JP2017132890A - Nonaqueous inkjet composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous inkjet composition that has excellent storage stability and makes it possible to obtain a recorded matter having excellent chroma.SOLUTION: A nonaqueous inkjet composition comprises a pigment comprising a diketopyrrolopyrrole pigment and an organic solvent. The organic solvent comprises a glycol monoether, and a saturated hydrocarbon having an alicyclic structure.SELECTED DRAWING: None

Description

  The present invention relates to a non-aqueous inkjet composition.

  The ink jet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields. Among them, various studies have been made on obtaining a more stable and high-quality recorded matter.

  For example, Patent Document 1 discloses a novel organic solvent-based pigment-dispersed ink composition having excellent dispersion stability, in particular, a liquid aliphatic composition that is suitable for ink jet printing inks. An ink composition in which hydrocarbon is used as a dispersion medium, a colorant which is a fine particle of carbon or organic pigment is dispersed in the medium using a polymer dispersant that is conventionally known as a dispersant and is soluble in the medium. In order to improve the dispersion of the colorant pigment and its stability, N, N-dialkylaminoethyl acrylate and N- (1′-sulfoxy-3′-methyl-5′-chloro) -3- A solvent-based pigment dispersion ink composition in which hydroxy-2-naphthalenecarboxamide or N- (3′-sulfoxy) -3-hydroxy-2-naphthalenecarboxamide coexists is disclosed.

JP 2008-1851 A

  However, when a red color material is included in the ink composition described in Patent Document 1, although the dispersion stability of the red color material is excellent, the resulting recorded matter has poor wettability. The recorded matter with excellent saturation cannot be obtained.

  Accordingly, the present invention has been made to solve at least a part of the above-described problems, and provides a non-aqueous inkjet composition that is excellent in storage stability and can obtain a recorded matter with excellent saturation. The purpose is to provide.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have obtained a pigment containing a diketopyrrolopyrrole pigment and an organic solvent containing a glycol monoether and a saturated hydrocarbon having an alicyclic structure. It has been found that by using the non-aqueous ink composition containing the ink, a recorded material having excellent storage stability and excellent chroma can be obtained, and the present invention has been completed.

  That is, the present invention includes a pigment containing a diketopyrrolopyrrole pigment and an organic solvent, and the organic solvent contains a glycol monoether and a saturated hydrocarbon having an alicyclic structure. It is an inkjet composition. The reason why such a non-aqueous ink jet composition can solve the problems of the present invention is considered as follows. However, the factor is not limited to this. That is, the conventional non-aqueous composition has a recording medium that has a red color material in the recording material due to insufficient wettability of the recording material obtained immediately after being ejected by the ink jet method. The recorded matter cannot be made sufficiently excellent in saturation. On the other hand, the non-aqueous inkjet composition of the present embodiment has sufficient wettability of the recorded matter obtained mainly due to the organic solvent contained therein containing glycol monoether, and The dispersibility of the red color material in the composition can be favorably maintained mainly due to the inclusion of the saturated hydrocarbon having an alicyclic structure. As a result of these, it is possible to obtain a recorded matter having excellent storage stability and excellent saturation.

Moreover, in the non-aqueous inkjet composition according to the present invention, the saturated hydrocarbon having an alicyclic structure preferably has 8 to 14 carbon atoms, and the saturated hydrocarbon having the alicyclic structure has a content of It is preferable that it is 20 mass% or more and 70 mass% or less with respect to the total amount of the said non-aqueous inkjet composition, and it is preferable that the said glycol monoether contains the compound represented by following formula (1).
OH— (R ² O) _n —R ¹ (1)
(In formula (1), R ¹ represents an alkyl group having 2 to 7 carbon atoms, R ² represents an alkylene group having 1 to 3 carbon atoms, and n represents an integer of 1 to 7)

  In the non-aqueous inkjet composition according to the present invention, the glycol monoether content is preferably 20% by mass or less based on the total amount of the non-aqueous inkjet composition, and the diketopyrrolopyrrole pigment The average particle diameter is more preferably 100 nm or more and 240 nm or less, and the content of the pigment is preferably 1.0% by mass or less and 5.0% by mass or less based on the total amount of the non-aqueous inkjet composition, The organic solvent preferably further contains glycol diether, and the organic solvent preferably further contains a cyclic lactone, and preferably further contains a vinyl chloride resin.

  In addition, the ink jet recording method according to the present invention includes a step of recording on a recording medium by the ink jet method using the non-aqueous ink jet composition according to the present invention.

1 is a perspective view schematically illustrating a configuration of a printer according to an embodiment of the present invention.

  Hereinafter, a form 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. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, positional relationships such as up, down, left and right are based on the positional relationships shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Non-aqueous inkjet composition]
The non-aqueous ink jet composition of the present embodiment (hereinafter, also simply referred to as “ink jet composition”, “non-aqueous composition”, “composition”) includes a pigment containing a diketopyrrolopyrrole pigment, an organic solvent, including. The organic solvent contains glycol monoether and a saturated hydrocarbon having an alicyclic structure.

  The composition of the present embodiment contains a glycol containing a diketopyrrolopyrrole pigment and a saturated hydrocarbon having a glycan monoether and an alicyclic structure, so that a recorded matter with excellent storage stability and excellent saturation can be obtained. Can be obtained. This factor is inferred as follows (however, the factor is not limited to this). The conventional non-aqueous composition has a red color material in the recorded material in the recording medium due to insufficient wettability of the recorded material immediately after being ejected by the ink jet method. It is buried, and the saturation of the recorded matter cannot be sufficiently improved. On the other hand, the non-aqueous composition of the present embodiment can have sufficient wettability of the recorded matter obtained mainly due to the organic solvent contained therein containing glycol monoether. . In addition, the non-aqueous composition of the present embodiment has a red colorant in the composition mainly because the organic solvent contained therein contains a saturated hydrocarbon having an alicyclic structure. Dispersibility can be maintained well. As a result of these, the composition of the present embodiment is excellent in storage stability and can provide a recorded matter with excellent saturation.

