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WO2016002834A1 - Encre pour jet d'encre durcissable sous l'effet d'une lumière active, et procédé de formation d'image - Google Patents

Encre pour jet d'encre durcissable sous l'effet d'une lumière active, et procédé de formation d'image Download PDF

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Publication number
WO2016002834A1
WO2016002834A1 PCT/JP2015/068970 JP2015068970W WO2016002834A1 WO 2016002834 A1 WO2016002834 A1 WO 2016002834A1 JP 2015068970 W JP2015068970 W JP 2015068970W WO 2016002834 A1 WO2016002834 A1 WO 2016002834A1
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WIPO (PCT)
Prior art keywords
general formula
ink
inkjet ink
curable inkjet
compound
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PCT/JP2015/068970
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English (en)
Japanese (ja)
Inventor
由佳 矢崎
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2016531416A priority Critical patent/JP6569674B2/ja
Publication of WO2016002834A1 publication Critical patent/WO2016002834A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present invention relates to an actinic ray curable inkjet ink and an image forming method.
  • An ink jet recording system using an actinic ray curable ink jet ink is used in various printing fields because it can form an image easily and inexpensively.
  • an ultraviolet curable ink jet method in which droplets of ultraviolet curable ink jet ink are landed on a recording medium and then cured by irradiation with ultraviolet rays to form an image.
  • the ultraviolet curable ink jet recording method has been attracting attention in recent years because an image having high scratch resistance and adhesion can be formed even on a recording medium having no ink absorbability.
  • Patent Document 1 there is a method for printing on a substrate with radiation curable ink, (1) a step of preparing the substrate on a support, and (2) inkjet printing at an operating temperature.
  • This material is soluble in the carrier composition at the operating temperature of the ink jet print head and when received into the substrate.
  • the radiation curable ink to which a gelling agent is added causes a phase change instantaneously when landing on a recording medium such as plain paper, thereby preventing mixing of droplets, and high-speed printing. It is also possible to form an image.
  • the stealth type ink composition emits visible light when irradiated with ultraviolet rays without exhibiting significant absorption in the visible light region, and the recording speed is
  • a method for recording a stealth ink composition characterized in that it is 10 ips or more with respect to the traveling direction of the recording medium, and no post-treatment is performed after dot formation. According to Patent Document 2, it is possible to print at a high speed in order to process a large number of printed materials in a short time using various recording media.
  • Patent Document 3 an amorphous compound; and a phase change ink comprising a crystalline compound; wherein the phase change ink can crystallize with a total crystallization time of less than 15 seconds. It is disclosed.
  • the ink of Patent Document 3 can be suitably used for high-speed ink jet printing by adjusting the ratio of the amount of the amorphous material in the ink composition to adjust the crystallization speed of the ink composition.
  • the ink jet recording method using the actinic ray curable ink jet ink can cope with high-speed printing.
  • a gelling agent particularly a crystalline gelling agent may be added to the actinic ray curable inkjet ink.
  • the ink does not spread too much and the ink spreads uniformly, so that density unevenness of the printed image is suppressed.
  • the curability of the ink will be good, and stickiness of the ink surface will be suppressed.
  • the glossiness of the image required varies depending on the printing application, and there is an expectation to obtain an image with a glossiness different from that of an image obtained by simply adding a gelling agent by controlling the glossiness. To do.
  • the present invention has been made in view of the above circumstances, and actinic ray curing capable of controlling the image gloss while maintaining the pinning property and leveling property of the inkjet ink and suppressing density unevenness and surface stickiness. It is an object of the present invention to provide an ink jet ink and an image forming method using such an actinic ray curable ink jet ink.
  • the present inventor has an ester value having a branched structure of 2 or more in an actinic ray curable inkjet containing a gelling agent, particularly a crystalline gelling agent. It has been found that by adding a polyvalent ester compound containing at least one compound, it is possible to surprisingly form an image having an image glossiness different from an image using a conventional ink containing a gelling agent, The present invention has been completed.
  • an actinic ray curable inkjet ink comprising a gelling agent, a polyvalent ester compound, and a photopolymerizable compound
  • the gelling agent is a compound represented by the following general formula (G1), a compound represented by the following general formula (G2), a compound represented by the following general formula (G3), and the following general formula ( Including at least one compound selected from the group consisting of compounds represented by G4),
  • the content of the gelling agent is 1 to 10% by mass with respect to the total mass of the actinic ray curable inkjet ink
  • the polyvalent ester compound is at least one selected from the group consisting of a compound having a pentaerythritol structure and an ester value of 2 or more, and a compound having a dipentaerythritol structure and an ester value of 2 or more.
  • R3 and Each R4 independently represents a hydrocarbon group which includes a straight chain portion having 11 or more carbon atoms and may include a branched portion; in the general formula (G3), R5 includes a straight chain portion having 19 or more carbon atoms; Represents a hydrocarbon group that may include a branched portion, and in the general formula (G4), R6 represents a hydrocarbon group that includes a straight chain portion having 14 or more carbon atoms and may include a branched portion.
  • the gelling agent includes two or more compounds selected from the group consisting of the compound represented by the general formula (G1) and the compound represented by the general formula (G2), R1 and R2 in the general formula (G1) each independently represent a hydrocarbon group that includes a straight chain portion having 11 or more carbon atoms and may include a branched portion, and the R1 and R2 in the general formula (G2) R3 and R4 each independently represent a hydrocarbon group containing a straight chain part having 13 or more carbon atoms and optionally containing a branched part,
  • the content of the polyvalent ester compound is 0.01 to 5% by mass with respect to the total mass of the actinic radiation curable inkjet ink, according to (1) or (2) Actinic ray curable inkjet ink.
  • the gelling agent contains two or more kinds of compounds represented by the general formula (G2), In the general formula (G2), R3 and R4 each independently represent a hydrocarbon group containing a straight chain part having 15 or more carbon atoms and optionally containing a branched part, Item (1) to Item (3), wherein the content of the polyvalent ester compound is 0.01 to 3% by mass relative to the total mass of the actinic radiation curable inkjet ink.
  • the present invention also relates to an image forming method described in item (5) below.
  • (5) A step of ejecting the actinic radiation curable inkjet ink according to any one of items (1) to (4) onto a recording medium, and the actinic radiation curable inkjet ink ejected onto the recording medium And irradiating the actinic ray with an actinic ray to cure the actinic ray curable inkjet ink.
