "The Basic Science of Coatings," Chapter 3, page 35, 1977, Maki Shoten Publishing), and specifically, are values ​​calculated according to the following method. Fedors believes that both the cohesive energy density and the molar volume depend on the type and number of substituents, and proposes the following formula and constants depending on each substituent: δ=(ΔE / V) 1 / 2 =(ΣΔei / ΣΔvi) 1 / 2 In the formula, δ is the SP value (cal / cm 3 ) 1 / 2 , ΔE is the cohesive energy density, V is the molar volume, Δei is the evaporation energy of each atom or atomic group (cal / mol), Δvi is the molar volume of each atom or atomic group (cm 3 / mol). For compounds with a glass transition temperature Tg of 25°C or higher, the following value was added to the molar volume: if n is the number of main chain atoms in the repeating unit of the compound, 4n was added to Δvi when n<3, and 2n was added to Δvi when n≧3.

[0107] (average particle size) The average particle size of the particles in Table 1 was determined by observing and measuring the particle size of individual primary particles separated by grain boundaries using a transmission electron microscope (TEM), then determining the average major axis diameter and the average minor axis diameter of at least 100 particles, and then averaging the average major axis diameter and the average minor axis diameter to determine the particle size.

[0108] (specific surface area of ​​particles) The specific surface areas of the particles in Table 1 were measured by the multipoint nitrogen adsorption method (BET method).

[0109] (Preparation of White Ink Composition) First, a primary dispersion of colorant (pigment) was prepared as follows, using the blending amounts (unit: mass %) shown in Table 2. Specifically, the photopolymerizable compound HDDA, colorant CR60, aggregation inhibitor TTO55(B), and dispersant S33000 were weighed out and placed in a plastic bottle, to which 100 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and the mixture was dispersed in a paint conditioner for 1 hour. Next, a pigment ink was prepared using the primary dispersion as follows: The remaining components were added to the primary dispersion in the amounts (unit: mass %) shown in Table 2, and the mixture was stirred for 30 minutes using a magnetic stirrer. After stirring, the mixture was suction filtered using glass fiber filter paper GFP (Kiriyama Manufacturing, capture particle size 0.8 μm) to prepare a white ink composition.

[0110] (Preparation of Cyan Ink Composition) First, a primary dispersion of colorant (pigment) was prepared as follows, using the blending amounts (unit: mass %) shown in Table 2. Specifically, the photopolymerizable compound HDDA, colorant P-BFS, aggregation inhibitor TTO55(B), and dispersant S33000 were weighed out and placed in a plastic bottle, to which 100 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and the mixture was dispersed in a paint conditioner for 1 hour. Next, a pigment ink was prepared using the primary dispersion as follows: The remaining components were added to the primary dispersion in the amounts (unit: mass %) shown in Table 2, and the mixture was stirred for 30 minutes using a magnetic stirrer. After stirring, the mixture was suction filtered using glass fiber filter paper GFP (manufactured by Kiriyama Manufacturing, capture particle size 0.8 μm) to prepare a cyan ink composition.

[0111] (Preparation of Clear Ink Composition) The various components were weighed out in the amounts (unit: mass%) shown in Table 2 and stirred for 30 minutes using a magnetic stirrer. After stirring, the mixture was suction filtered using glass fiber filter paper GFP (manufactured by Kiriyama Manufacturing, capture particle size 0.8 μm) to prepare a clear ink composition.

[0112] (Ink pack production) Each ink composition was filled into an aluminum pouch (layer structure: from outer layer to outer layer: PET (thickness: 20 μm), aluminum (thickness: 10 μm), nylon (thickness: 20 μm), adhesive layer (thickness: 10 μm), LLDPE (thickness: 50 μm, crystallinity: 50%)) without allowing air to get in, and the pouch was heat-sealed. This pouch was then stored at 70°C for 4 days in an environmental tester, and then allowed to cool to 25°C.

[0113] (Analysis of Polyethylene in Ink Composition) 1) Agglomeration After storing at 70°C for 4 days and then allowing to cool to 25°C, the ink compositions of the Examples and Comparative Examples were subjected to suction filtration using a SUS mesh (pore size 5 μm), and the presence or absence of residue (residue A) on the mesh was confirmed using an optical microscope. If residue A was present, IR analysis was further performed on residue A under the following conditions. Detector: NEXUS470 (Thermo Fisher) Measurement method: Transmission method (microscope mode) Resolution: 4cm -1 Accumulation count: 64 times The main peak of polyethylene (2915 cm -1 , 2850cm-1 , 1465cm -1 , 720cm -1 By checking the peaks around the residue A, it was determined that residue A was polyethylene aggregates.