  In the present embodiment, “non-aqueous” is a composition in which an organic solvent or the like is a main solvent and water is not a main solvent. Here, the “main solvent” means that the content in the composition is 50% by mass or more with respect to 100% by mass of the composition, preferably 70% by mass or more, and 90% by mass. More preferably. Further, when water is contained, it is preferably a composition in which water is not intentionally added as a main solvent component in the preparation of the composition, but it may be a case where water is inevitably contained as an impurity. preferable. The content of water in the composition is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, still more preferably 1.0% by mass or less, relative to 100% by mass of the composition. A mass% or less is more preferable. The lower limit of the water content is not particularly limited, and may be below the detection limit or 0.01% by mass.

  As a method for adjusting the water content in the composition, for example, a method of removing water from each component of the composition, specifically, a method of removing water mixed in an organic solvent, or removing water from the composition The method and the method of suppressing mixing of water at the time of preparation of a composition are mentioned. Among these, as a method of removing water mixed in the organic solvent, more specifically, a method of purifying the organic solvent by distillation, a method of permeating the organic solvent through a semipermeable membrane that selectively permeates water, and water There is a method of selectively adsorbing water mixed in an organic solvent to the adsorbing water adsorbent. Among these, a distillation purification method is preferable from the viewpoint of more efficiently and reliably reducing the water content.

  The non-aqueous inkjet composition of this embodiment includes a pigment and an organic solvent described later. The composition containing a solvent is roughly classified into a real solvent (high organic solvent) composition and an eco solvent (low organic solvent) composition. Eco solvent composition is a low odor and environmentally friendly composition, and does not fall under the organic solvent stipulated by the Industrial Safety and Health Act. Is not applicable, or organic solvents that are not subject to the obligation of local exhaust ventilation are used in indoor workplaces with installation environments stipulated by the Fire Service Act. As the non-aqueous composition of the present embodiment, any of an organic solvent that can be used for a real solvent composition and an organic solvent that can be used for an eco solvent composition can be used, and among them, it can be used for an eco solvent composition. It is preferable to include an organic solvent.

  In the present embodiment, the “inkjet composition” can be used for various applications as a composition used by being ejected by an inkjet method, and the application is not limited. Specifically, the use is for ink. Hereinafter, the case where the composition of the present embodiment is used as an ink composition for ink jet recording (hereinafter, also simply referred to as “ink composition”), which is one embodiment of the ink jet composition, will be described in more detail. The composition of the embodiment is not limited to this.

<Pigment>
The pigment of the present embodiment is not particularly limited as long as it contains a diketopyrrolopyrrole pigment, but may be only a diketopyrrolopyrrole pigment, or a pigment other than a diketopyrrolopyrrole pigment and a diketopyrrolopyrrole pigment (hereinafter, It may also be a mixture with “other pigments”.

  The diketopyrrolopyrrole pigment is not particularly limited as long as it has a diketopyrrolopyrrole skeleton. The diketopyrrolopyrrole skeleton may have a substituent such as an alkyl group on the diketopyrrolopyrrole skeleton. The group may be all hydrogen atoms). Although it does not specifically limit as a specific example of a diketopyrrolopyrrole pigment, For example, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 270, and C.I. I. Red organic pigments such as CI Pigment Red 272; I. Pigment orange 71, C.I. I. Pigment orange 73, and C.I. I. Examples thereof include orange-based organic pigments such as CI Pigment Orange 81. Among these, C.I. from the viewpoint of obtaining a recorded matter with better saturation. I. Pigment red 254, C.I. I. Pigment red 255, and C.I. I. Pigment Red 264, a red organic pigment, is preferable. I. Pigment Red 254 is more preferable from the viewpoint of obtaining superior saturation. These diketopyrrolopyrrole pigments may be used alone or in combination of two or more.

The diketopyrrolopyrrole pigment is preferably a diketopyrrolopyrrole red pigment. The diketopyrrolopyrrole red pigment exhibits red color and has a diketopyrrolopyrrole skeleton, and examples thereof include the diketopyrrolopyrrole red pigment which is the red pigment described above. Here, “presenting red” means a CIE table obtained by measuring the color of a recorded material coated with an inkjet composition so as to cover the entire surface of a white recording medium, using Spectrolino (manufactured by Gretag Macbeth). In the L ^* C ^* h color space in the color system, h is −30 ° to 45 °, h is preferably −30 ° to 32 °, and h is −30 ° to 30 °. More preferably, h is more preferably −30 ° to 25 °.

  The content of the diketopyrrolopyrrole pigment is not particularly limited, but is 30% by mass or more and 100% by mass or less, 50% by mass or more and 100% by mass or less, and 70% by mass with respect to the total amount of pigment (100% by mass). It is not less than 100% by mass. By using a composition in which the content of the diketopyrrolopyrrole pigment is in such a range, the saturation tends to be more excellent.