  • an actinic ray curable inkjet ink capable of controlling the image gloss while maintaining the pinning property and leveling property of the inkjet ink.
  • FIG. 1A is a side view showing an example of a configuration of a main part of an ink jet recording apparatus 10 of a line recording system, which is one aspect of an ink jet recording apparatus using an actinic ray curable ink jet ink according to the present invention.
  • FIG. 1B is a top view illustrating an example of a configuration of a main part of a line recording type inkjet recording apparatus 10 which is one aspect of an inkjet recording apparatus in which the actinic ray curable inkjet ink according to the present invention is used.
  • FIG. 2 is a top view showing an example of a configuration of a main part of a serial recording type inkjet recording apparatus 20 in which the actinic ray curable inkjet ink according to the present invention is used.
  • Actinic ray curable inkjet ink includes a gelling agent, a polyvalent ester compound, a photopolymerizable compound, An actinic ray curable ink-jet ink comprising a compound represented by the following general formula (G1), a compound represented by the following general formula (G2), and the following general formula (G3) And at least one compound selected from the group consisting of compounds represented by the following general formula (G4), and the gelling agent content is the total mass of the actinic radiation curable inkjet ink: 1 to 10% by mass of the polyvalent ester compound, a compound having a pentaerythritol structure and an ester value of 2 or more, and dipentaerythris An actinic ray curable inkjet ink comprising at least one compound selected from the group consisting of compounds having a lithol structure and an este
  • R1 and R2 each independently represent a hydrocarbon group that includes a straight chain portion having 9 or more carbon atoms and may include a branched portion.
  • R3 and R4 each represent Independently, it represents a hydrocarbon group that includes a straight chain portion having 11 or more carbon atoms and may include a branched portion.
  • R5 includes a straight chain portion having 19 or more carbon atoms and includes a branched portion.
  • R6 represents a hydrocarbon group that includes a straight chain portion having 14 or more carbon atoms and may include a branched portion.
  • the actinic radiation curable inkjet ink of the present invention contains a gelling agent, pinning and leveling properties equivalent to those of conventional inkjet inks containing a gelling agent can be maintained. Since the actinic ray curable inkjet ink of the present invention contains a polyvalent ester compound in addition to the gelling agent, the glossiness of the image is controlled to form an image having a lower glossiness than that of the conventional inkjet ink. be able to.
  • the gelling agent contained in the conventional ink-jet ink has a clean crystal structure with a plate-like surface structure and a uniform arrangement. Therefore, the surface of the cured ink is smooth, has high reflectivity, and high gloss. An image is formed.
  • the polyvalent ester compound having a branched structure contained in the actinic ray curable inkjet ink of the present invention becomes an amorphous crystal having no plate-like surface structure. Therefore, in the actinic ray curable ink-jet ink of the present invention, unevenness is formed on the surface by the crystal of the polyvalent ester compound having a branched structure, and an image with low glossiness can be formed.
  • the gelling agent contained in the actinic radiation curable inkjet ink of the present invention includes a compound represented by the following general formula (G1), a compound represented by the following general formula (G2), and the following general formula (G3). And at least one compound selected from the group consisting of compounds represented by the following general formula (G4).
  • R1 and R2 each independently represent a hydrocarbon group that includes a straight chain portion having 9 or more carbon atoms and may include a branched portion.
  • R3 and R4 each represent Independently, it represents a hydrocarbon group that includes a straight chain portion having 11 or more carbon atoms and may include a branched portion.
  • R5 includes a straight chain portion having 19 or more carbon atoms and includes a branched portion.
  • R6 represents a hydrocarbon group that includes a straight chain portion having 14 or more carbon atoms and may include a branched portion.
  • the gelling agent contained in the actinic radiation curable inkjet ink of the present invention has a function of reversibly sol-gel phase transition of the actinic radiation curable inkjet ink according to the present invention depending on temperature.
  • the gelling agent is preferably soluble in the photopolymerizable compound at a temperature higher than the gelation temperature, and may be crystallized in the actinic ray curable inkjet ink according to the present invention at a temperature equal to or lower than the gelation temperature.
  • the gelling agent is crystallized in the inkjet ink, it is preferable to form a space three-dimensionally surrounded by plate crystals which are crystallized products of the gelling agent, and encapsulate the photopolymerizable compound in the space.
  • the structure in which the photopolymerizable compound is encapsulated in the space three-dimensionally surrounded by the plate crystal is sometimes referred to as “card house structure”.
  • the liquid photopolymerizable compound can be held, and the droplets of the actinic ray curable inkjet ink can be pinned. Thereby, coalescence of droplets can be suppressed.
  • the photopolymerizable compound dissolved in the ink and the gelling agent are compatible.
  • the photopolymerizable compound dissolved in the ink and the gelling agent are phase-separated, it may be difficult to form a card house structure.
  • the gelling agent contained in the actinic ray curable inkjet ink of the present invention is easily compatible with the photopolymerizable compound in the ink and easily forms a card house structure.
  • the gelling agent contained in the actinic radiation curable inkjet ink of the present invention includes a compound represented by the above general formula (G1), a compound represented by the above general formula (G2), and the above general formula (G3). Two or more compounds selected from the group consisting of the compound represented by formula (G4) and the compound represented by the above general formula (G4) may be included, and pinning properties and leveling of the ink can be achieved by including two or more compounds. Improves the properties and suppresses uneven density and surface stickiness.
  • the gelling agent contained in the actinic radiation curable inkjet ink of the present invention is selected from the group consisting of the compound represented by the general formula (G1) and the compound represented by the general formula (G2).
  • the gelatinizer contained in the actinic-light curable inkjet ink of this invention contains 2 or more types of compounds represented by general formula (G2).
  • general formula (G1) or the general formula (G2) nonpolar hydrocarbon groups are arranged on both sides of an ester group or a ketone group which is a polar group. Crystals of these compounds tend to gather around an ester group or a ketone group in a solvent, and at that time, a card house structure is easily formed by taking a clean crystal structure with a planar structure. For this reason, the pinning property and leveling property are improved, and it is considered that density unevenness and surface stickiness of the formed image are suppressed.
