WO2022239625A1 - インクジェットインク、インクセット、及び画像記録方法 - Google Patents

インクジェットインク、インクセット、及び画像記録方法 Download PDF

Info

Publication number
WO2022239625A1
WO2022239625A1 PCT/JP2022/018651 JP2022018651W WO2022239625A1 WO 2022239625 A1 WO2022239625 A1 WO 2022239625A1 JP 2022018651 W JP2022018651 W JP 2022018651W WO 2022239625 A1 WO2022239625 A1 WO 2022239625A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
mass
silicon compound
pretreatment liquid
image
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/018651
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
剛生 井腰
大我 溝江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to CN202280034377.1A priority Critical patent/CN117295798A/zh
Priority to EP22807328.4A priority patent/EP4338961A4/en
Priority to JP2023520952A priority patent/JPWO2022239625A1/ja
Publication of WO2022239625A1 publication Critical patent/WO2022239625A1/ja
Priority to US18/505,741 priority patent/US20240067837A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
    • B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
    • 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
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
    • B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
    • B41J2/2117—Ejecting white liquids
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • 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
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • 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
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • 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
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying

Definitions

  • the present disclosure relates to inkjet inks, ink sets, and image recording methods.
  • Patent Document 1 discloses a white pigment composition capable of improving sedimentation stability and whiteness in a well-balanced manner, which includes core particles and a shell layer made of titanium dioxide and covering the surface of the core particles, A white pigment composition is disclosed that includes core-shell titanium dioxide particles having an average particle size of 50 nm or more and 5000 nm or less, silicon oxide particles having an average particle size of 3 nm or more and 100 nm or less, and a resin. Patent Document 1 also discloses the use of the white pigment composition as an ink in an inkjet recording method. Further, Japanese Patent Laid-Open No.
  • 2002-100000 describes a recording method that is less prone to cracking while maintaining good image quality.
  • a recording method is disclosed that contains a white pigment and inorganic fine particles having a volume average particle diameter smaller than that of the white pigment.
  • hiding property means a property of hiding a base (for example, a base material, other images recorded on the base material, etc.).
  • the inkjet head for ejecting the inkjet ink is likely to be worn and deteriorated.
  • the abrasion deterioration of the inkjet head is the deterioration caused by polishing the portion of the inkjet head that comes into contact with the inkjet ink by titanium dioxide particles.
  • the inventors of the present invention have also found that when an image is recorded under conditions intended to suppress abrasion and deterioration of the ink jet head, the image concealability may be lowered.
  • An object of one aspect of the present disclosure is to provide an inkjet ink, an ink set, and an image recording method capable of recording an image with excellent concealability and suppressing wear and deterioration of an inkjet head.
  • ⁇ 1> Containing water, titanium dioxide particles, and a silicon compound,
  • the average primary particle size of the titanium dioxide particles is 100 nm or more
  • the silicon compound is at least one selected from the group consisting of silicates and colloidal silica
  • the content of the silicon compound with respect to the total amount of titanium dioxide particles is 0.0020% by mass or more
  • the ratio of the volume average particle size of colloidal silica to the average primary particle size of titanium dioxide particles is 0.04 or less.
  • inkjet ink ⁇ 2> the silicon compound contains a silicate, the silicate is at least one selected from the group consisting of alkali metal silicate and ammonium silicate; The inkjet ink according to ⁇ 1>.
  • ⁇ 3> Furthermore, it contains a polymer dispersant, The polymer dispersant contains a block polymer or a polymer having a crosslinked structure,
  • ⁇ 4> The content of the silicon compound relative to the total amount of titanium dioxide particles is 0.040% by mass to 2.0% by mass.
  • White ink which is the inkjet ink according to any one of ⁇ 1> to ⁇ 4>; a color ink containing water and a color pigment; ink set, including ⁇ 6>
  • the silicon compound contained in the white ink is the first silicon compound
  • the color ink further contains a second silicon compound that is at least one selected from the group consisting of silicates and colloidal silica;
  • the X1/X2 ratio is less than 1.0.
  • the color ink further contains a second silicon compound that is at least one selected from the group consisting of silicates and colloidal silica; the first silicon compound comprises a silicate; the second silicon compound comprises colloidal silica;
  • ⁇ 8> Furthermore, including a pretreatment liquid containing water and a flocculant, The ink set according to any one of ⁇ 5> to ⁇ 7>.
  • the image recording method according to ⁇ 10>.
  • ⁇ 12> Using the ink set according to any one of ⁇ 5> to ⁇ 9>, A color ink application step of ejecting color ink from an inkjet head and applying it onto a non-permeable substrate; A white ink application step of ejecting white ink from an inkjet head using the ink set and applying it onto a region to which color ink has been applied on a non-permeable substrate to which color ink has been applied;
  • An image recording method comprising: ⁇ 13> Prior to the color ink application step, further comprising a pretreatment liquid application step of applying a pretreatment liquid containing water and a coagulant onto the impermeable substrate, In the color ink application step, color ink is applied onto the pretreatment liquid-applied region of the non-permeable substrate to which the pretreatment liquid has been applied.
  • the image recording method according to ⁇ 12>.
  • an inkjet ink an ink set, and an image recording method that can record an image with excellent concealability and can suppress wear and deterioration of the inkjet head.
  • a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
  • the amount of each component in the composition means the total amount of the above substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. do.
  • the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described step by step, Alternatively, the values shown in the examples may be substituted.
  • the term "process” includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In the present disclosure, combinations of preferred aspects are more preferred aspects.
  • image means the entire film formed by applying ink
  • image recording means formation of the film.
  • image in this disclosure also includes a solid image.
  • the inkjet ink of the present disclosure (hereinafter also simply referred to as "ink") Containing water, titanium dioxide particles, and a silicon compound,
  • the average primary particle size of the titanium dioxide particles is 100 nm or more
  • the silicon compound is at least one selected from the group consisting of silicates and colloidal silica;
  • the content of the silicon compound with respect to the total amount of titanium dioxide particles is 0.0020% by mass or more,
  • the ratio of the volume average particle size of colloidal silica to the average primary particle size of titanium dioxide particles is 0.04 or less.
  • the inkjet ink of the present disclosure contains water, titanium dioxide particles, and a silicon compound
  • the titanium dioxide particles have an average primary particle size of 100 nm or more
  • the silicon compound comprises a silicate and a colloidal It is at least one selected from the group consisting of silica
  • the content of the silicon compound with respect to the total amount of the titanium dioxide particles is 0.0020% by mass or more
  • the silicon compound contains colloidal silica
  • a ratio of the volume average particle size of the colloidal silica to the average primary particle size of the titanium dioxide particles is 0.04 or less.
  • the ink of the present disclosure it is possible to record an image with excellent hiding properties, and to suppress wear and deterioration of the inkjet head when recording the image.
  • the reason why such an effect is produced is presumed as follows.
  • the titanium dioxide particles have a high refractive index and that the average primary particle diameter of the titanium dioxide particles is 100 nm or more contributes to the effect of the image hiding property (that is, the property of hiding the background). It is thought that
  • the effect of suppressing abrasion and deterioration of the inkjet head includes a specific silicon compound contained in the ink, more specifically, a silicate and/or colloidal silica with a small particle size (specifically, an average primary particle size of dioxide It is considered that colloidal silica having an average primary particle size of 0.04 or less (the same shall apply hereinafter) contributes to the average primary particle size of the titanium particles. Specifically, it is believed that the wear and deterioration of the inkjet head is caused by polishing the portion of the inkjet head that contacts the ink with titanium dioxide particles, which are hard particles contained in the ink.
  • a specific silicon compound (specifically, silicate and/or colloidal silica with a small particle size) enters between the titanium dioxide particles and the contact portion of the inkjet head to create a cushion. As a result, it is thought that wear deterioration of the inkjet head is suppressed.