  The average particle size of the diketopyrrolopyrrole pigment is not particularly limited, but is preferably 50 nm or more and 300 nm or less, more preferably 100 nm or more and 240 nm or less, and further preferably 150 nm or more and 220 nm or less. When the average particle size of the diketopyrrolopyrrole pigment is 50 nm or more, it tends to be more excellent in the chroma of the obtained recorded matter. Moreover, when the average particle diameter of the diketopyrrolopyrrole pigment is 300 nm or less, the discharge stability tends to be superior. In order to obtain a diketopyrrolopyrrole pigment having an average particle diameter in the above range, although not particularly limited, a commercially available diketopyrrolopyrrole pigment having a regulated particle diameter may be prepared, and a plurality of particles having different particle diameters may be prepared. It may be prepared by adjusting the average particle size to the above range by mixing various diketopyrrolopyrrole pigments, or after mixing a commercially available diketopyrrolopyrrole pigment in a solvent, ball mill, bead mill, ultrasonic crushing The average particle size or particle size distribution may be adjusted to a desired value by appropriately pulverizing the mixture using a jet mill or the like. Furthermore, as another method for adjusting the average particle size, a pigment having a small primary particle size is prepared, and when this is mixed with a solvent (part or all), dispersion is performed by changing the addition amount of the dispersant. Can be adopted. In other words, if enough dispersant is added, aggregation of primary particles can be prevented, so that it can be dispersed with a particle size not much different from primary particles, and the average particle size can be made based on a small primary particle size. By reducing the amount, the primary particles can be aggregated to obtain an average particle size based on the particle size of the secondary particles. In this case, it is more preferable to use a smaller primary particle diameter of the starting pigment because the degree of freedom in adjusting the average particle diameter increases. Furthermore, when it is desired to increase the degree of freedom in adjusting the average particle size, the obtained pigment is once pulverized by a ball mill or the like as described above, and then made smaller, and then the average particle size is adjusted with a dispersant. Also good. The average particle diameter is measured by a laser microscope or a Coulter counter method. Here, the “average particle diameter” means the volume average particle diameter.

  As other pigments, for example, pigments such as inorganic pigments and organic pigments usually used in conventional non-aqueous ink compositions can be used. These other pigments may be used alone or in combination of two or more.

  Examples of the organic pigment include, but are not limited to, azo pigments (for example, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, Dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments), dye lakes (eg, basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments .

  Although it does not specifically limit as an inorganic pigment, For example, carbon black, titanium dioxide, a silica, and an alumina are mentioned.

  In addition, as other pigments, red organic pigments other than diketopyrrolopyrrole pigments (hereinafter also referred to as “other red organic pigments”) and orange organic pigments other than diketopyrrolopyrrole pigments (hereinafter referred to as “other red pigments”) , "Other orange organic pigments") is also preferable from the viewpoint of ejection stability and abrasion resistance.

  Other red organic pigments are not particularly limited. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 170, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 194, C.I. I. Pigment red 209, C.I. I. Pigment red 222, and C.I. I. Pigment red 224.

  Other orange organic pigments are not particularly limited, and examples thereof include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, and C.I. I. Pigment orange 64.

  The content of the pigment is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and 5.0% by mass or less, with respect to the total amount (100% by mass) of the composition. More preferably, it is 2.0 mass% or more and 4.0 mass% or less. When the pigment content is 0.5% by mass or more, the chroma of the obtained recorded product tends to be more excellent, and when the pigment content is 10% by mass or less, It tends to be more excellent in abrasion resistance and ejection stability.

<Organic solvent>
The organic solvent of this embodiment contains glycol monoether and saturated hydrocarbon having an alicyclic structure, and may further contain glycol diether and / or lactone as necessary. By including a saturated hydrocarbon having no hydroxyl group and having a stable alicyclic structure and glycol monoether having a hydroxyl group and easily absorbing moisture, it is possible to achieve both storage stability and saturation of the obtained recorded matter. it can. That is, when used in combination with glycol monoether, diketopyrrolopyrrole pigment is better in terms of saturation, but may not be sufficiently excellent in storage stability. By further containing a hydrocarbon, the storage stability is also excellent.

  The alicyclic structure of the saturated hydrocarbon is not particularly limited. For example, cyclopropane structure, cyclobutane structure, cyclopentane structure, cyclohexane structure, cycloheptane structure, cyclooctane structure, cyclononane structure, cyclodecane structure, cycloundecane structure. , Cyclododecane structure, cyclotridecane structure, and cyclotetradecane structure. The saturated hydrocarbon having an alicyclic structure is not particularly limited as long as it is a compound having an alicyclic structure, and may have an alkyl group or a cycloalkyl group. Therefore, the saturated hydrocarbon having an alicyclic structure is not limited to a cycloalkane having one alicyclic structure, but a saturated hydrocarbon having a bicycloalkane having two alicyclic structures and other alicyclic structures. There may be. By containing a saturated hydrocarbon having such an alicyclic structure, the storage stability tends to be further improved. The saturated hydrocarbon having an alicyclic structure does not have a hydrophilic group. The hydrophilic group is not particularly limited, and examples thereof include a hydroxyl group, an amine group, an imine group, an alcohol group, a thiol group, a sulfonic acid group, and a carboxylic acid group. By not having a hydrophilic group, the stability is further improved. Among these, a cycloalkane having one alicyclic structure is preferable, an unsubstituted cycloalkane is more preferable, a cycloalkane having 8 to 12 carbon atoms is more preferable, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, More preferred are cyclotridecane and cyclotetradecane. By using a cycloalkane having one alicyclic structure, the discharge stability tends to be improved, and by using an unsubstituted cycloalkane, the storage stability tends to be further improved in addition to the discharge stability. In addition to the discharge stability and the storage stability, the saturation tends to be further improved by using a cycloalkane having 8 to 12 carbon atoms. The saturated hydrocarbon having an alicyclic structure may be used alone or in combination of two or more.