  • the compatibility between the photopolymerizable compound and the gelling agent is good in the sol-like ink (at high temperature). It is necessary to be. Furthermore, in order to stably suppress coalescence of droplets even during high-speed printing, after the inkjet ink droplets have landed on the recording medium, the gelling agent quickly crystallizes to form a strong card house structure. It is preferable.
  • R1 and R2 each independently represents a hydrocarbon group containing a straight chain part having 9 or more carbon atoms and optionally containing a branched part. It is preferable that the straight chain part contained in R1 and R2 has 11 or more carbon atoms. If the number of carbon atoms in the straight chain portion contained in R1 and R2 is 9 or more, it functions well as a gelling agent because it has sufficient crystallinity, and in the card house structure described above, a photopolymerizable compound is used. A sufficient space for inclusion can be formed. On the other hand, in order to appropriately suppress the melting point of the gelling agent and increase the solubility of the gelling agent in the ink, the number of carbon atoms in the linear portion contained in R1 and R2 is preferably less than 25.
  • Examples of the compound represented by the above general formula (G1) include dilignoceryl ketone (C23-C23), dibehenyl ketone (C21-C21, melting point 88 ° C.), distearyl ketone (C17-C17, melting point 84 ° C.).
  • Examples of commercially available compounds represented by the general formula (G1) include 10-Nonadecanone (manufactured by Tokyo Chemical Industry Co., Ltd.), 12-Tricosanone (manufactured by Tokyo Chemical Industry Co., Ltd.), 16-Hentriacontanone (manufactured by Tokyo Chemical Industry Co., Ltd.) , 18-Pentriacontanon (AlfaAlAeser), Hentriacontan-16-on (AlfaesAeser), Kao Wax T1 (Kao Corporation), and the like.
  • R3 and R4 each independently represent a hydrocarbon group that includes a straight chain portion having 11 or more carbon atoms and may include a branched portion.
  • the number of carbon atoms in the linear portion contained in R3 and R4 is preferably 13 or more, and more preferably 15 or more.
  • the number of carbon atoms in the straight chain portion contained in R3 and R4 is 11 or more, it functions well as a gelling agent because it has sufficient crystallinity, and in the card house structure described above, a photopolymerizable compound is used. A sufficient space for inclusion can be formed.
  • the number of carbon atoms in the linear portion contained in R1 and R2 is preferably less than 26.
  • Examples of the compound represented by the general formula (G2) include behenyl behenate (C21-C22, melting point 70 ° C.), icosyl icosanoate (C19-C20), behenyl stearate (C17-C22, melting point 70 ° C.), Stearyl stearate (C17-C18, melting point 60 ° C.), palmityl stearate (C17-C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16, melting point 54 ° C.), stearyl palmitate (C15- C18), myristyl myristate (C13-C14, melting point 43 ° C.), cetyl myristate (C13-C16, melting point 50 ° C.), octyldodecyl myristate (C13-C20), stearyl oleate (C17-C18), erucic acid Stearyl (C21-
  • Examples of commercial products of the compound represented by the general formula (G2) include Unistar M-2222SL (manufactured by NOF Corporation), EXCEPARL SS (manufactured by Kao Corporation, melting point 60 ° C.), EMALEXCC-18 (Japan Emulsion Co., Ltd.) Company), Amreps PC (manufactured by Higher Alcohol Industry Co., Ltd.), EXCEPARL MY-M (manufactured by Kao Corporation), SPALM ACETI (manufactured by NOF Corporation), EMALEX® CC-10 (manufactured by Nippon Emulsion Co., Ltd.), etc. . Since these commercial products are often a mixture of two or more types, they may be separated and purified as necessary.
  • R5 represents a hydrocarbon group that includes a straight chain portion having 19 or more carbon atoms and may include a branched portion.
  • the straight chain portion contained in R5 preferably has 21 or more carbon atoms.
  • the number of carbon atoms in the straight chain portion contained in R5 is 19 or more, it functions well as a gelling agent because it has sufficient crystallinity, and includes the photopolymerizable compound in the card house structure described above. Sufficient space can be formed.
  • the number of carbon atoms in the linear portion contained in R5 is preferably less than 31.
  • Examples of the compound represented by the general formula (G3) include behenic acid (C21), arachidic acid (C19) and the like.
  • the number of carbons in parentheses represents (the number of carbons in R5).
  • Examples of commercially available compounds represented by the general formula (G3) include Lunac BA (manufactured by NOF Corporation), Arachidic acid (Wako Pure Chemical Industries, Reagents) and the like.
  • R6 represents a hydrocarbon group that includes a straight chain portion having 14 or more carbon atoms and may include a branched portion.
  • the straight chain portion contained in R6 preferably has 16 or more carbon atoms, more preferably 18 or more.
  • the number of carbon atoms in the straight chain portion contained in R5 is 14 or more, it functions well as a gelling agent because it has sufficient crystallinity, and includes the photopolymerizable compound in the card house structure described above. Sufficient space can be formed.
  • the number of carbon atoms in the linear portion contained in R6 is preferably less than 34.
  • Examples of the compound represented by the general formula (G4) include myristyl alcohol (C14), palmityl alcohol (C16) stearyl alcohol (C18), behenyl alcohol (C22) and the like.
  • the carbon number in parentheses represents (the carbon number of R6).
  • Examples of commercial products of the compound represented by the general formula (G4) include calcoal 4098 (manufactured by Kao), cetanol H (manufactured by higher alcohol industry), calcoal 8098 (manufactured by Kao), behenyl alcohol 80R (manufactured by higher alcohol industry), and the like. Is included.
  • the content of the gelling agent is 1 to 10% by mass, preferably 1 to 5% by mass, and preferably 1 to 3% by mass with respect to the total mass of the actinic ray curable inkjet ink of the present invention. Is more preferable.
  • the compound represented by the general formula (G1) R1 and R2 are each independently a straight chain having 11 or more carbon atoms.
  • a compound represented by the general formula (G2) R3 and R4 each independently include a straight chain portion having 13 or more carbon atoms, and a branched portion.
  • the polyvalent ester compound contained in the actinic radiation curable inkjet ink of the present invention includes a compound having a pentaerythritol structure and an ester value of 2 or more, and a compound having a dipentaerythritol structure and an ester value of 2 or more, Including at least one compound selected from the group consisting of: 2 or more compounds.