  • the average primary particle diameter of the titanium dioxide particles is 100 nm or more also contributes to the effect of suppressing wear and deterioration of the inkjet head.
  • the reason for this is thought to be that the average primary particle size of the titanium dioxide particles is not too small, thereby suppressing minute polishing scratches that have a large effect on deterioration due to wear.
  • the inks of the present disclosure contain water.
  • the water content is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and still more preferably 60% by mass or more, relative to the total amount of the ink.
  • the upper limit of the water content is appropriately determined according to the content of other components.
  • the upper limit of water content is, for example, 90% by mass, 80% by mass, and the like.
  • the inks of the present disclosure contain at least one type of titanium dioxide particles. Since titanium dioxide particles have a large refractive index, they contribute to an improvement in the concealability of an image. In the inks of the present disclosure, titanium dioxide particles preferably function as white pigments. The inks of the present disclosure are preferably white inks.
  • the average primary particle size of the titanium dioxide particles contained in the ink of the present disclosure is 100 nm or more. This improves the concealability of the image. Furthermore, the effect of suppressing wear and deterioration of the inkjet head can also be obtained.
  • the average primary particle size of the titanium dioxide particles is preferably 150 nm or more, more preferably 200 nm or more.
  • the average primary particle size of the titanium dioxide particles is preferably 400 nm or less, more preferably 300 nm or less, from the viewpoint of ink ejection properties.
  • the average primary particle size of titanium dioxide particles is a value measured using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a transmission electron microscope 1200EX manufactured by JEOL Ltd. can be used for the measurement. Specifically, after dropping a 1,000-fold diluted ink onto a Cu200 mesh (manufactured by JEOL Ltd.) to which a carbon film was attached and drying, the image was magnified 100,000 times with a TEM. Equivalent circle diameters of 300 titanium dioxide particles that do not overlap are measured, and the measured values are averaged to determine the average particle diameter.
  • the content of titanium dioxide particles in the ink of the present disclosure is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 20% by mass, and 5% by mass, relative to the total amount of the ink. It is more preferably to 20% by mass, more preferably 6% to 20% by mass, and even more preferably 7% to 15% by mass.
  • the content of titanium dioxide particles in the ink is 1% by mass or more with respect to the total amount of the ink, the image hiding property is further improved.
  • the content of the titanium dioxide particles in the ink is 20% by mass or less with respect to the total amount of the ink, it is advantageous in terms of improving the ink ejection property and suppressing abrasion and deterioration of the inkjet head.
  • the ink of the present disclosure contains at least one silicon compound (hereinafter also referred to as "specific silicon compound") selected from the group consisting of silicates and colloidal silica.
  • the specific silicon compound contributes to suppressing abrasion deterioration of the inkjet head.
  • the specific silicon compound for example, known documents such as Japanese Patent No. 5430316 may be appropriately referred to.
  • the specific silicon compound also contributes to suppression of dissolution deterioration of the inkjet head.
  • the dissolution deterioration of the inkjet head is the deterioration caused by the dissolution of components in the ink-contacting portion of the inkjet head into the ink.
  • silicon (Si) in the specific silicon compound contributes to the effect of suppressing dissolution deterioration of the inkjet head. Specifically, when dissolution deterioration occurs in the inkjet head (specifically, when the component of the ink contact portion of the inkjet head is eluted into the ink), the portion where dissolution deterioration occurs is included in the ink. This is thought to be due to the fact that silicon (Si) in a specific silicon compound exerts a repairing effect. This repair effect is particularly effective when at least a portion of the ink-contacting portion of the inkjet head contains silicon. However, it is believed that the above-mentioned repair effect can be obtained even when the above-mentioned part does not contain silicon.
  • the portions of the inkjet head that come into contact with the ink include, for example, the nozzle plate and the ink flow path of the inkjet head.
  • silicate A water-soluble silicate is preferable as the silicate that can constitute the specific silicon compound.
  • water-soluble means the property that the amount dissolved in 100 g of distilled water at 25°C is 1 g or more.
  • the "water solubility” is preferably 2 g or more, more preferably 5 g or more, and still more preferably 10 g or more, in distilled water at 25°C.
  • the silicate may be a metasilicic acid salt or an orthosilicic acid salt.
  • a commercially available compound for example, water glass
  • one obtained by preparation may be used.
  • silicates include: Alkali metal salts of silicic acid such as sodium silicate and potassium silicate; Alkaline earth metal salts of silicic acid such as calcium silicate and magnesium silicate; ammonium salts of silicic acid; etc. From the viewpoint of the effect of suppressing abrasion and deterioration of the inkjet head, the silicate is preferably at least one selected from the group consisting of alkali metal silicate and ammonium silicate.
  • the specific silicon compound contains a silicate, and the silicate is at least one selected from the group consisting of alkali metal silicate and ammonium silicate.
  • the silicate is at least one selected from the group consisting of alkali metal silicate and ammonium silicate.
  • the silicate is at least one selected from the group consisting of alkali metal silicate and ammonium silicate.
  • colloidal silica The colloidal silica that can constitute the specific silicon compound is colloidal silica having a volume average particle size of 0.04 or less with respect to the average primary particle size of the titanium dioxide particles.
  • the role of the cushion described above is exhibited, and the effect of suppressing wear and deterioration of the inkjet head is exhibited.
  • the volume average particle size of the colloidal silica is 0.04 or less relative to the average primary particle size of the titanium dioxide particles
  • the surface area of the colloidal silica increases to some extent (that is, the surface area of the colloidal silica becomes too small. As a result, the effect of suppressing dissolution deterioration of the inkjet head is exhibited.
  • the lower limit of the ratio of the volume average particle size of colloidal silica to the average primary particle size of titanium dioxide particles is determined by the effect of suppressing abrasion and deterioration of the inkjet head. As far as I can see, there is no particular limitation.
  • the lower limit of the particle size ratio [colloidal silica/titanium dioxide particles] may be, for example, 0.001, 0.05, 0.01, or the like.
  • the upper limit of the particle size ratio [colloidal silica/titanium dioxide particles] is 0.04, but may be, for example, 0.03, 0.02, or the like.
  • Colloidal silica is a colloid composed of fine particles of inorganic oxides containing silicon.
  • Colloidal silica contains silicon dioxide (including its hydrates) as a major component and may contain an aluminate as a minor component. Aluminates that may be included as minor components include sodium aluminate, potassium aluminate, and the like.
  • colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic and organic salts act, for example, as colloid stabilizers.
  • a dispersion medium for colloidal silica is not particularly limited, and may be water, an organic solvent, or a mixture thereof.
  • the organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent, but is preferably a water-soluble organic solvent.
  • Specific examples of water-soluble organic solvents include methanol, ethanol, isopropyl alcohol, n-propanol, and the like.
  • colloidal silica there is no particular limitation on the production method of colloidal silica, and it can be produced by a commonly used method. For example, it can be produced from aerosil synthesis by thermal decomposition of silicon tetrachloride or from water glass. Alternatively, it can be produced by a liquid phase synthesis method such as hydrolysis of alkoxide (see, for example, "Textiles and Industry", Vol. 60, No. 7 (2004) P376).
  • the volume average particle size of colloidal silica should satisfy the particle size ratio [colloidal silica/titanium dioxide particles] of 0.04 or less.
  • the volume average particle size of the colloidal silica is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less. It is preferably 25 nm or less, more preferably 20 nm or less. Examples of the lower limit of the volume average particle size of colloidal silica include 1 nm and 3 nm.
  • the volume average particle size of colloidal silica is determined by a dynamic light scattering method.
  • a dynamic light scattering method for example, Nanotrac UPA manufactured by Microtrac Co., Ltd. is used.
  • the shape of the colloidal silica is not particularly limited as long as it does not hinder the ink ejection performance.
  • it may be spherical, elongated, acicular, or beaded.
  • a spherical shape is preferable from the viewpoint of ink ejection property.