  The carbon number of the saturated hydrocarbon having an alicyclic structure is preferably 8 or more, more preferably 9 or more. Moreover, the carbon number of the saturated hydrocarbon having an alicyclic structure is preferably 14 or less, more preferably 13 or less, and still more preferably 12 or less. When the saturated hydrocarbon having an alicyclic structure has 8 or more carbon atoms, the drying property of the non-aqueous composition is further reduced, and the non-aqueous composition is sufficiently wet spread on the recording medium. The image quality such as degree tends to be improved. In addition, when the saturated hydrocarbon having an alicyclic structure has 14 or less carbon atoms, the viscosity of the composition tends to be relatively lowered, and the discharge stability tends to be further improved. When the carbon number of hydrogen is 12 or less, ejection stability and drying properties tend to be further improved.

  The content of the saturated hydrocarbon having an alicyclic structure is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably with respect to the total amount (100% by mass) of the non-aqueous composition. 30% by mass or more. The content of saturated hydrocarbons having an alicyclic structure is preferably 70% by mass or less, more preferably 65% by mass or less, based on the total amount (100% by mass) of the non-aqueous composition. Preferably it is 50 mass% or less. When the content of the saturated hydrocarbon having an alicyclic structure is 20% by mass or more, the storage stability tends to be further improved. Further, when the content of the saturated hydrocarbon having an alicyclic structure is 70% by mass or less, the rub resistance of the obtained recorded matter tends to be further improved.

As the glycol monoether, a compound represented by the following formula (1) is preferable.
OH— (R ² O) _n —R ¹ (1)
In Formula (1), R ¹ represents an alkyl group having 1 to 7 carbon atoms, R ² represents an alkylene group having 1 to 3 carbon atoms, and n represents an integer of 1 to 7.

  The compound represented by formula (1) is not particularly limited, but ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol Monobutyl ether , Pentaethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether and the like. Among these, diethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, pentaethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether are exemplified.

  By containing the above-mentioned preferable glycol monoether, the chroma and the abrasion resistance of the obtained recorded matter are excellent, and there is a tendency that more excellent ejection stability can be obtained. A glycol monoether may be used individually by 1 type, or may use 2 or more types together.

  The glycol monoether described above preferably has a molecular weight of 251 or less, and more preferably has a molecular weight of 210 or less. Within such a range, the saturation tends to be good due to the difficulty of aggregation.

  The content of glycol monoether is preferably 20% by mass or less, more preferably 1.0% by mass or more and 15% by mass or less, and still more preferably 3% with respect to the total amount (100% by mass) of the composition. It is 0.0 mass% or more and 7.0 mass% or less. When the content of glycol monoether is 20% by mass or less, the storage stability tends to be more excellent. Further, when the content of glycol monoether is 1.0% by mass or more, the recorded matter obtained tends to be more excellent in chroma. In addition, content of the glycol monoether in a composition here is content containing the glycol monoether used for the dispersion liquid, for example.

  When the organic solvent further contains glycol diether, there is a tendency that a recorded matter that is more excellent in saturation and abrasion resistance is obtained. Specific examples of the glycol diether include, but are not limited to, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol Ethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol Methyl ether, and, dipropylene glycol diethyl ether. Among these, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and tetraethylene glycol dimethyl ether are preferable, and diethylene glycol ethyl methyl ether is more preferable.

  By containing the preferred glycol diether described above, the chroma and the abrasion resistance of the obtained recorded matter are excellent, and there is a tendency that a superior discharge stability can be obtained. A glycol diether may be used individually by 1 type, or may use 2 or more types together.

  The content of glycol diether is preferably 5.0% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, with respect to the total amount (100% by mass) of the composition. More preferably, it is 30 mass% or more and 70 mass% or less. When the content of glycol diether is in such a range, the chroma of the obtained recorded product tends to be more excellent. In addition, content of the glycol diether in a composition here is content containing also the glycol diether used for the dispersion liquid, for example.

  The total content of glycol diether and glycol monoether is preferably 30% by mass or more and 99.5% by mass or less, more preferably 40% by mass or more and 95% by mass with respect to the total amount (100% by mass) of the composition. % Or less, and more preferably 50% by mass or more and 80% by mass or less. When the total content of the glycol diether and the glycol monoether is within such a range, the chroma of the recorded matter obtained tends to be more excellent. The total content of glycol diether and glycol monoether in the composition here is, for example, a content including glycol diether and glycol monoether used in the dispersion.

  When the organic solvent further contains a cyclic lactone, there is a tendency that a recorded matter having excellent abrasion resistance can be obtained. The cyclic lactone is not particularly limited as long as it is a compound having a cyclic structure by an ester bond. For example, γ-lactone having a 5-membered ring structure, δ-lactone having a 6-membered ring structure, and ε- Examples include lactones. Specific examples of cyclic lactones are not particularly limited, but γ-butyrolactone, γ-valerolactone, γ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone, γ-decalactone, and γ-undeca. Examples include lactone, δ-valerolactone, δ-hexalactone, δ-heptalactone, δ-octalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, and ε-caprolactam. Among these, γ-lactone having a 5-membered ring structure and δ-lactone having a 6-membered ring structure are preferable, γ-butyrolactone, γ-valerolactone, and δ-valerolactone are more preferable, and γ-butyrolactone is further preferable. By containing such cyclic lactones, the abrasion resistance tends to be further improved. Cyclic lactones may be used alone or in combination of two or more.