  • the polyvalent ester compound contained in the actinic radiation curable inkjet ink of the present invention is a compound having a branched structure and an ester value of 2 or more.
  • the compound having a pentaerythritol structure and an ester value of 2 or more and the compound having a dipentaerythritol structure and an ester value of 2 or more are compounds represented by the following general formulas (1) to (11). However, it is not limited to the compounds represented by the general formulas (1) to (11) as long as the object of the present invention is achieved and the effects of the present invention are achieved.
  • R 1 to R 39 in the general formulas (1) to (11) each independently represents a linear alkyl group having 9 or more carbon atoms, and represents a linear alkyl group having 14 or more carbon atoms. And more preferably a linear alkyl group having 16 or more carbon atoms.
  • the polyvalent ester compound contained in the actinic radiation curable inkjet ink of the present invention may contain one type of compound selected from the compounds represented by the general formulas (1) to (11), and two or more types of compounds May be included.
  • Specific examples of the compounds represented by the general formulas (1) to (11) include pentaerythritol trimyristate (C13, general formula 3), pentaerythritol distearate (C17, general formula 2), pentaerythritol tetra Palmitic acid ester (C15, general formula 3), dipentaerythritol tetralignoceric acid ester (C23, general formula 6 or 7), dipentaerythritol tetrabehenate ester (C21, general formula 6 or 7), pentaerythritol tetraarachi Diester (C19, general formula 1), dipentaerythritol hexastearate (C17, general formula 4), dipentaerythritol pentapalmitate (C15, general formula 5) dipentaerythritol tribehenate (C21, General formula 8 or 9), dipentaerythritol myristate (C13, the
  • the content of the polyvalent ester compound may be any amount as long as the object of the present invention can be achieved and the effects of the present invention can be achieved, but 0.01% with respect to the total mass of the actinic radiation curable inkjet ink of the present invention. It is preferably from 10% to 10% by mass, preferably from 0.01% to 5% by mass, more preferably from 0.01% to 3% by mass, and 0.3% by mass. % To 3% by mass, more preferably 0.5% to 1% by mass.
  • the content of the polyvalent ester compound is 10% by mass or more, the surface of the cured ink derived from the crystal of the polyvalent ester compound becomes more sticky, and as a result, the glossiness of the image is increased. End up.
  • the content of the polyvalent ester compound is 5% by mass or less, the stickiness of the surface of the cured ink can be further suppressed and the glossiness can be further lowered.
  • the content of the polyvalent ester compound is 3% by mass or less, the stickiness of the surface of the cured ink can be further suppressed and the glossiness can be further lowered.
  • the content of the polyvalent ester compound which is a more preferable embodiment, is 0.01 to 3% by mass
  • two or more kinds of compounds represented by the general formula (G2) R3 and R4 are each Independently, a gelling agent containing a straight chain part having 15 or more carbon atoms and a hydrocarbon part which may contain a branched part) is suitably used for the actinic ray curable inkjet ink of the present invention. The inventor has newly found out.
  • the actinic ray curable inkjet ink according to the present invention contains a photopolymerizable compound.
  • the photopolymerizable compound is a compound that crosslinks or polymerizes when irradiated with actinic rays.
  • the actinic rays are, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays, and are preferably ultraviolet rays.
  • the photopolymerizable compound can be a radical polymerizable compound or a cationic polymerizable compound. A radical polymerizable compound is preferred.
  • the radical polymerizable compound is a compound (monomer, oligomer, polymer or mixture thereof) having an ethylenically unsaturated bond capable of radical polymerization. Only one kind of radically polymerizable compound may be contained in the ink, or two or more kinds thereof may be contained.
  • Examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include an unsaturated carboxylic acid and a salt thereof, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid urethane compound, an unsaturated carboxylic acid amide compound and an anhydride thereof, Examples include acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane.
  • Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.
  • the radical polymerizable compound is preferably an unsaturated carboxylic acid ester compound, and more preferably a (meth) acrylate compound.
  • the (meth) acrylate compound may be not only a monomer described later, but also an oligomer, a mixture of a monomer and an oligomer, a modified product, an oligomer having a polymerizable functional group, and the like.
  • “(meth) acrylate” refers to both and / or “acrylate” and “methacrylate”
  • (meth) acryl” refers to both and / or “acryl” and “methacryl”.
  • Examples of (meth) acrylate compounds include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) ) Acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, Methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl ( Acrylate),
  • Monofunctional monomers triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, reethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene group Cold di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Dimethylol-tricyclodecane di (meth) acrylate, bisphenol A PO adduct di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, etc.
  • stearyl (meth) acrylate lauryl (meth) acrylate, isostearyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isobornyl (meth) acrylate, tetraethylene glycol di (meth) acrylate , Glycerin propoxytri (meth) acrylate and the like are preferable.
  • the (meth) acrylate compound may be a modified product.
  • examples thereof include ethylene oxide-modified (meth) acrylate compounds such as ethylene oxide-modified trimethylolpropane tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetraacrylate; Caprolactone-modified (meth) acrylate compounds such as caprolactone-modified trimethylolpropane tri (meth) acrylate; and caprolactam-modified (meth) acrylate compounds such as caprolactam-modified dipentaerythritol hexa (meth) acrylate and the like are included.
  • an ethylene oxide-modified (meth) acrylate compound is preferable from the viewpoint of high photosensitivity and easy formation of a card house structure described later when gelling at a low temperature.
  • the ethylene oxide-modified (meth) acrylate compound is easily dissolved in other ink components at high temperatures and has little curing shrinkage, so that curling of the printed matter hardly occurs.
  • Examples of ethylene oxide-modified (meth) acrylate compounds include 4EO-modified hexanediol diacrylate CD561 (molecular weight 358), 3EO-modified trimethylolpropane triacrylate SR454 (molecular weight 429), 6EO-modified trimethylolpropane triacrylate SR499 manufactured by Sartomer. (Molecular weight 560), 4EO-modified pentaerythritol tetraacrylate SR494 (molecular weight 528); Shin-Nakamura Chemical Co., Ltd.