[0114] 2) Dispersion The ink compositions of the examples and comparative examples were stored at 70°C for 4 days and then allowed to cool to 25°C. The ink compositions were then suction-filtered through a SUS mesh (pore size: 5 μm), resulting in filtrate B. Filtrate B was then centrifuged using a batch centrifuge, H-9R (Kokusan Co., Ltd., angle rotor radius: 14.1 cm, 7500 rpm), to sediment the solid component (solid component C). The supernatant (supernatant D) after sedimentation was then diluted with dipropylene glycol monomethyl ether acetate (DPMA) to approximately 0.001 to 10% to obtain the scattering intensity and detection sensitivity of the particle size distribution analyzer. This was used as the measurement sample. The hydrodynamic diameter, which analyzes particle size using the Stokes-Einstein equation, was measured using a dynamic light scattering particle size distribution analyzer (Otsuka Electronics Co., Ltd., FPAR1000). Furthermore, IR analysis of the supernatant D was performed to confirm the presence of polyethylene. When the scattering intensity increased in the particle size distribution measurement compared to when only the dilution solvent was measured, and when the particle diameter was counted and polyethylene was detected in the IR analysis, it was determined that polyethylene was dispersed in the ink composition.

[0115] 3) adsorption and 4) dissolution The solid component C precipitated by centrifugation in 2) above was immersed in a solvent (1,2,4-trichlorobenzene) and shaken at 140°C for 1 hour. After shaking, the solid component was precipitated by centrifugation, and the supernatant (supernatant E) was subjected to preparative GPC (gel permeation chromatography) to obtain a fraction (fraction F) corresponding to the pigment and nanoparticles. The GPC conditions are as follows: Measuring equipment: HLC-8321GPC / HT (Tosoh Corporation) Column: TSKgel GMH HR -H(20)HT (Tosoh Corporation) Detector: RI (differential refractometer) Eluent: 1,2,4-trichlorobenzene Temperature: 140°C (column) Flow rate: 1mL / min Furthermore, the presence or absence of polyethylene was confirmed by IR analysis of fraction F. If polyethylene was detected in fraction F by IR analysis, it was determined that polyethylene was adsorbed to the nanoparticles. Furthermore, if polyethylene was not detected in fraction F by IR analysis but was detected in the supernatant D, it was determined that polyethylene was dissolved in the ink composition.

[0116] [Table 2]

[0117] (Viscosity measurement) The viscosity of the ink compositions of the Examples and Comparative Examples after storing at 70°C for 4 days and then allowing to cool to 25°C was measured using an R100 viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25°C and a cone rotation speed of 5 rpm.

[0118] (Measurement of coarse particles) The ink compositions of the examples and comparative examples were stored at 70°C for 4 days and then allowed to cool to 25°C. Using a liquid particle sensor KS-42D (manufactured by Rion Co., Ltd., measurement range 2 to 100 μm), the number of coarse particles with a particle size of 2 μm or more was measured under the conditions of 100 ml of sample and 25°C, and the results were evaluated according to the following criteria. ○: Less than 10,000 △: Over 10,000, less than 100,000 ×: Over 100,000

[0119] (Preparation of printed sample for evaluation) The ink compositions of the examples and comparative examples, which had been stored at 70°C for 4 days and then allowed to cool to 25°C, were applied to a 188 μm thick polyethylene terephthalate film (a white PET film manufactured by Teijin DuPont Films, product name "U292W") using a bar coater to form a 15 μm thick solid ink coating film. A high-pressure mercury lamp (peak irradiance: 300 mW / cm) was used as irradiation means. 2) with a total irradiation dose of 500mJ / cm 2 The ink was cured by irradiating it with ultraviolet light so as to obtain a solid print.

[0120] (curing speed) The solid print formed by the above procedure was touched with a finger and the curability was evaluated according to the following criteria. 〇: Not sticky and ink does not stick to fingers △: Sticky, and ink sticks slightly to fingers ×: Very sticky, ink sticks to fingers

[0121] (adhesion) The solid print formed by the above procedure was cross-cut, and the adhesive layer side of an adhesive sheet [Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.)] was attached to the cross-cut, and then peeled off. The adhesion was evaluated according to the following criteria. ○: No peeling at all △: Slight peeling ×: The entire area where the adhesive sheet was attached peeled off.