  • Colloidal silica may be manufactured or commercially available. Specific examples of commercially available products include; Ludox AM, Ludox AS, Ludox LS, Ludox TM, Ludox HS, etc. (manufactured by EI Du Pont de Nemouvs &Co); Snowtex S, Snowtex XS, Snowtex 20, Snowtex 30, Snowtex 40 , Snowtex N, Snowtex C, Snowtex O, etc. (manufactured by Nissan Chemical Industries, Ltd.); Syton C-30, SytonZOO, etc.
  • beaded colloidal silica examples include Snowtex ST-UP, Snowtex PS-S, Snowtex PS-M, Snowtex ST-OUP, PS-SO, and PS-MO (manufactured by Nissan Chemical Industries, Ltd.). and those commercially available under the trade name of
  • the content of the specific silicon compound with respect to the total amount of titanium dioxide particles is 0.0020% by mass or more. As a result, the effect of suppressing wear and deterioration of the inkjet head is exhibited.
  • the content of the specific silicon compound with respect to the total amount of titanium dioxide particles is preferably 0.0030% by mass or more, more preferably 0.0050% by mass or more, still more preferably 0.010% by mass or more, and further It is preferably 0.020% by mass or more, more preferably 0.040% by mass or more.
  • the content of the specific silicon compound relative to the total amount of titanium dioxide particles.
  • the upper limit may be, for example, 5.0% by weight, 4.0% by weight, 3.0% by weight, 2.0% by weight, or 0.050% by weight.
  • a preferred range for the content of the specific silicon compound relative to the total amount of titanium dioxide particles is, for example, 0.040% by mass to 2.0% by mass.
  • the content of the specific silicon compound with respect to the total amount of the ink is preferably 0.0003% by mass or more, more preferably 0.0004% by mass or more, and more preferably 0.001% by mass, from the viewpoint of the effect of suppressing abrasion and deterioration of the ink jet head. It is at least 0.003% by mass, and more preferably at least 0.003% by mass.
  • the inks of the present disclosure may contain polymeric dispersants.
  • the polymer dispersant contained in the ink may be of only one type, or may be of two or more types.
  • the polymer dispersant has the function of dispersing the titanium dioxide particles in the ink. Therefore, when the ink contains a polymer dispersant, the dispersibility of the titanium dioxide particles in the ink is further improved.
  • the ink includes a polymeric dispersant, the ink is believed to contain dispersed particles comprising titanium dioxide particles and a polymeric dispersant that interacts with (eg, adsorbs) the titanium dioxide particles.
  • the ink of the present disclosure contains, for example, self-dispersing titanium dioxide particles as the titanium dioxide particles, the dispersibility of the titanium dioxide particles can be ensured without containing a polymer dispersant. . Therefore, from the standpoint of titanium dioxide particle dispersibility, the polymeric dispersant is not an essential component in the inks of the present disclosure. However, from the viewpoint of further suppressing abrasion deterioration of the inkjet head, the ink of the present disclosure preferably contains a polymer dispersant. The reason for this is thought to be that, like the specific silicon compound, the polymer dispersant functions as a cushion for reducing abrasion of the inkjet head by the titanium dioxide particles.
  • the ink of the present disclosure is prepared, for example, by first preparing a dispersion containing a polymer dispersant, a dispersion medium, and titanium dioxide particles, and using the resulting dispersion to prepare an ink. can be manufactured.
  • Inks of the present disclosure when containing a polymeric dispersant may also be prepared by a phase inversion emulsification process.
  • Polymer in the present disclosure means a compound having a weight average molecular weight (Mw) of 1000 or more.
  • weight average molecular weight means a value measured by gel permeation chromatography (GPC).
  • Measurement by gel permeation chromatography uses HLC (registered trademark)-8020GPC (manufactured by Tosoh Corporation) as a measuring device, and TSKgel (registered trademark) Super Multipore HZ-H (4.6 mm ID ⁇ 15 cm) as a column. , manufactured by Tosoh Corporation), and THF (tetrahydrofuran) is used as an eluent.
  • the measurement is performed with a sample concentration of 0.45% by mass, a flow rate of 0.35 ml/min, a sample injection amount of 10 ⁇ L, a measurement temperature of 40° C., and an RI detector.
  • the calibration curve is "Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40", “F-20”, “F-4”, “F-1”, “A-5000”, “A- 2500”, “A-1000”, and “n-propylbenzene”.
  • polymer dispersant known ones can be used without particular limitation.
  • the polymer dispersant for example, JP 2016-145312, paragraphs 0080 to 0096, WO 2013/180074, paragraphs 0078 to 0108, etc. can be used polymer dispersants described in known documents. .
  • an acrylic resin is preferred.
  • the acrylic resin is at least one selected from the group consisting of acrylic acid, derivatives of acrylic acid (e.g., acrylic acid esters, etc.), methacrylic acid, and derivatives of methacrylic acid (e.g., methacrylic acid esters, etc.). It means a polymer (homopolymer or copolymer) of raw material monomers containing seeds.
  • the weight average molecular weight (Mw) of the polymer dispersant is preferably 3,000 to 100,000, more preferably 4,000 to 80,000, even more preferably 5,000 to 60,000.
  • the polymer dispersant preferably contains a structural unit having an adsorptive group and a structural unit having an anionic group.
  • a structural unit having an anionic group is a structural unit that contributes to dispersibility.
  • the polymer dispersant may contain only one type of structural unit having an anionic group, or may contain two or more types.
  • Anionic groups include acid groups and salts thereof. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, and the like, with the carboxy group being particularly preferred.
  • As the acid group salt an alkali metal salt is preferable, and a sodium salt or a potassium salt is more preferable.
  • the structural unit having an anionic group at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from a salt of (meth)acrylic acid is preferable.
  • a structural unit derived from compound A means a structural unit formed by polymerizing compound A (for example, (meth)acrylic acid).
  • the adsorptive group in the structural unit having the adsorptive group has the function of adsorbing to the titanium dioxide particles.
  • the polymer dispersant may contain only one type of structural unit having an adsorptive group, or may contain two or more types.
  • the adsorptive group preferably contains at least one selected from the group consisting of an aromatic ring structure, an alicyclic structure, and an alkyl group having 6 or more carbon atoms, and is selected from the group consisting of an aromatic ring structure and an alicyclic structure. It is more preferable to include at least one of
  • the structural unit having an adsorptive group is preferably a structural unit derived from a (meth)acrylate having an adsorptive group.
  • the polymer dispersant may be a random polymer (that is, random copolymer), a block polymer (that is, block copolymer), or a polymer having a crosslinked structure. .
  • the polymer dispersant preferably contains a block polymer or a polymer having a crosslinked structure. In this case, the polymer dispersant may contain both a block polymer and a polymer having a crosslinked structure.
  • the polymer dispersant contains a block polymer or a polymer having a crosslinked structure, abrasion deterioration of the inkjet head can be further suppressed.
  • the reason for this is that when the polymer dispersant contains a block polymer or a polymer having a crosslinked structure, the titanium dioxide particles are more densely coated with the polymer dispersant in the ink, and as a result, the cushioning function ( That is, it is considered that the function of the titanium dioxide particles as a cushion for reducing abrasion of the ink jet head) is exhibited more effectively.
  • a block polymer is also called a block copolymer, and is a copolymer in which at least two polymers are bonded in the molecule.
  • the block polymer preferably contains a structural unit derived from a hydrophobic monomer and a structural unit derived from a monomer containing an anionic group (hereinafter, "anionic group-containing monomer").
  • the structural unit derived from the hydrophobic monomer contained in the block polymer may be of only one type, or may be of two or more types.
  • the structural unit derived from the anionic group-containing monomer contained in the block polymer may be of only one type, or may be of two or more types.
  • Structural units derived from hydrophobic monomers include ethylenically unsaturated compounds having an aromatic ring structure or an alicyclic structure, and (meth)acrylates having an alkyl group with 1 to 20 carbon atoms.