  • polyethylene glycol diacrylate NK ester A-400 (molecular weight 508), polyethylene glycol diacrylate NK ester A-600 (molecular weight 742) , Polyethylene glycol dimethacrylate NK ester 9G (molecular weight 536), polyethylene glycol dimethacrylate NK ester 4G (molecular weight 770); Tetraethylene glycol diacrylate V # 335HP (molecular weight 302) manufactured by Osaka Organic Chemical Co .; 3PO-modified trimethylolpropane triacrylate Photomer 4072 (molecular weight 471) manufactured by Cognis; 1 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the (meth) acrylate compound may be a polymerizable oligomer.
  • polymerizable oligomers examples include epoxy (meth) acrylate oligomers, aliphatic urethane (meth) acrylate oligomers, aromatic urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and linear (meth) acrylic. Oligomers and the like are included.
  • the content of the photopolymerizable compound is preferably 1 to 97% by mass and more preferably 30 to 95% by mass with respect to the total mass of the ink.
  • the amount of the photopolymerizable compound is too small, the coloring material cannot be sufficiently dispersed, and the ink dischargeability from the ink jet recording apparatus is lowered.
  • the amount of the photopolymerizable compound is excessive, the amount of the gelling agent and the photopolymerization initiator is relatively small, and the sol-gel phase transition may not be sufficiently performed or the curing is insufficient. there is a possibility.
  • the actinic radiation curable inkjet ink according to the present invention may further contain a photopolymerization initiator.
  • a photopolymerization initiator when the actinic ray is an electron beam, a photopolymerization initiator may ordinarily not be included. However, when the actinic ray is an ultraviolet ray, a photopolymerization initiator is preferably contained.
  • the photopolymerization initiator is a radical polymerization initiator when the photopolymerizable compound is a radical polymerizable compound, and a photoacid generator when the photopolymerizable compound is a carion polymerizable compound.
  • the radical polymerization initiator includes an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type.
  • intramolecular bond cleavage type photopolymerization initiators examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2.
  • intramolecular hydrogen abstraction type photopolymerization initiators examples include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl.
  • Benzophenones such as sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 -Thioxanthone series such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone series such as Michler ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethyl Anthraquinone, 9,10-phenanthrene Quinone, include camphor quinone and the like.
  • photoacid generators examples include chemically amplified photoresists and compounds used for photocationic polymerization (Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187. See page 192).
  • the content of the photopolymerization initiator in the actinic ray curable inkjet ink according to the present invention is preferably 0.01% by mass to 10% by mass, although it depends on the type of actinic ray or photopolymerizable compound. More preferably, it is ⁇ 8% by mass.
  • the actinic ray curable inkjet ink according to the present invention may further contain a photopolymerization initiator auxiliary agent, a polymerization inhibitor, and the like, if necessary.
  • the photopolymerization initiator assistant may be a tertiary amine compound, preferably an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included.
  • N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. These compounds may be used alone or in combination of two or more.
  • polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone , Nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino- 1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime
  • the actinic ray curable ink-jet ink may further contain a coloring material as necessary.
  • the coloring material can be a dye or a pigment, but is preferably a pigment because it has good dispersibility with respect to the components of the ink and is excellent in weather resistance.
  • the pigment is not particularly limited, and may be, for example, an organic pigment or an inorganic pigment having the following numbers described in the color index.
  • red or magenta pigments examples include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, etc. are included.
  • Examples of blue or cyan pigments include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36. , 60 and the like.
  • Examples of green pigments include Pigment Green 7, 26, 36, and 50.
  • Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137. 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193 and the like.
  • Examples of the black pigment include Pigment Black 7, 28, 26 and the like.
  • Examples of commercially available pigments include chromofine yellow 2080, 5900, 5930, AF-1300, 2700L, chromofine orange 3700L, 6730, chromofine scarlet 6750, chromofine magenta 6880, 6886, 6891N, 6790, 6887, chromo Fine Violet RE, Chromo Fine Red 6820, 6830, Chromo Fine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromofine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chromofine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY
  • the pigment can be dispersed by, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like.
  • the pigment is dispersed such that the volume average particle diameter of the pigment particles is preferably 0.08 to 0.5 ⁇ m, and the maximum particle diameter is preferably 0.3 to 10 ⁇ m, more preferably 0.3 to 3 ⁇ m. It is preferable.
  • the dispersion of the pigment is adjusted by the selection of the pigment, the dispersant, and the dispersion medium, the dispersion conditions, the filtration conditions, and the like.
  • the actinic ray curable inkjet ink according to the present invention may further contain a dispersant in order to enhance the dispersibility of the pigment.
  • the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester , Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate and the like are included.
  • Examples of commercially available dispersants include Avecia
  • the actinic ray curable inkjet ink according to the present invention may further contain a dispersion aid as necessary.
  • the dispersion aid may be selected according to the pigment.
  • the total amount of the dispersing agent and the dispersing aid is preferably 1 to 50% by mass with respect to the pigment.
  • the actinic ray curable inkjet ink according to the present invention may further include a dispersion medium for dispersing the pigment, if necessary.
  • a solvent may be included in the ink as a dispersion medium, in order to suppress the residual solvent in the formed image, a photopolymerizable compound as described above (particularly a monomer having a low viscosity) is used as the dispersion medium. Is preferred.
  • the dye can be an oil-soluble dye or the like.
  • oil-soluble dyes include the following various dyes.
  • magenta dyes include MS Magenta VP, MS Magenta HM-1450, MS Magenta HSo-147 (above, manufactured by Mitsui Toatsu), AIZEN SOT Red-1, AIZEN SOT Red-2, AIZEN SOT Red-3, AIZEN SOT Pink-1, SPIRON Red GEH SPECIAL (above, manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN Red FB 200%, MACROLEX Red Violet R, MACROLEX ROT5B (above, manufactured by Bayer Japan, Inc.), KAYASETR KAYASET Red 802 (Nippon Kayaku Co., Ltd.), PHLOXIN, ROSE Bengal, ACID Red (hereafter , Manufactured by Daiwa Kasei Co., Ltd.), HSR-31, DIARESIN Red K (manufactured by Mitsubishi Kas
  • cyan dyes examples include MS Cyan HM-1238, MS Cyan HSo-16, Cyan HSo-144, MS Cyan VPG (manufactured by Mitsui Toatsu), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN BR. Blue BGLN 200%, MACROLEX Blue RR, CERES Blue GN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIUS SUTRA TURQ. Blue FB-LL 330% (from Bayer Japan), KAYASET Blue FR, KAYASET Blue N, KAYASET Blue 814, Turq.