  The content of the cyclic lactone is preferably 1.0% by mass or more and 50% by mass or less, more preferably 3.0% by mass or more and 40% by mass or less, with respect to the total amount (100% by mass) of the composition. More preferably, it is 5.0 mass% or more and 30 mass% or less. When the content of the cyclic lactone is 1.0% by mass or more, it tends to be excellent in abrasion resistance, and when the content of the cyclic lactone is 50% by mass or less, it tends to be excellent in chroma. It is in. In addition, content of cyclic lactone in the composition here is content which also contains cyclic lactone used for the dispersion liquid, for example.

  The content of the organic solvent is preferably 35% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and still more preferably with respect to the total amount (100% by mass) of the composition. It is 60 mass% or more and 90 mass% or less. In addition, content of the organic solvent in a composition here is content containing the organic solvent used for the dispersion liquid, for example.

<Resin>
The composition of this embodiment may further contain a resin mainly for the purpose of adjusting the viscosity of the composition. The resin is not particularly limited. For example, vinyl chloride such as acrylic resin, styrene acrylic resin, rosin modified resin, phenol resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride vinyl acetate copolymer resin, etc. Examples thereof include resin, fiber-based resin such as cellulose acetate butyrate, and vinyltoluene-α-methylstyrene copolymer resin. Among these, vinyl chloride resin is preferable, and vinyl chloride vinyl acetate copolymer resin is more preferable. By including such a resin, the rub resistance of the obtained recorded matter tends to be further improved. These resins may be used alone or in combination of two or more.

  The content of the resin is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5.0% by mass or less, with respect to the total amount (100% by mass) of the composition. More preferably, it is 0.5 mass% or more and 3.0 mass% or less. A composition having a resin content in such a range tends to be more excellent in abrasion resistance.

  The composition of this embodiment may contain 1 type, or 2 or more types of the arbitrary components which can be used for the conventional non-aqueous inkjet ink composition other than said each component. As such optional components, specifically, coloring materials such as dyes, surfactants, dispersants, penetrants, humectants, solubilizers, viscosity adjusters, pH adjusters, antioxidants, preservatives, Examples include antifungal agents, corrosion inhibitors, and chelating agents and other additives and solvents for capturing metal ions that affect dispersion. Each of these is used alone or in combination of two or more.

[Inkjet recording method]
The ink jet recording method of the present embodiment includes a step of recording on a recording medium by the ink jet method using the above-described non-aqueous composition. Specifically, droplets of the non-aqueous composition are ejected, and the droplets are attached to a recording medium, preferably a low-absorbing recording medium, to record an image.

In the present specification, the “low-absorbency recording medium” refers to a recording medium having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method. It is only necessary that the recording surface has this property. According to this definition, the “low-absorbing recording medium” in the present invention includes a non-absorbing recording medium that does not absorb water at all. This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  Specific examples of the low-absorbency recording medium include sheets, films, and textile products containing a low-absorbency material. The low-absorbency recording medium is a layer containing a low-absorbency material on the surface of a base material (for example, paper, fiber, leather, plastic, glass, ceramics, metal, etc.). May also be provided. Although it does not specifically limit as a low absorptive material, For example, an olefin resin, ester resin, urethane type resin, acrylic resin, and vinyl chloride type resin are mentioned.

  Among these, as the low-absorbency recording medium, a medium having a recording surface containing a vinyl chloride resin can be preferably used. Thereby, it exists in the tendency which can obtain the more outstanding chroma resulting from being excellent in the wet spreading property of the recorded matter obtained. Specific examples of the vinyl chloride resin include, for example, polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl ether copolymer, vinyl chloride-vinylidene chloride copolymer, Examples include vinyl chloride-maleic acid ester copolymers, vinyl chloride- (meth) acrylic acid copolymers, vinyl chloride- (meth) acrylic acid ester copolymers, and vinyl chloride-urethane copolymers. Note that there are no particular restrictions on the various properties such as thickness, shape, color, softening temperature, and hardness of the low-absorbency recording medium.

  By having the above composition, the non-aqueous composition of the present embodiment has an effect of excellent chroma and abrasion resistance, particularly for a low-absorbency recording medium, particularly a recording medium containing a vinyl chloride resin. Can be demonstrated. Therefore, according to the ink jet recording method according to the present embodiment, by attaching droplets of the non-aqueous composition to a low-absorbency recording medium, particularly a recording medium containing a vinyl chloride resin, saturation and An image having further excellent abrasion resistance can be recorded.

  The ink jet recording apparatus used in the ink jet recording method of the present embodiment is not particularly limited, but a drop-on-demand ink jet recording apparatus is preferable. The drop-on-demand ink jet recording apparatus employs a piezoelectric element recording method in which recording is performed using a piezoelectric element disposed in a recording head, and heat generated by a heater of a heating resistance element disposed in the recording head. There are methods that employ a thermal jet recording method in which recording is performed using energy, and any recording method can be employed. Hereinafter, an example of the ink jet recording apparatus of the present embodiment will be described in more detail.

[Inkjet recording apparatus]
A conventionally known ink jet printer can be used for the ink jet recording apparatus of the present embodiment. Examples of the ink jet printer include an ink jet printer as shown in FIG. 1 (hereinafter, also simply referred to as “printer”).