  • the content of the structural unit derived from the hydrophobic monomer is preferably 35% by mass to 95% by mass, more preferably 50% by mass to 95% by mass, and 70% by mass with respect to the total amount of the block polymer. More preferably, it is up to 90% by mass.
  • the hydrophobic monomer preferably contains an ethylenically unsaturated compound having an aromatic ring structure or an alicyclic structure from the viewpoint of adsorptivity with the pigment, and may contain an ethylenically unsaturated compound having an alicyclic structure. More preferably, it contains an ethylenically unsaturated compound having an alicyclic structure with 6 or more carbon atoms.
  • the content of structural units derived from an ethylenically unsaturated compound having an aromatic ring structure or an alicyclic structure is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, based on the total amount of the block polymer. It is more preferably 30% by mass to 70% by mass, even more preferably 30% by mass to 60% by mass.
  • the structural unit derived from the hydrophobic monomer also preferably contains a (meth)acrylate having an alkyl group with 1 to 20 carbon atoms.
  • Alkyl groups may be linear or branched.
  • Examples of (meth)acrylates having an alkyl group having 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl. (meth)acrylates and octyl (meth)acrylates.
  • the content of the structural unit derived from (meth)acrylate having an alkyl group having 1 to 20 carbon atoms is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, based on the total amount of the block polymer. %, more preferably 30% by mass to 70% by mass, and particularly preferably 40% by mass to 60% by mass.
  • the anionic group includes, for example, a carboxy group, a salt of a carboxy group, a sulfo group, a salt of a sulfo group, a phosphate group, a salt of a phosphate group, a phosphonic acid group, and Salts of phosphonic acid groups are mentioned.
  • Counterions in the salt include alkali metal ions such as sodium ion, potassium ion and lithium ion; alkaline earth metal ions such as calcium ion and magnesium ion; and ammonium ion.
  • the anionic group is preferably a carboxy group or a salt of a carboxy group.
  • Anionic group-containing monomers include (meth)acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid and crotonic acid.
  • the anionic group-containing monomer is preferably (meth)acrylic acid.
  • the content of the structural unit derived from the anionic group-containing monomer is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 25% by mass, relative to the total amount of the block polymer. More preferably, it is in the range of 20% by mass to 20% by mass.
  • Whether or not the polymer contained in the ink is a block polymer can be determined, for example, by the following method.
  • a separation method such as solvent extraction is applied to the ink to separate the polymer.
  • the separated polymer is analyzed using various analysis methods such as nuclear magnetic resonance (NMR), infrared spectroscopy (IR), and thermal analysis, and physical properties such as the glass transition temperature are measured to identify the block polymer. It is possible to comprehensively determine whether or not there is.
  • the weight average molecular weight (Mw) of the block polymer is not particularly limited, it is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, from the viewpoint of pigment dispersibility. , 10,000 to 60,000 are more preferred.
  • the polymer having a crosslinked structure is not particularly limited as long as it has at least one crosslinked structure in its molecule.
  • a polymer having a crosslinked structure (hereinafter also referred to as a “crosslinked polymer”) is formed, for example, by crosslinking an uncrosslinked polymer with a crosslinking agent.
  • the uncrosslinked polymer is a water-soluble polymer.
  • uncrosslinked polymers examples include polyvinyl, polyurethane and polyester. Among them, the uncrosslinked polymer is preferably polyvinyl.
  • the uncrosslinked polymer is preferably a polymer having functional groups that can be crosslinked with a crosslinking agent.
  • Crosslinkable functional groups include carboxy groups or salts thereof, isocyanate groups, and epoxy groups.
  • the crosslinkable functional group is preferably a carboxy group or a salt thereof, and particularly preferably a carboxy group. That is, the uncrosslinked polymer is preferably a polymer containing carboxy groups.
  • the uncrosslinked polymer is preferably a copolymer containing structural units derived from a carboxy group-containing monomer (hereinafter referred to as "carboxy group-containing monomer").
  • the number of structural units derived from the carboxy group-containing monomer contained in the copolymer may be one, or two or more.
  • the copolymer may be a random copolymer or a block copolymer, but is preferably a random copolymer.
  • Carboxy group-containing monomers include, for example, (meth)acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid and crotonic acid.
  • the carboxy group-containing monomer is preferably (meth)acrylic acid or ⁇ -carboxyethyl acrylate, more preferably (meth)acrylic acid.
  • the content of the structural unit derived from the carboxy group-containing monomer, which may be contained in the uncrosslinked polymer, is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 25% by mass, relative to the total amount of the block polymer. and more preferably 3% by mass to 20% by mass.
  • the uncrosslinked polymer preferably contains structural units derived from hydrophobic monomers in addition to structural units derived from carboxy group-containing monomers.
  • the number of structural units derived from the hydrophobic monomer may be one, or two or more.
  • Structural units derived from hydrophobic monomers that may be contained in the uncrosslinked polymer include structural units derived from ethylenically unsaturated compounds having an aromatic ring structure or an alicyclic structure, and alkyl groups having 1 to 20 carbon atoms.
  • Structural units derived from (meth)acrylates having Preferred aspects of these structural units that can be included in the uncrosslinked polymer are the same as preferred aspects of these structural units that can be included in the block polymer.
  • the content of structural units derived from a hydrophobic monomer in the uncrosslinked polymer is preferably 35% to 95% by mass, more preferably 50% to 95% by mass, based on the total amount of the uncrosslinked polymer. is more preferable, and 70% by mass to 90% by mass is even more preferable.
  • the content of structural units derived from hydrophobic monomers in the crosslinked polymer is preferably 35% to 95% by mass, more preferably 50% to 95% by mass, relative to the total amount of the crosslinked polymer. is more preferable, and 70% by mass to 90% by mass is even more preferable.
  • the uncrosslinked polymer and the crosslinked polymer each include a (meth)acrylate structural unit having a benzene ring and a (meth)acrylate structural unit having an alkyl group having 12 or more carbon atoms as structural units derived from a hydrophobic monomer, may contain
  • the content of the (meth)acrylate structural unit having a benzene ring is preferably 20% by mass to 60% by mass with respect to the total amount of the polymer (ie, uncrosslinked polymer or crosslinked polymer).
  • the content of the (meth)acrylate structural unit having an alkyl group of 12 or more carbon atoms is preferably 10% by mass to 40% by mass based on the total amount of the polymer (ie, uncrosslinked polymer or crosslinked polymer).
  • the acid value of the uncrosslinked polymer is preferably 67 mgKOH/g to 200 mgKOH/g, more preferably 67 mgKOH/g to 150 mgKOH/g, from the viewpoint of pigment dispersibility.
  • acid value is a value measured by the method described in JIS K0070:1992.
  • the acid value of the crosslinked polymer is preferably 35 mgKOH/g to 185 mgKOH/g, more preferably 50 mgKOH/g to 150 mgKOH/g, from the viewpoint of suppressing cracking of the recorded image and improving the image quality of the recorded image. is more preferred, and 80 mgKOH/g to 130 mgKOH/g is even more preferred.
  • the acid value of the crosslinked polymer is 50 mgKOH/g or more, the image quality of the recorded image is more excellent. Further, when the acid value of the crosslinked polymer is 150 mgKOH/g or less, cracking of the recorded image is further suppressed.
  • the weight average molecular weight (Mw) of the uncrosslinked polymer is not particularly limited, but from the viewpoint of pigment dispersibility, it is preferably 3,000 to 100,000, more preferably 4,000 to 80,000. More preferably 5,000 to 60,000, even more preferably 10,000 to 60,000.
  • the preferred range of the weight average molecular weight (Mw) of the crosslinked polymer is also the same as the preferred range of the weight average molecular weight (Mw) of the uncrosslinked polymer.