[0122] (filtration test) The ink compositions of the examples and comparative examples were stored at 70°C for 4 days and then allowed to cool to 25°C by natural cooling. After this, the ink compositions were suction filtered using a SUS mesh (pore size 5 μm). The state of the residue on the mesh was observed using an optical microscope, and the storage stability of the ink compositions was evaluated according to the following criteria. ○: No residue △: Slight residue ×: Large amount of residue

[0123] (Dischargeability) The ink compositions of the examples and comparative examples were stored at 70°C for 4 days and then allowed to cool to 25°C. Then, the ink compositions were printed on a commercially available LED-UV curing inkjet printer (droplet size 7pl, resolution 720 × 600 dpi, LED wavelength 385 nm, peak irradiance 1200 mW / cm). 2 , cumulative light intensity 2600mJ / cm 2The ink was filled in an inkjet head (with a UV lamp installed next to the head) and ejected from the inkjet head onto a PET substrate (Teijin DuPont Films U292W). Each time an ink droplet landed on the substrate, it was simultaneously irradiated with UV light, and 10 consecutive printed letters were produced on the PET substrate from the printer stage. The ejection properties were evaluated according to the following criteria. 〇: No missing ink droplets, no misalignment of ink droplets △: Missing ink, misaligned ink droplets, practical problems ×: Many missing inks, unable to form characters

[0124] The evaluation results are shown in Table 3. [Table 3]

Claims

1. An ink composition comprising a polymerizable compound, a polyolefin, and a polyolefin agglomeration inhibitor.

2. The composition of claim 1 , wherein the flocculation inhibitor comprises nanoparticles and / or polymeric dispersants.

3. The composition of claim 2 , wherein the polyolefin is at least partially adsorbed onto nanoparticles.

4. The composition of claim 2 wherein the polyolefin is at least partially dispersed in the composition.

5. 10. The composition of claim 1, wherein the polyolefin is at least partially dissolved in the composition.

6. The polymerizable compound has an SP value of 7.8 (cal / cm ３ ) １／２ More than 9.6 (cal / cm ３ ) １／２ The composition of claim 1 , comprising a monofunctional monomer (A):

7. The polymerizable compound has an SP value of 7.8 (cal / cm ３ ) １／２ Less than or equal to 9.6 (cal / cm ３ ) １／２ The composition of claim 6 further comprising more than one monofunctional monomer (B).

8. The composition according to claim 7, wherein the mass ratio of the monofunctional monomers (A) and (B) is 1:1 to 10:

1.

9. The composition according to claim 1, wherein the weight ratio of the polymerizable compound to the aggregation inhibitor is 10:1 to 200:

1.

10. The composition of claim 1 , wherein the polyolefin comprises polyethylene.

11. 3. The composition of claim 2, wherein the nanoparticles comprise at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, strontium titanate, lithopone, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silicon dioxide, tin oxide, phosphorus-containing tin oxide (PTO), antimony oxide, antimony-containing tin oxide (ATO), aluminum-containing zinc oxide (AZO), gallium-containing zinc oxide (GZO), indium oxide, and tin-containing indium oxide (ITO).

12. The composition according to claim 2 , wherein the polymeric dispersant comprises a polyester polyamide having a weight average molecular weight of 1,000 or more and 70,000 or less.

13. The composition of claim 1 which is free of colorants.

14. The composition of claim 1 further comprising a colorant.

15. The composition of claim 14 , wherein the colorant comprises a white pigment.

16. The composition of claim 1 which is packaged in a container.

17. The composition of claim 16 , wherein a liquid-contacting part in the container that comes into contact with the ink composition comprises a polyolefin.

18. 18. The composition of claim 17, wherein the polyolefin comprises polyethylene having a crystallinity of 35% or more and 55% or less.

19. The composition of claim 1 which is an ink-jet ink composition.

20. An ink set comprising the composition according to claim 13 and / or the composition according to claim 14.

21. An ink pack filled with an ink composition, In the ink pack, a liquid-contacting portion that comes into contact with the ink composition contains polyolefin, The ink composition includes a polymerizable compound, a polyolefin derived from a liquid-contacting portion of the ink pack, and an aggregation inhibitor for the polyolefin.

22. 22. The ink pack according to claim 21, wherein the polyolefin comprises polyethylene having a crystallinity of 35% or more and 55% or less.

23. The ink pack according to claim 21, wherein the ink pack is a laminate including at least one layer selected from the group consisting of a gas barrier layer, an adhesive layer, and a heat seal layer.

24. 24. The ink pack of claim 23, wherein the heat seal layer comprises the polyolefin of claim 22.

25. A step of ejecting the composition according to claim 1 onto a substrate from an inkjet head; and A step of photocuring the composition dispensed onto the substrate. An inkjet recording method comprising:

Images