  FIG. 1 is a perspective view illustrating a configuration of a printer 1 according to the present embodiment. As shown in FIG. 1, a printer 1 includes an ink jet recording head 2 and a carriage 4 on which an ink cartridge 3 is detachably mounted, and is disposed below the ink jet recording head (ink jet head) 2 and is to be recorded. A platen 5 to which the medium 6 is conveyed, a carriage moving mechanism 7 for moving the carriage 4 in the medium width direction (main scanning direction S) of the recording medium 6, and a medium feeding mechanism for conveying the recording medium 6 in the medium feeding direction. 8. In addition, the printer 1 has a control unit CONT that controls the operation of the entire printer 1.

  The recording head 2 includes a cavity that discharges the accommodated non-aqueous composition from the nozzle, a discharge driving unit that is provided for each cavity, and applies a driving force for discharging the non-aqueous composition. And a nozzle for discharging the non-aqueous composition to the outside of the head. A plurality of cavities, and ejection drive units and nozzles provided for each cavity may be provided in one head independently of each other. The discharge drive unit uses an electromechanical conversion element such as a piezoelectric element that changes the volume of the cavity by mechanical deformation, or an electrothermal conversion element that generates and discharges bubbles in a non-aqueous composition by generating heat. Can be formed. The printer 1 may be provided with one head or a plurality of heads per one non-aqueous composition.

  The ink cartridge 3 is composed of a plurality of independent cartridges, and the above-described non-aqueous composition is filled in each cartridge. Note that the cartridge filled with the non-aqueous composition does not have to be mounted on the carriage 4 during normal printing, and if it is mounted on the carriage 4 at least when cleaning the flow path of the non-aqueous composition. Good.

  The platen 5 includes a platen heater and is configured to heat the recording medium to a set temperature. The recording head 2 has no built-in heater. However, the temperature of the recording head increases as a result of heating the recording medium, and the temperature of the non-aqueous composition contained in the recording head 2 tends to increase. Although not shown, the printer 1 may include an after heater in the recording medium discharge path downstream of the platen heater.

  The non-aqueous composition of this embodiment described above is ejected from the recording head 2. Here, the temperature of the platen when the non-aqueous composition is discharged from the recording head 2 is preferably 35 ° C. or higher, and more preferably 40 ° C. or higher. Further, the temperature of the platen when the non-aqueous composition is discharged from the recording head 2 is preferably 80 ° C. or less, more preferably 70 ° C. or less, still more preferably 60 ° C. or less, and particularly preferably 50 ° C. or less. It is preferable in that the quality of the recorded matter can be further improved by setting the platen to a temperature within the above range with a platen heater.

  In the present embodiment, it is preferable that the ejection frequency when ejecting from the recording head 2 is 1.0 kHz or more and 200 kHz or less. When the discharge frequency is less than or equal to the above, it is preferable from the viewpoint that the discharge stability is more excellent. A discharge frequency means the discharge frequency of the discharge unit of 1 non-aqueous composition droplet. The discharge frequency is preferably 2.0 kHz or more, more preferably 3.0 kHz or more, still more preferably 5.0 kHz or more, and particularly preferably 10 kHz or more from the viewpoint of further increasing the recording speed. The discharge frequency is preferably 200 kHz or less, more preferably 150 kHz or less, still more preferably 100 kHz or less, and particularly preferably 50 kHz or less, from the viewpoint of further improving discharge stability. Furthermore, the discharge frequency is preferably 20 kHz or less, and more preferably 15 kHz or less, from the viewpoint of further improving the discharge stability while ensuring the recording speed. On the other hand, the discharge frequency is preferably 15 kHz or more, and more preferably 20 kHz or more, from the viewpoint of further improving the recording speed while ensuring the discharge stability.

  As the printer 1 of this embodiment, a so-called on-carriage type printer in which the ink cartridge 3 is mounted on the carriage 4 is illustrated, but the printer 1 is not limited to this. For example, a so-called off-carriage in which an ink container (for example, ink pack, ink cartridge, etc.) filled with a non-aqueous composition is attached to the housing of the printer 1 and supplied to the head 2 via an ink supply tube. It may be a type of printer.

  In the ink jet recording apparatus of the present embodiment, an ink set having a plurality of non-aqueous compositions can be used. The ink set of the present embodiment may have a plurality of non-aqueous inkjet compositions of the present embodiment, and in addition, a non-aqueous composition different from the non-aqueous inkjet composition of the present embodiment (others It may further have a non-aqueous composition). In this case, the ink set may be an ink set having the non-aqueous composition of the present embodiment as magenta ink and the other non-aqueous composition as yellow ink and cyan ink. An ink set having a non-aqueous composition as a red ink and other non-aqueous compositions as a magenta ink, a yellow ink, and a cyan ink may be used. From the viewpoint of more excellent color reproducibility, it is preferable to use the non-aqueous composition of this embodiment as a red ink and to use it together with other non-aqueous compositions, magenta ink, yellow ink, and cyan ink. .

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples and comparative examples as long as the gist thereof is not exceeded.