  • Blue GL-5 200 Light Blue BGL-5 200 (Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, Olesol Fast Blue GL (Daiwa Kasei Co., Ltd.), DIARESIN Blue P (Mitsubishi Chemical Co., Ltd.) Blue 670, NEOPEN Blue 808, ZAPON Blue 806 (above, manufactured by BASF Japan Ltd.) and the like are included.
  • yellow dyes examples include MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (manufactured by Mitsui Toatsu), AIZEN SOT Yellow-1, AIZEN SOT Yellow W-3, AIZEN SOT Yellow-6 (above, Manufactured by Hodogaya Chemical Co., Ltd.), MACROLEX Yellow 6G, MACROLEX FLUOR.
  • black dyes examples include MS Black VPC (Mitsui Toatsu Co., Ltd.), AIZEN SOT Black-1, AIZEN SOT Black-5 (above, manufactured by Hodogaya Chemical Co., Ltd.), RESORIN Black GSN 200%, RESOLIN BlackBS (above, Bayer Japan), KAYASET Black AN (Nippon Kayaku), DAIWA Black MSC (Daiwa Kasei), HSB-202 (Mitsubishi Kasei), NEPTUNE Black X60, NEOPEN Black X58 (above, BASF) Japan product).
  • the content of the pigment or dye is preferably 0.1 to 20% by mass, more preferably 0.4 to 10% by mass with respect to the actinic ray curable inkjet ink. This is because if the content of the pigment or dye is too small, the color of the resulting image is not sufficient, and if it is too large, the viscosity of the ink increases and the jetting property decreases.
  • the actinic ray curable inkjet ink of the present invention may further contain other components as necessary.
  • Other components may be various additives, other resins, and the like.
  • the additive include a surfactant, a leveling additive, a matting agent, an ultraviolet absorber, an infrared absorber, an antibacterial agent, and a basic compound for enhancing the storage stability of the ink.
  • basic compounds include basic alkali metal compounds, basic alkaline earth metal compounds, basic organic compounds such as amines, and the like.
  • other resins include resins for adjusting the physical properties of the cured film, such as polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes. It is.
  • the gelling agent, polyvalent ester compound and photopolymerizable compound contained in the actinic radiation curable ink jet ink of the present invention, and the colorant and photopolymerization initiator suitably contained can be obtained by mixing under heating.
  • a pigment dispersion in which a color material (particularly a pigment) is dispersed in a part of the photopolymerizable compound is prepared and mixed with the pigment dispersion and other ink components.
  • the obtained ink is preferably filtered through a predetermined filter.
  • the viscosity of the ink at a high temperature is preferably not more than a certain level.
  • the viscosity of the actinic ray curable inkjet ink at 80 ° C. is preferably 3 to 20 mPa ⁇ s.
  • the image forming method includes 1) a step of ejecting the actinic ray curable inkjet ink of the present invention onto a recording medium, and 2) a step of irradiating the ink ejected onto the recording medium with an actinic ray to cure the ink. It is characterized by including these.
  • the inkjet ink stored in the ejection recording head may be ejected as droplets toward the recording medium through the nozzles.
  • the ink that has landed on the recording medium is irradiated with light.
  • the light to be irradiated may be appropriately selected depending on the type of the photopolymerizable compound, and may be ultraviolet rays or electron beams.
  • the recording medium may be paper or a resin film.
  • paper examples include coated paper for printing, coated paper B for printing, and the like.
  • the resin film examples include a polyethylene terephthalate film and a vinyl chloride film.
  • Actinic ray curable inkjet recording apparatuses include a line recording method (single pass recording method) and a serial recording method.
  • the line recording method is preferable from the viewpoint of high-speed recording, although it may be selected according to the required image resolution and recording speed.
  • FIG. 1A and FIG. 1B are diagrams showing an example of a configuration of a main part of a line recording type ink jet recording apparatus.
  • FIG. 1A is a side view
  • FIG. 1B is a top view.
  • the inkjet recording apparatus 10 includes a head carriage 16 that accommodates a plurality of ejection recording heads 14 and covers the entire width of the recording medium 12, and the head carriage 16 (recording medium conveyance).
  • Direction having an actinic ray irradiation unit 18 disposed on the downstream side, and a temperature control unit 19 disposed on the lower surface of the recording medium 12.
  • the head carriage 16 is fixedly arranged so as to cover the entire width of the recording medium 12, and accommodates a plurality of ejection recording heads 14 provided for each color.
  • Ink is supplied to the ejection recording head 14.
  • the ink may be supplied directly or by an ink supply unit (not shown) from an ink cartridge (not shown) that is detachably attached to the inkjet recording apparatus 10.
  • a plurality of ejection recording heads 14 are arranged in the transport direction of the recording medium 12 for each color.
  • the number of ejection recording heads 14 arranged in the conveyance direction of the recording medium 12 is set according to the nozzle density of the ejection recording head 14 and the resolution of the print image. For example, when an image having a resolution of 1440 dpi is formed using the ejection recording head 14 having a droplet amount of 2 pl and a nozzle density of 360 dpi, the four ejection recording heads 14 are shifted with respect to the conveyance direction of the recording medium 12. What is necessary is just to arrange.
  • dpi represents the number of ink droplets (dots) per 2.54 cm.
  • the actinic ray irradiation unit 18 covers the entire width of the recording medium 12 and is arranged on the downstream side of the head carriage 16 in the conveyance direction of the recording medium.
  • the actinic ray irradiation unit 18 irradiates the droplets ejected by the ejection recording head 14 and landed on the recording medium with actinic rays to cure the droplets.
  • examples of the active light irradiation unit 18 include a fluorescent tube (low pressure mercury lamp, germicidal lamp), a cold cathode tube, an ultraviolet laser, and an operating pressure of several hundred Pa to 1 MPa. These include low pressure, medium pressure, high pressure mercury lamps, metal halide lamps and LEDs. From the viewpoint of curability, ultraviolet irradiation means for irradiating ultraviolet rays having an illuminance of 100 mW / cm 2 or more; specifically, high-pressure mercury lamps, metal halide lamps, and LEDs are preferable, and LEDs are more preferable from the viewpoint of low power consumption. Specifically, a 395 nm, water-cooled LED manufactured by Phoseon Technology can be used.