  • the cross-linking agent used for cross-linking the uncross-linked polymer is preferably a compound having two or more reaction sites with the un-cross-linked polymer (eg, polymer having a carboxyl group). Only one type of cross-linking agent may be used, or two or more types may be used.
  • a preferred combination of a cross-linking agent and an uncrosslinked polymer is a combination of a compound having two or more epoxy groups (that is, a difunctional or more epoxy compound) and a polymer having a carboxy group.
  • a crosslinked structure is formed by the reaction of the epoxy group and the carboxy group. Formation of a crosslinked structure with a crosslinking agent is preferably carried out after dispersing the pigment with an uncrosslinked polymer.
  • Di- or higher-functional epoxy compounds include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and dipropylene glycol diglycidyl.
  • Ethers polypropylene glycol diglycidyl ether and trimethylolpropane triglycidyl ether.
  • the di- or more functional epoxy compound is preferably polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, or trimethylolpropane triglycidyl ether.
  • Cross-linking agents may be commercially available. Examples of commercially available products include Denacol EX-321, EX-821, EX-830, EX-850 and EX-851 (manufactured by Nagase ChemteX Corporation).
  • the molar ratio of the reactive site (e.g., epoxy group) in the cross-linking agent and the reactive site (e.g., carboxy group) in the uncrosslinked polymer is 1:1 from the viewpoint of the cross-linking reaction rate and dispersion stability after cross-linking. .1 to 1:10 is preferred, 1:1.1 to 1:5 is more preferred, and 1:1.1 to 1:3 is even more preferred.
  • the ink of the present disclosure preferably contains at least one water-soluble organic solvent. This further improves the ejection property of the ink from the inkjet head.
  • the content of the water-soluble organic solvent is preferably 5% by mass to 60% by mass, preferably 10% by mass to 40% by mass, and 15% by mass to 30% by mass with respect to the total amount of the ink. is more preferred.
  • boiling point means boiling point under 1 atmosphere (101,325 Pa).
  • water-soluble organic solvents having a boiling point of less than 220°C examples include 1,2-propanediol (also known as propylene glycol; PG) (boiling point of 188°C), 1,3-propanediol (boiling point of 213°C), propylene glycol monomethyl ether ( boiling point 121°C), ethylene glycol (boiling point 197°C), ethylene glycol monomethyl ether (boiling point 124°C), propylene glycol monoethyl ether (boiling point 133°C), ethylene glycol monoethyl ether (boiling point 135°C), propylene glycol monopropyl ether (boiling point 149°C), ethylene glycol monopropyl ether (boiling point 151°C), propylene glycol monobutyl ether (boiling point 170°C), ethylene glycol monobutyl ether (boiling point 17
  • the content of the water-soluble organic solvent with a boiling point of less than 220°C is preferably 1% by mass to 50% by mass relative to the total amount of the ink. , More preferably 5% to 40% by mass, still more preferably 10% to 40% by mass, still more preferably 15% to 35% by mass.
  • the content of the water-soluble organic solvent having a boiling point of 220°C or higher (hereinafter also referred to as “high-boiling solvent”) in the ink of the present disclosure is preferably 5% by mass or less. This further improves the drying property of the ink (that is, the drying property of the recorded image).
  • the content of the water-soluble organic solvent having a boiling point of 220°C or higher in the ink is 5% by mass or less
  • the ink does not contain a water-soluble organic solvent having a boiling point of 220°C or higher (i.e., The content of the water-soluble organic solvent with a boiling point of 220°C or higher in the ink is 0% by mass), or even if it is contained, the content of the water-soluble organic solvent with a boiling point of 220°C or higher is 5% relative to the total amount of the ink % or less.
  • the content of the water-soluble organic solvent having a boiling point of 220° C. or higher in the ink is more preferably 3% by mass or less, still more preferably 2% by mass or less, even more preferably 1% by mass or less, and still more preferably It is 0% by mass.
  • water-soluble organic solvents having a boiling point of 220° C. or higher examples include glycerin (boiling point 290° C.), 1,2-hexanediol (HDO) (boiling point 223° C.), diethylene glycol (boiling point 245° C.), diethylene glycol monobutyl ether (boiling point 230° C.
  • triethylene glycol (boiling point 285°C), dipropylene glycol (boiling point 232°C), tripropylene glycol (boiling point 267°C), trimethylolpropane (boiling point 295°C), 2-pyrrolidone (boiling point 245°C), tripropylene glycol monomethyl ether (boiling point 243°C), triethylene glycol monomethyl ether (boiling point 248°C), and the like.
  • the ink of the present disclosure may contain at least one type of resin particles.
  • resin particles are distinguished from polymer dispersants in that they are particles made of resin.
  • a water-insoluble resin is preferable as the resin constituting the resin particles.
  • the ink contains resin particles, the increase in viscosity of the ink is suppressed more than when the ink contains the same mass of water-soluble resin.
  • the ink is used as an inkjet ink, the ejection property of the ink from the inkjet head (hereinafter also simply referred to as "ink ejection property”) is further improved.
  • Water-insoluble means the property that the amount dissolved in 100 g of distilled water at 25° C. is less than 1 g.
  • the glass transition temperature of the resin particles there is no particular limitation on the glass transition temperature of the resin particles (that is, the glass transition temperature of the resin in the resin particles).
  • the glass transition temperature (Tg) of the resin particles is preferably 20° C. or higher, more preferably 50° C. or higher, and even more preferably 80° C. or higher.
  • the glass transition temperature (Tg) of the resin particles is preferably 200° C. or lower, more preferably 150° C. or lower, and still more preferably 130° C. or lower.
  • the resin particles are preferably acrylic resin particles (hereinafter also referred to as acrylic resin particles), polyester resin particles (hereinafter also referred to as polyester resin particles), and polyurethane resin particles (hereinafter also referred to as polyurethane resin particles). ), or particles made of polyolefin resin (hereinafter also referred to as polyolefin resin particles).
  • polyester resin means a polymer compound containing an ester bond in its main chain.
  • Polyester resins include polycondensates of polyvalent carboxylic acids (eg, dicarboxylic acids) and polyalcohols (eg, diols).
  • polyolefin resin means a polymer (homopolymer or copolymer) of raw material monomers containing olefin.
  • Polyolefin resins include polymers of one olefin, copolymers of two or more olefins, copolymers of one or more olefins and one or more other monomers, and the like.
  • Olefins include ⁇ -olefins having 2 to 30 carbon atoms.
  • polyurethane resin means a polymer compound containing urethane bonds.
  • the resin particles contained in the ink preferably contain acrylic resin particles from the viewpoint of further improving the adhesion and abrasion resistance of the image.
  • the ratio of the acrylic resin particles to the resin particles contained in the ink is preferably 60% by mass or more, more preferably 80% by mass or more, More preferably, it is 90% by mass or more.
  • the ratio of the acrylic resin particles to the resin particles contained in the ink is 60% by mass or more, the adhesion of the image is further improved.
  • self-dispersible resin particles are preferred.
  • the self-dispersing resin particles include self-dispersing polymer particles described in paragraphs 0062 to 0076 of JP-A-2016-188345 and paragraphs 0109 to 0140 of WO 2013/180074.
  • the resin in the resin particles preferably contains an alicyclic structure or an aromatic cyclic structure, and more preferably contains an alicyclic structure.
  • the alicyclic structure is preferably an alicyclic hydrocarbon structure having 5 to 10 carbon atoms, such as cyclohexane ring structure, dicyclopentanyl ring structure, dicyclopentenyl ring structure, norbornane ring structure, isobornane ring structure, norbornene ring structure. , an isobornene ring structure, or an adamantane ring structure is preferred.
  • the aromatic ring structure is preferably a naphthalene ring or a benzene ring, more preferably a benzene ring.
  • the amount of the alicyclic structure or aromatic ring structure is, for example, preferably 0.01 mol to 1.5 mol, more preferably 0.1 mol to 1 mol, per 100 g of the resin in the resin particles.