The main materials for non-aqueous compositions used in the following examples and comparative examples are as follows.
[For non-aqueous compositions]
[Pigment]
C. I. Pigment Red 254 (PR-254, average particle size 170 nm) (trade name Pigment Red 254, manufactured by Tokyo Chemical Industry Co., Ltd.)
C. I. Pigment Red 177 (PR-177, average particle size 170 nm) (trade name Pigment Red 177 manufactured by Hangzhou Xcolor Chemical Company)
C. I. Pigment Red 179 (PR-179, average particle size 170 nm) (trade name Pigment Red 179, manufactured by Gaoyou Auxiliary Factory)
C. I. Pigment Red 224 (PR-224, average particle size 170 nm) (trade name Pigment Red 224, manufactured by Hangzhou Xcolor Chemical Company)
〔Organic solvent〕
Cyclooctane (C ₈ H ₁₆ ) (Tokyo Chemical Industry Co., Ltd., trade name Cyclooctane)
Cyclononane (C ₉ H ₁₈ ) (HONEST JOY HOLDINGS LIMITED, trade name Cyclononane)
Cyclodecane (C ₁₀ H ₂₀ ) (manufactured by Tokyo Chemical Industry Co., Ltd., trade name Cyclodecane)
Cycloundecane (C ₁₁ H ₂₂ )
Cyclododecane (C ₁₂ H ₂₄ ) (Tokyo Chemical Industry Co., Ltd., trade name Cyclododecane)
Cyclotridecane (C ₁₃ H ₂₆ ) (CARBONE SCIENTIFIC CO., LTD, trade name CYCLOTRIDECANE)
Cyclotetradecane (C ₁₄ H ₂₈ ) (CARBONE SCIENTIFIC CO., LTD, CYCLOTETRADECANE)
Cyclooctanol (C ₈ H ₁₆ O) (manufactured by Tokyo Chemical Industry Co., Ltd., trade name Cyclooctanol)
Cyclononanol (C ₉ H ₁₈ O)
Decane (C ₁₀ H ₂₂ ) (trade name Decane, manufactured by Tokyo Chemical Industry Co., Ltd.)
Diethylene glycol methyl ethyl ether (flash point 64 ° C) (manufactured by Nippon Emulsifier Co., Ltd., trade name MEDG)
Diethylene glycol diethyl ether (flash point 71 ° C) (made by Nippon Emulsifier Co., Ltd., trade name DEDG)
Diethylene glycol monomethyl ether (flash point 105 ° C) (manufactured by Nippon Emulsifier Co., Ltd., trade name MDG)
Dipropylene glycol monomethyl ether (flash point 76.5 ° C) (Tokyo Chemical Industry Co., Ltd., trade name Dipropylene Glycol Monomethyl Ether)
Triethylene glycol monobutyl ether (flash point 156 ° C) (manufactured by Tokyo Chemical Industry Co., Ltd., trade name Triethylen Glycol Monobutyl Ether)
Tripropylene glycol monomethyl ether (flash point: 123 ° C) (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: Tripropylene Glycol Monomethyl Ether)
Tetraethylene glycol monobutyl ether (flash point 166 ° C.) (KH Neochem, trade name butysenol 40)
Pentaethylene glycol monomethyl ether (flash point 154.7 ° C.) (trade name: Pentaethylene Glycol Monomethyl Ether, manufactured by Tokyo Chemical Industry Co., Ltd.)
γ-Butyrolactone (trade name γ-Butyrolactone, manufactured by Tokyo Chemical Industry Co., Ltd.)
δ-Valerolactone (trade name δ-Valerolactone, manufactured by Tokyo Chemical Industry Co., Ltd.)
[Dispersant]
BYK-2050 (Bic Chemie Japan product name)
[Surfactant]
Neugen LP-70 (trade name, manufactured by Daiichi Kogyo Co., Ltd.)
〔resin〕
Solvain CL (vinyl chloride vinyl acetate copolymer resin, trade name manufactured by Nissin Chemical Industry Co., Ltd.)

(Preparation of pigment dispersion)
Pigment Red 254 (PR-254) having a primary particle diameter of 170 nm was prepared as a pigment. Next, by using BYK-2050 (trade name, manufactured by Big Chemie Japan Co., Ltd.) as a dispersant, a dispersion is prepared by changing the addition amount of the dispersant within a mass ratio of 0.1 to 20% by mass with respect to the pigment. By doing so, dispersion with a desired volume average particle size dispersion was performed. As a dispersion medium, a pigment dispersion liquid was prepared using a solvent having the largest content as a solvent for each ink composition as a dispersion medium. In addition, about PR-254 which has a volume average particle diameter smaller than a primary particle size, it grind | pulverized with the ball mill and obtained PR-254 of the desired volume average particle diameter.

  The volume average particle size of the pigment is measured by a laser diffraction / scattering method (Microtrac UPA250, manufactured by Nikkiso Co., Ltd.) in an environment of 20 ° C. by diluting the obtained pigment dispersion with diethylene glycol diethyl ether to 1000 ppm or less. The volume average particle diameter (median diameter D50) was measured. As a result, C.I. having an average particle size of 50 nm, 100 nm, 240 nm, and 300 nm. I. Pigment Red 254 was obtained.

[Preparation of non-aqueous composition]
Each material was mixed by the composition shown in the following Table 1 and Table 2, and stirred sufficiently to obtain each composition. In Tables 1 and 2 below, the unit of numerical values is mass%, and the total is 100.0 mass%.

[Preparation of recorded material]
A transparent PET medium (manufactured by Lintec Corporation, model number “E-1000ZC”), which is a recording medium, is carried into an ink jet printer (trade name “SC-S70650” manufactured by Seiko Epson Corporation), and examples and comparative examples are provided in the discharge head. Each composition obtained was filled and discharged under the conditions of 100% concentration, resolution 720 × 1440 dpi, 18 mg / inch ² and dried at 25 ° C. and 65% RH (relative humidity) for 1 day. Each recorded matter was obtained.