  • examples of the actinic ray irradiating unit 18 include electron beam irradiating means such as a scanning method, a curtain beam method, and a broad beam method. Therefore, a curtain beam type electron beam irradiation means is preferable.
  • Examples of electron beam irradiation means include “Curetron EBC-200-20-30” manufactured by Nissin High Voltage Co., Ltd., “Min-EB” manufactured by AIT Co., Ltd., and the like.
  • the temperature control unit 19 is disposed on the lower surface of the recording medium 12 and maintains the recording medium 12 at a predetermined temperature.
  • the temperature control unit 19 can be, for example, various heaters.
  • the recording medium 12 is conveyed between the head carriage 16 and the temperature control unit 19 of the inkjet recording apparatus 10. On the other hand, the recording medium 12 is adjusted to a predetermined temperature by the temperature control unit 19. Next, high-temperature ink is ejected from the ink ejection recording head 14 of the head carriage 16 and adhered (landed) on the recording medium 12. Then, the actinic ray irradiating unit 18 irradiates the ink droplets attached on the recording medium 12 with an actinic ray to cure.
  • the temperature of the ink in the ejection recording head 14 is 10 to 30 ° C. higher than the gelation temperature of the ink in order to improve the ink ejection property. It is preferable to set to.
  • the ink temperature in the ejection recording head 14 is less than (gelation temperature + 10) ° C., the ink gels in the ejection recording head 14 or on the nozzle surface, and the ink ejection property is likely to deteriorate.
  • the temperature of the ink in the ejection recording head 14 exceeds (gelation temperature + 30) ° C., the ink becomes too high, and the ink component may deteriorate.
  • the amount of droplets ejected from each nozzle of the ink ejection recording head 14 is preferably 1 pl to 10 pl in order to form a high resolution image, although it depends on the resolution of the image. More preferably, it is 0.5 to 4.0 pl.
  • Irradiation with actinic rays is performed within 10 seconds, preferably within 0.001 seconds to 5 seconds, more preferably after the ink droplets are deposited on the recording medium, in order to prevent adjacent ink droplets from coalescing. It is preferable to carry out within 0.01 second to 2 seconds. Irradiation with actinic rays is preferably performed after ink is ejected from all the ink ejection recording heads 14 accommodated in the head carriage 16.
  • the acceleration voltage for electron beam irradiation is preferably 30 to 250 kV and more preferably 30 to 100 kV in order to perform sufficient curing.
  • the electron beam irradiation amount is preferably 30 to 100 kGy, and more preferably 30 to 60 kGy.
  • the total ink film thickness after curing is preferably 2 to 25 ⁇ m.
  • the “total ink film thickness” is the maximum value of the ink film thickness drawn on the recording medium.
  • FIG. 2 is a top view showing an example of a configuration of a main part of the serial recording type inkjet recording apparatus 20.
  • the inkjet recording apparatus 20 has a width narrower than the entire width of the recording medium, instead of the head carriage 16 fixedly arranged so as to cover the entire width of the recording medium, and a plurality of ink ejection devices.
  • 1A and 1B can be configured except that a head carriage 26 that accommodates the recording head 24 and a guide portion 27 for moving the head carriage 26 in the width direction of the recording medium 12 are provided.
  • the head carriage 26 is ejected from the ejection recording head 24 accommodated in the head carriage 26 while moving in the width direction of the recording medium 12 along the guide portion 27. After the head carriage 26 has completely moved in the width direction of the recording medium 12 (for each pass), the recording medium 12 is fed in the transport direction. Except for these operations, an image is recorded in substantially the same manner as the line recording type inkjet recording apparatus 10 described above.
  • An actinic ray curable inkjet ink was prepared using the following components (gelator (wax), photopolymerizable compound, polymerization inhibitor, photopolymerization initiator, pigment dispersion).
  • [Gelling agent (wax)] (Compound represented by General Formula (G1)) 10-Nonadecanone (10-Nonadecanone, Tokyo Chemical Industry) 12-Tricosanone (12-Tricosanone, Tokyo Chemical Industry) Distearyl ketone (Kao wax T1, Kao) Dipalmityl ketone (16-Hentriacontanone, Tokyo Chemical Industry) (Compound represented by formula (G2)) Lauryl stearate (Dodecyl Stearate, Tokyo Chemical Industry) Cetyl palmitate (Amreps PC, higher alcohol industry) Stearyl stearate (AmrepSS SS, higher alcohol industry) Behenyl stearate (synthesized by the following method) Behenyl behenate (Unistar M-2222SL, NOF) Lignoceryl lignocerate (synthesized by the following method) (Compound represented by General Formula (G3)) Behenic acid (Lunac BA, NOF) (Compound represented by formula (G
  • Behenyl stearate was synthesized as follows. A flask was charged with 326.6 g of behenyl alcohol (calcol 220-80, Kao), 284.5 g of stearic acid (Lunac S-50V, Kao), 19.6 g of concentrated sulfuric acid and 2 L of toluene, and esterified at 80 ° C. for 4 hours. The reaction was carried out. Next, the ester was separated by column chromatography to obtain 59.3 g of behenyl stearate.
  • Lignoceryl lignocerate was synthesized as follows. Charge 70.529 g of lignoceryl alcohol (LignocerylAlcohol, Tokyo Kasei Kogyo), lignoceric acid (Tetracosanoic Acid, Tokyo Kasei Kogyo) 368.64 g, concentrated sulfuric acid 19.6 g, and toluene 2 L at 80 ° C. for 4 hours. The reaction was carried out. Next, the ester was separated by column chromatography to obtain 70.5 g of lignoceryl lignocerate.
  • Pentaerythritol trimyristate (synthesized by the following method) Pentaerythritol distearate (Unistar H-476D, NOF) Pentaerythritol tetrapalmitate (synthesized by the following method) Dipentaerythritol tetralignocerate (synthesized by the following method)
  • Pentaerythritol trimyristate was synthesized as follows. A flask was charged with 136.2 g of pentaerythritol (Pentaerythritol, Tokyo Chemical Industry), 913.6 g of myristic acid (manufactured by Myristic Acid Wako Pure Chemical Industries), 19.6 g of concentrated sulfuric acid, and 2 L of toluene at 4O 0 C. A time esterification reaction was performed. Next, separation for each ester value was performed by column chromatography to obtain 38 g of pentaerythritol trimyristate.