  • the resin in the resin particles preferably has an ionic group in its structure.
  • the ionic group may be an anionic group or a cationic group, but an anionic group is preferred.
  • the anionic group is not particularly limited, but is preferably a carboxy group, a salt of a carboxy group, a sulfo group, or a salt of a sulfo group.
  • the resin in the resin particles more preferably, at least one selected from the group consisting of benzyl (meth)acrylate units, phenoxyethyl (meth)acrylate units, and alicyclic structure-containing (meth)acrylate units; ) acrylic acid units, more preferably selected from the group consisting of benzyl (meth)acrylate units, phenoxyethyl (meth)acrylate units, and alicyclic structure-containing (meth)acrylate units It is an acrylic resin containing at least one type, a (meth)acrylic acid unit, and an alkyl (meth)acrylate unit containing an alkyl group having 1 to 4 carbon atoms.
  • Examples of (meth)acrylates containing an alicyclic structure include alkyl (meth)acrylates having a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclohexyl (meth)acrylate), isobornyl (meth)acrylate, adamantyl (meth)acrylate, and dicyclopentanyl (meth)acrylate is preferable, and at least one selected from isobornyl (meth)acrylate, adamantyl (meth)acrylate, and dicyclopentanyl (meth)acrylate is more preferable.
  • alkyl (meth)acrylates having a cycloalkyl group having 3 to 10 carbon atoms e.g., cyclohexyl (meth)acrylate
  • isobornyl (meth)acrylate e.g., cyclohexyl (meth)acrylate
  • adamantyl (meth)acrylate e.g.
  • the acid value of the resin in the resin particles is preferably 25 mgKOH/g to 100 mgKOH/g, more preferably 30 mgKOH/g to 90 mgKOH/g, from the viewpoint of self-dispersibility, cohesiveness during image recording, and the like. More preferably, it is 35 mgKOH/g to 80 mgKOH/g.
  • the weight-average molecular weight of the resin in the resin particles is preferably 1,000 to 300,000, more preferably 2,000 to 200,000, and even more preferably 5,000 to 100,000. Weight average molecular weight is measured by gel permeation chromatography (GPC). The details of GPC are as described above.
  • the volume average particle diameter of the resin particles is preferably 1 nm to 200 nm, more preferably 3 nm to 200 nm, even more preferably 5 nm to 50 nm.
  • the content of the resin particles with respect to the total amount of the ink is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, and 2% by mass. It is more preferably 15% by mass, more preferably 2% by mass to 10% by mass.
  • the inks of the present disclosure may contain at least one surfactant.
  • surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants, and the like.
  • Preferred surfactants include acetylene glycol-based surfactants, which are a kind of nonionic surfactants.
  • acetylene glycol-based surfactant for example, acetylene glycol-based surfactants described in paragraphs 0070 to 0080 of WO 2017/149917 can be used.
  • acetylene glycol surfactants include polyalkylene oxide adducts (preferably polyethylene oxide adducts) of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6- Polyalkylene oxide adduct of dimethyl-4-octyne-3,6-diol (preferably polyethylene oxide adduct), Polyalkylene oxide of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol Examples include adducts (preferably polyethylene oxide adducts), polyalkylene oxide adducts (preferably polyethylene oxide adducts) of 2,5-dimethyl-3-hexyne-2,5-diol, and the like.
  • acetylene glycol-based surfactants include the Surfynol series manufactured by Air Products Co., Ltd. or Nissin Chemical Industry Co., Ltd. (e.g., Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485), or Fin series (eg, Olfine E1010, Olfine E1020), Dynol series (eg, Dynol 604), etc.; acetylenol manufactured by Kawaken Fine Chemicals Co., etc.; Commercially available acetylene glycol-based surfactants are also available from Dow Chemical Company, General Aniline, and the like.
  • Surfactants may include fluorosurfactants.
  • Commercially available fluorosurfactants include Capstone FS-63, Capstone FS-61 (manufactured by Dupont), Futergent 100, Futergent 110, Futergent 150 (manufactured by Neos Co., Ltd.), and CHEMGUARD S-760P. (manufactured by Chemguard Inc.).
  • surfactant pp. 37-38 of JP-A-59-157636 and Research Disclosure No. 308119 (1989) as surfactants.
  • fluorine (fluorinated alkyl) surfactants and silicone surfactants described in JP-A-2003-322926, JP-A-2004-325707, and JP-A-2004-309806 are also included. .
  • the content of the surfactant in the ink is appropriately adjusted in consideration of the surface tension of the ink.
  • the content of the surfactant in the ink is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, and 0.1% by mass to 2% by mass, relative to the total amount of the ink. is more preferred.
  • the ink may contain other components than the above components.
  • Other components include, for example, urea, urea derivatives, waxes, antifading agents, emulsion stabilizers, penetration accelerators, UV absorbers, preservatives, antifungal agents, pH adjusters, antifoaming agents, viscosity adjusters, Known additives such as dispersion stabilizers and chelating agents are included.
  • the viscosity of the ink of the present disclosure is preferably 1.2 mPa s or more and 15.0 mPa s or less, more preferably 2 mPa s or more and less than 13 mPa s, and 2.5 mPa s or more and 10 mPa s. It is preferably less than Viscosity is a value measured at 25° C. using a viscometer.
  • a viscometer for example, a VISCOMETER TV-22 type viscometer (manufactured by Toki Sangyo Co., Ltd.) can be used.
  • the surface tension of the ink of the present disclosure is preferably 25 mN/m or more and 40 mN/m or less, more preferably 27 mN/m or more and 37 mN/m or less.
  • Surface tension is a value measured at a temperature of 25°C.
  • Surface tension can be measured using, for example, Automatic Surface Tentiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • the pH of the ink of the present disclosure at 25° C. is preferably pH 6 to 11, more preferably pH 7 to 10, and even more preferably pH 7 to 9, from the viewpoint of dispersion stability.
  • the pH of the ink at 25°C is measured using a commercially available pH meter.
  • a first embodiment of the ink set of the present disclosure includes the above-described white ink, which is the ink of the present disclosure, and color inks containing water and color pigments.
  • a multicolor image can be printed with white ink and color ink.
  • a multicolor image for example; A color pattern image (characters, figures, etc.) recorded with color ink and a solid white image recorded with white ink so as to cover the pattern image are arranged in this order on a substrate.
  • color image B A white pattern image (characters, figures, etc.) recorded with white ink and a solid color image recorded with color ink so as to cover the pattern image are arranged in this order on the substrate.
  • multicolor image C A solid white image recorded with white ink and a color pattern image (characters, figures, etc.) recorded on the white image with color ink are arranged in this order on a substrate.
  • Next color image D etc.
  • the pattern image is viewed through the substrate from the back side of the substrate (ie, the non-imaging side). Such a mode of image recording is sometimes commonly referred to as "reverse printing".
  • the ink set of the first embodiment includes the ink of the present disclosure described above, it exhibits the same effect as the ink of the present disclosure.
  • color in the first embodiment includes both chromatic colors such as cyan, magenta, yellow, red, blue, and green, and black.
  • the ink set of the first embodiment includes color inks containing water and color pigments.
  • the ink set of the first embodiment may contain only one type of color ink, or two or more types of color inks.
  • (water) Color inks contain water.
  • the water content is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and still more preferably 60% by mass or more, relative to the total amount of the color ink. be.
  • the upper limit of the water content is appropriately determined according to the content of other components.
  • the upper limit of water content is, for example, 90% by mass, 80% by mass, and the like.
  • Color inks contain at least one color pigment.
  • color ink means ink other than the white ink.
  • Color pigments include chromatic pigments such as cyan, magenta, yellow, red, blue, green, violet, pink, orange, and brown, and black pigments.