(Evaluation 1) Storage stability Each composition obtained in Examples and Comparative Examples was placed in a sealed container and allowed to stand for 4 weeks in an environment at 60 ° C., and the viscosity of the composition before and after being left was measured as HAAKE Rheometer RS75 (Product) Name, Thermo Fisher Scientific viscometer). Next, the rate of change in the viscosity of the ink was determined by the following formula, and the storage stability was evaluated according to the following evaluation criteria. The obtained results are shown in Tables 1 and 2.
Viscosity change rate = {(viscosity value after 4 weeks) / (initial viscosity value) × 100} -100 (%)
(Evaluation criteria)
3: Viscosity change rate is less than 2% 2: Viscosity change rate is 2% or more and less than 3% 1: Viscosity change rate is 3% or more

(Evaluation 2) Image quality (saturation)
Each recorded matter was evaluated for saturation (C ^* ). Specifically, the a * value and b * value were measured using Spectrolino (trade name, a spectrophotometer manufactured by Gretag Macbeth Co., Ltd.) for each recorded matter, C * was calculated, and the following evaluation was performed. The saturation was evaluated according to the standard. The value of C * was an integer value obtained by rounding off the decimal point of the calculated value of C *. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
4: C ^* value is 100 or more 3: C ^* value is 90 to 99
2: C ^* value is 80-89
1: C ^* value is 79 or less

(Evaluation 3) Discharge stability Each composition obtained in Examples and Comparative Examples was filled in an ink jet printer (trade name “SC-S70650” manufactured by Seiko Epson Corporation). Subsequently, ejection was performed at a frequency of 5 kHz from an inkjet head having 360 nozzles, and a solid pattern was continuously formed on a transparent PET medium (manufactured by Lintec Corporation, model number “E-1000ZC”) for 300 seconds ( After L dots (600 × 600 dpi), the ejection was stopped and this was taken as one sequence. Thereafter, the same operation was repeated 10 sequences. From the solid pattern of the recorded matter thus obtained, missing ink dots, flying curves, and scattering were confirmed. The nozzles in which these phenomena were confirmed were determined as defective nozzles, and the ratio of defective nozzles among all nozzles was counted to evaluate the ejection stability. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
3: The number of defective nozzles is 0 2: The number of defective nozzles is 1 to 4 1: The number of defective nozzles is 5 or more

(Evaluation 4) Abrasion resistance Each of the obtained recorded materials was subjected to a cotton cloth (trade name “AB-301”, manufactured by Tester Sangyo Co., Ltd.) according to JIS K5701 (ISO11628). With a friction element attached with a gold width No. 20), the load was rubbed 20 times with a load of 500 g. And the rubbing trace and peeling of the recorded matter of the recording medium were visually observed, and the abrasion resistance was evaluated according to the following evaluation criteria. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
3:20 After reciprocating rubbing, the cotton cloth is free from dirt (attachment), and the recorded matter is not damaged.
2: After two-way rubbing, dirt (adhered matter) is observed on the cotton cloth, but no scratches are observed on the recorded matter.
After 1:20 reciprocating rubbing, the cotton cloth is soiled (attachment) and scratches are observed on the recorded matter.

  By comparing the Examples and Comparative Examples shown in Tables 1 and 2, it was found that the non-aqueous ink jet composition according to the present invention can provide a recorded material with excellent abrasion resistance and saturation. Furthermore, it was found that the non-aqueous inkjet composition is excellent in ejection stability and storage stability.

  DESCRIPTION OF SYMBOLS 1 ... Printer, 2 ... Inkjet recording head, 3 ... Ink cartridge, 4 ... Carriage, 5 ... Platen, 6 ... Recording medium, 7 ... Carriage moving mechanism, 8 ... Medium feed mechanism, 70 ... Ink pack, 72 ... Cartridge Case, 74 ... Ink supply port, 76 ... Main body case, 78 ... Cover

Claims (11)

A pigment containing a diketopyrrolopyrrole pigment, and an organic solvent,
The organic solvent is a non-aqueous inkjet composition containing glycol monoether and a saturated hydrocarbon having an alicyclic structure.   The non-aqueous inkjet composition according to claim 1, wherein the saturated hydrocarbon having an alicyclic structure has 8 or more and 14 or less carbon atoms.   The non-aqueous inkjet composition according to claim 1 or 2, wherein a content of the saturated hydrocarbon having an alicyclic structure is 20% by mass or more and 70% by mass or less with respect to a total amount of the non-aqueous inkjet composition. . The non-aqueous inkjet composition according to any one of claims 1 to 3, wherein the glycol monoether includes a compound represented by the following formula (1).
OH— (R ² O) _n —R ¹ (1)
(In formula (1), R ¹ represents an alkyl group having 1 to 7 carbon atoms, R ² represents an alkylene group having 1 to 3 carbon atoms, and n represents an integer of 1 to 7)   The non-aqueous inkjet composition according to any one of claims 1 to 4, wherein a content of the glycol monoether is 20% by mass or less based on a total amount of the non-aqueous inkjet composition.   The non-aqueous inkjet composition according to any one of claims 1 to 5, wherein an average particle size of the diketopyrrolopyrrole pigment is 100 nm or more and 240 nm or less.   The non-aqueous inkjet according to any one of claims 1 to 6, wherein a content of the pigment is 1.0% by mass or more and 5.0% by mass or less with respect to a total amount of the non-aqueous inkjet composition. Composition.   The non-aqueous inkjet composition according to any one of claims 1 to 7, wherein the organic solvent further contains glycol diether.   The non-aqueous inkjet composition according to any one of claims 1 to 8, wherein the organic solvent further contains a cyclic lactone.   The non-aqueous inkjet composition according to any one of claims 1 to 9, further comprising a vinyl chloride resin.   The inkjet recording method which has the process of recording on a recording medium by the inkjet method using the inkjet composition as described in any one of Claims 1-10.

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