  • Pentaerythritol tetrapalmitate was synthesized as follows. 136.2 g of pentaerythritol (Pentaerythritol, Tokyo Chemical Industry), 1089.8 g of palmitic acid (manufactured by Palmitic Acid Wako Pure Chemical Industries, Ltd.), 19.6 g of concentrated sulfuric acid, and 2 L of toluene were charged into a flask at 80 ° C. for 4 hours. An esterification reaction was performed. Next, separation for each ester value was performed by column chromatography to obtain 27 g of pentaerythritol tetrapalmitate.
  • Dipentaerythritol tetraglycenate was synthesized as follows. Dipentaerythritol (Dipentaerythritol, Tokyo Kasei Kogyo) 254.3 g, lignoceric acid (Tetracosanoic Acid, Tokyo Kasei Kogyo) 1656.9 g, concentrated sulfuric acid (19.6 g, and toluene 2 L) were charged into a flask at 4O 0 C. Next, the ester value was separated by column chromatography, and 25 g of dipentaerythritol tetrabehenate was obtained.
  • Pigment dispersion Preparation of pigment dispersion
  • the following dispersant, photopolymerizable compound and polymerization inhibitor were placed in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C. After cooling the resulting solution to room temperature, 21% by mass of the following magenta pigment was added, sealed in a glass bottle with 200 g of zirconia beads having a diameter of 0.5 mm, and dispersed with a paint shaker for 8 hours. Thereafter, the zirconia beads were removed to prepare a pigment dispersion having the following composition.
  • composition of pigment dispersion Dispersant: Azisper PB824 (Ajinomoto Fine Techno Co., Ltd.) 9% by mass
  • Photopolymerizable compound APG-200 (tripropylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 70% by mass
  • Polymerization inhibitor Irgastab UV10 (manufactured by Ciba Japan) 0.02% by mass
  • Magenta pigment Pigment Red 122 (manufactured by Dainichi Seika, Chromo Fine Red 6112JC) 21% by mass
  • a piezo head having a nozzle diameter of 20 ⁇ m and 512 nozzles (256 nozzles ⁇ 2 rows, staggered arrangement, 1 row nozzle pitch 360 dpi) was used.
  • the ejection conditions were such that the amount of one droplet was 2.5 pl, and ejection was performed at a droplet velocity of about 6 m / s, and recording was performed at a resolution of 1440 dpi ⁇ 1440 dpi.
  • the recording speed was 500 mm / s.
  • Image formation was performed in an environment of 23 ° C. and 55% RH. dpi represents the number of dots per inch (2.54 cm).
  • Concentration 0.35 or more Concentration 0.30 or more and less than 0.35 2: Concentration 0.25 or more and less than 0.30 3: Concentration 0.20 or more and less than 0.25 4: Concentration 0.13 or more and less than 0.20 5: Concentration less than 0.13
  • the content of the polyvalent ester compound was 5% by mass or less, so that the surface stickiness was further suppressed.
  • two or more kinds of compounds represented by the general formula (G2) were included, so that density unevenness and surface stickiness were further suppressed. It was. Further, in the images using the actinic ray curable inkjet inks of Examples 14 to 24, the surface gloss was further suppressed, and therefore the image gloss was further lowered.
  • the actinic ray curable inkjet ink of Comparative Example 1 contained only a gelling agent and did not contain a polyvalent ester compound.
  • the actinic ray curable inkjet ink of Comparative Example 2 contained only a polyvalent ester compound and did not contain a gelling agent. Therefore, the ink did not gel well, and evaluation of density unevenness and surface tackiness was poor. It was.
  • the actinic ray curable inkjet ink of Comparative Example 3 had a large amount of gelling agent, and therefore had poor emission stability, and therefore uneven density occurred. In the actinic ray curable inkjet ink of Comparative Example 4, since the amount of the gelling agent was small, the ink did not sufficiently gel, and the image glossiness, density unevenness, and surface tackiness were poor.
  • the effect of reducing the glossiness is achieved by containing the polyvalent ester compound in the actinic ray curable inkjet ink, and in particular, the polyvalent ester compound content is small (for example, 0.1% by mass to 5% by mass). %), The level of gloss reduction was large and good.
  • density unevenness if the content of the gelling agent was less than 1% by mass, the pinning function of the ink was not exhibited, and density unevenness and surface stickiness occurred. The emission stability tended to deteriorate when the amount of gelling agent added exceeded 10% by mass. When two kinds of gelling agents were used, the pinning property and leveling property were improved, and surface stickiness and density unevenness were eliminated.
  • the actinic ray curable ink-jet ink of the present invention is suitable for forming an image on an ink-jet recording system on a recording medium because the image glossiness can be controlled while maintaining pinning and leveling image quality.

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Abstract

La présente invention aborde le problème consistant à fournir une encre pour jet d'encre pouvant durcir sous l'effet d'une lumière active, à l'aide de laquelle une bonne image puisse être formée par régulation du brillant de l'image tout en conservant les propriétés de séchage intermédiaire et les propriétés de séchage intermédiaire et d'étalement de l'encre pour jet d'encre. Cette encre pour jet d'encre pouvant durcir sous l'effet d'une lumière active comprend un agent gélifiant spécifié, un composé ester polyvalent et un composé photopolymérisable. La teneur en l'agent gélifiant est de 1 à 10 % en masse par rapport à la masse totale de l'encre pour jet d'encre pouvant durcir sous l'effet d'une lumière active. Le composé ester polyvalent comprend au moins un type de composé choisi dans le groupe consistant en les composés ayant une structure de pentaérythritol et un indice d'ester de 2 ou plus et les composés ayant une structure de dipentaérythritol et un indice d'ester de 2 ou plus.
PCT/JP2015/068970 2014-07-02 2015-07-01 Encre pour jet d'encre durcissable sous l'effet d'une lumière active, et procédé de formation d'image Ceased WO2016002834A1 (fr)

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JP2021147582A (ja) * 2020-03-23 2021-09-27 コニカミノルタ株式会社 活性線硬化型インクおよび画像形成方法
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