  • color pigments for example, Seishiro Ito, "Dictionary of Pigments” (published in 2000); Herbst, K.; Hunger “Industrial Organic Pigments”, Isao Hashimoto “Organic Pigment Handbook” (published in 2006), JP-A-2002-12607, JP-A-2002-188025, JP-A-2003-26978, JP-A-2003-342503 Examples thereof include pigments described in publications and the like.
  • the content of the color pigment is preferably 0.5% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, relative to the total amount of the color ink.
  • the color ink preferably contains at least one silicon compound selected from the group consisting of silicates and colloidal silica.
  • At least one silicon compound selected from the group consisting of silicate and colloidal silica contained in the white ink is referred to as the first silicon compound, and the silicate and colloidal silica contained in the color ink are referred to as the first silicon compound.
  • At least one silicon compound selected from the group consisting of may be referred to as a second silicon compound.
  • Preferred aspects of the second silicon compound are the same as those of the first silicon compound.
  • X1/X2 the ratio is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 1.0 or less, still more preferably less than 1.0, from the viewpoint of image definition, It is more preferably 0.9 or less, and still more preferably 0.5 or less.
  • the X1/X2 ratio is 5.0 or less, the image definition is further improved.
  • the effect of improving image definition by limiting the X1/X2 ratio to 5.0 or less is particularly obtained by applying a pretreatment liquid, color ink, and white ink, which will be described later, in this order onto the substrate to form an image. It is particularly effective in the mode of recording. Specifically, when the X1/X2 ratio is limited to 5.0 or less in the above embodiment, the content of the silicon compound is limited in the white ink applied after the color ink, thereby reducing the white ink. The increase in pH is restricted, and as a result, the aggregation effect of the components in the white ink by the pretreatment liquid can be exhibited more effectively. As a result, the definition of an image is further improved in a multicolor image using color inks and white ink.
  • Examples of the above-described mode include a mode in which a pattern image such as characters and graphics is recorded with color ink, and a white image (for example, a solid white image) is recorded with white ink so as to cover the pattern image. .
  • the pattern image is viewed through the substrate from the image non-recording surface side of the substrate.
  • the lower limit of the X1/X2 ratio is preferably 0.01, more preferably 0.02, from the viewpoint of more effectively exhibiting the effect of the first silicon compound in the white ink.
  • the first silicon compound contains silicate and the second silicon compound contains colloidal silica, from the viewpoint of further improving image definition.
  • the effect of improving the definition of an image when the first silicon compound contains a silicate and the second silicon compound contains colloidal silica is obtained by applying a pretreatment liquid, a color ink, and a white ink, which will be described later, on the substrate in this order. It is particularly effective in a mode in which an image is recorded by application. The reason for this is presumed as follows. Specifically, in image recording corresponding to the above, the aggregating agent in the pretreatment liquid is consumed by the specific silicon compound (ie, colloidal silica and/or silicate) in the ink.
  • the amount of flocculant consumption by colloidal silica is considered to be less than that by silicate. Therefore, by including colloidal silica in the second silicon compound in the color ink, it is possible to suppress the consumption of the flocculant at the stage where the color ink is applied and to leave the flocculant. It is considered that the amount of aggregating agent acting on the white ink to be applied later can be ensured. As a result, the aggregation effect of the components in the white ink by the pretreatment liquid can be exhibited more effectively, and it is believed that the definition of the image is further improved in the multicolor image using the color ink and the white ink. .
  • the ink set of the first embodiment preferably contains a pretreatment liquid containing water and a coagulant.
  • the function of the flocculant in the pretreatment liquid is to flocculate the components in the ink.
  • the pretreatment liquid is applied to the base material before the color ink and the white ink are applied. Color ink and white ink are applied respectively. As a result, for example, the above-described multicolor image is recorded.
  • the pretreatment liquid contains water.
  • the water content is preferably 50% by mass or more, more preferably 60% by mass or more, relative to the total amount of the pretreatment liquid.
  • the upper limit of the water content is preferably 90% by mass or less with respect to the total amount of the pretreatment liquid, although it depends on the amount of other components.
  • the pretreatment liquid contains at least one coagulant.
  • the aggregating agent is a component for aggregating the components in the ink on the impermeable substrate. At least one selected from the group consisting of organic acids, organic acid salts, polyvalent metal compounds, metal complexes, and water-soluble cationic polymers is preferable as the flocculant.
  • Organic acids include organic compounds having an acidic group.
  • acidic groups include phosphoric acid groups, phosphonic acid groups, phosphinic acid groups, sulfuric acid groups, sulfonic acid groups, sulfinic acid groups, and carboxy groups.
  • the acidic group is preferably a phosphoric acid group or a carboxy group, more preferably a carboxy group, from the viewpoint of ink aggregation speed.
  • Organic compounds having a carboxy group include polyacrylic acid, acetic acid, formic acid, benzoic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, succinic acid, glutaric acid, fumaric acid, Citric acid, tartaric acid, phthalic acid, adipic acid, pimelic acid, 4-methylphthalic acid, lactic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid , pimelic acid, etc. are preferred. These compounds may be used singly or in combination of two or more.
  • a carboxylic acid having a valence of 2 or more (hereinafter also referred to as a polyvalent carboxylic acid) is preferable from the viewpoint of ink aggregation speed.
  • the polycarboxylic acid is preferably dicarboxylic acid or tricarboxylic acid, more preferably glutaric acid, malonic acid, succinic acid, adipic acid, pimelic acid, malic acid, maleic acid, fumaric acid, tartaric acid, or citric acid, and glutaric acid.
  • malonic acid succinic acid, adipic acid, pimelic acid, malic acid, fumaric acid, tartaric acid, or citric acid, and more preferably glutaric acid, malonic acid, succinic acid, adipic acid, or pimelic acid.
  • the organic acid has a low pKa (eg, 1.0 to 5.0).
  • pKa eg, 1.0 to 5.0
  • the surface charge of particles such as pigments and polymer particles in the ink, which are dispersed and stabilized by weakly acidic functional groups such as carboxyl groups, is reduced by bringing them into contact with an organic acidic compound having a lower pKa, thereby improving the dispersion stability. can be reduced.
  • the organic acid preferably has a low pKa, a high solubility in water, and a valence of 2 or more.
  • a divalent or trivalent acidic substance having a high buffering capacity in a low pH range is more preferable.
  • Organic acid salts include salts of the organic acids exemplified above.
  • Organic acid salts include alkaline earth metals of group 2 of the periodic table (e.g. magnesium, calcium), transition metals of group 3 of the periodic table (e.g. lanthanum), cations from group 13 of the periodic table (e.g. Examples include organic acid salts including aluminum) and lanthanides (eg, neodymium).
  • an organic acid salt containing an alkaline earth metal is preferable, and an organic acid salt containing calcium (e.g., calcium lactate, calcium acetate, etc.) or an organic acid salt containing magnesium (e.g., magnesium lactate, magnesium acetate , etc.) are preferred.
  • Polyvalent metal compounds include alkaline earth metals of group 2 of the periodic table (e.g. magnesium, calcium), transition metals of group 3 of the periodic table (e.g. lanthanum), cations from group 13 of the periodic table. (eg, aluminum) and lanthanides (eg, neodymium) (excluding organic acid salts) containing at least one selected from the group consisting of. Nitrates, chlorides or thiocyanates are suitable as polyvalent metal compounds. Particularly preferred polyvalent metal compounds are calcium or magnesium nitrate, calcium chloride, magnesium chloride, or calcium or magnesium thiocyanate. At least a part of the polyvalent metal compound is preferably dissociated into polyvalent metal ions and counter ions in the pretreatment liquid.
  • alkaline earth metals of group 2 of the periodic table e.g. magnesium, calcium
  • transition metals of group 3 of the periodic table e.g. lanthanum
  • cations from group 13 of the periodic table e.g, aluminum
  • a metal complex containing at least one selected from the group consisting of zirconium, aluminum, and titanium as a metal element is preferable.
  • the ligand is selected from the group consisting of acetate, acetylacetonate, methylacetoacetate, ethylacetoacetate, octylene glycolate, butoxyacetylacetonate, lactate, lactate ammonium salt, and triethanolamine. are preferred.
  • metal complexes are commercially available as metal complexes, and in the present disclosure, commercially available metal complexes may be used.
  • the content of the flocculant there is no particular limitation on the content of the flocculant.
  • the content of the aggregating agent relative to the total amount of the pretreatment liquid is preferably 0.1% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass. It is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, and particularly preferably 2% by mass to 8% by mass.
  • the pretreatment liquid preferably contains at least one resin.
  • the pretreatment liquid contains a resin, the adhesion of the image is further improved.
  • the glass transition temperature (Tg) of the resin contained in the pretreatment liquid is preferably 0° C. or higher, more preferably 10° C. or higher, and still more preferably 20° C. or higher. and more preferably 30° C. or higher.
  • the glass transition temperature (Tg) of the resin contained in the pretreatment liquid is preferably 120° C. or lower, more preferably 100° C. or lower, and still more preferably 80° C. or lower. and more preferably 70° C. or less.
  • the glass transition temperature of a resin means a value measured using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • a specific measurement of the glass transition temperature is performed according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011).
  • the glass transition temperature in the present disclosure is the extrapolated glass transition initiation temperature (hereinafter sometimes referred to as Tig).
  • Tig extrapolated glass transition initiation temperature
  • a method for measuring the glass transition temperature will be described more specifically.
  • heating rate 20° C./min. Heat up to 30° C. higher temperature and create a differential thermal analysis (DTA) curve or DSC curve.
  • DTA differential thermal analysis
  • the extrapolated glass transition start temperature (Tig) that is, the glass transition temperature in the present disclosure, is a straight line obtained by extending the baseline on the low temperature side of the DTA curve or DSC curve to the high temperature side, and the curve of the stepped change part of the glass transition. It is obtained as the temperature at the point of intersection with the tangent line drawn at the point where the gradient is maximum.
  • the glass transition temperature (Tg) of the resin in the pretreatment liquid means the weighted average value of the glass transition temperatures of the individual resins.
  • Resins that can be contained in the pretreatment liquid include acrylic resins, polyester resins, polyolefin resins, polyurethane resins, polyurea resins, polyamide resins, polycarbonate resins, polystyrene resins, and the like.
  • the resin that can be contained in the pretreatment liquid preferably contains a polyester resin or an acrylic resin, and more preferably contains a polyester resin.
  • the resin that can be contained in the pretreatment liquid may be a water-soluble resin or a water-insoluble resin, but a water-insoluble resin is preferable.
  • the pretreatment liquid preferably contains resin particles.
  • the resin particles preferably consist of a water-insoluble resin.
  • the resin particles are preferably acrylic resin particles, polyester resin particles, a kneaded mixture of acrylic resin particles and polyester resin particles, or composite particles containing an acrylic resin and a polyester resin.
  • the weight average molecular weight (Mw) of the resin in the resin particles is preferably 1,000 to 300,000, more preferably 2,000 to 200,000, even more preferably 5,000 to 100,000.
  • the volume average particle size of the resin particles is preferably 1 nm to 300 nm, more preferably 3 nm to 200 nm, and even more preferably 5 nm to 150 nm.
  • the volume average particle diameter of resin particles means a value measured by a particle size distribution measuring device using light scattering (for example, Microtrac UPA (registered trademark) EX150 manufactured by Nikkiso Co., Ltd.).
  • a commercially available aqueous dispersion of resin particles may be used.
  • Commercially available aqueous dispersions of resin particles include Pesresin A124GP, Pesresin A645GH, Pesresin A615GE, Pesresin A520 (manufactured by Takamatsu Yushi Co., Ltd.), Eastek1100, Eastek1200 (manufactured by Eastman Chemical Co., Ltd.), Plascoat RZ570, Pluscoat Z687, Pluscoat Z565, Pluscoat RZ570, Pluscoat Z690 (manufactured by GOO Chemical Industry Co., Ltd.), Vylonal MD1200 (manufactured by Toyobo Co., Ltd.), EM57DOC (manufactured by Daicel Finechem), and the like.
  • the content of the resin particles relative to the total amount of the pretreatment liquid is preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass. More preferably, it is particularly preferably 1% by mass to 15% by mass.
  • the pretreatment liquid preferably contains at least one water-soluble organic solvent.
  • water-soluble organic solvent any known one can be used without particular limitation.
  • alkanediols e.g., ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2- octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, etc.), polyalkylene glycols (e.g., diethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,3-butanedi
  • the content of the water-soluble organic solvent with respect to the total amount of the pretreatment liquid is preferably 0.5% by mass to 30% by mass, and 1% by mass to 20% by mass. is more preferable, and 1% by mass to 15% by mass is particularly preferable.
  • a water-soluble organic solvent having a boiling point of less than 220° C. is also preferable as the water-soluble organic solvent that can be contained in the pretreatment liquid.
  • the pretreatment liquid does not contain an organic solvent with a boiling point of 220°C or higher, or the content of the organic solvent with a boiling point of 220°C or higher is 5% relative to the total amount of the pretreatment liquid. % by mass or less (more preferably 3 mass % or less, still more preferably 1 mass % or less).
  • Specific examples of the water-soluble organic solvent having a boiling point of less than 220° C. and the organic solvent having a boiling point of 220° C. or more can be referred to the section “Step of preparing the first ink” described later.
  • the pretreatment liquid may contain other components than those described above, if necessary.
  • Other ingredients that can be contained in the pretreatment liquid include surfactants, solid wetting agents, silicic compounds (e.g. colloidal silica), inorganic salts, anti-fading agents, emulsion stabilizers, penetration accelerators, UV absorbers, preservatives. agents, antifungal agents, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, water-soluble polymer compounds other than water-soluble cationic polymers (for example, paragraphs 0026 to 0080 of JP-A-2013-001854. known additives such as water-soluble polymer compounds).
  • the pretreatment liquid preferably has a pH of 0.1 to 3.5 at 25°C.
  • the pH of the pretreatment liquid is 0.1 or more, the roughness of the resin substrate is further reduced, and the adhesion of the image portion is further improved.
  • the pH of the pretreatment liquid is 3.5 or less, the aggregation speed is further improved, coalescence of ink dots (ink dots) on the surface of the resin base material is further suppressed, and roughness of the image is further reduced.
  • the pH of the pretreatment liquid at 25° C. is more preferably 0.2 to 2.0.
  • the viscosity of the pretreatment liquid is preferably in the range of 0.5 mPa ⁇ s to 10 mPa ⁇ s, more preferably in the range of 1 mPa ⁇ s to 5 mPa ⁇ s, from the viewpoint of ink aggregation speed. more preferred.
  • the surface tension of the pretreatment liquid is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, even more preferably 30 mN/m to 45 mN/m.
  • a second embodiment of the ink set of the present disclosure includes the ink of the present disclosure described above and a pretreatment liquid containing water and a coagulant.
  • the second embodiment includes a pretreatment liquid, but is not limited to including color inks. In this respect, the second embodiment differs from the first embodiment.
  • the second embodiment is the same as the first embodiment, and preferred aspects of the second embodiment (for example, preferred aspects of each of the ink and the pretreatment liquid) are also the same as the preferred aspects of the first embodiment. be.
  • the ink set of the second embodiment also contains the ink of the present disclosure described above, and thus exhibits the same effect as the ink of the present disclosure.
  • the image recording method of the present disclosure includes an ink application step of applying the ink of the present disclosure onto a substrate by an inkjet method.
  • the image recording method of the present disclosure may include other steps as necessary.
  • the ink applying step is a step of applying the ink of the present disclosure onto the substrate by an inkjet method. Through this process, an image is recorded with the ink of the present disclosure.
  • the substrate is not particularly limited, and known substrates can be used.
  • substrates include paper substrates, resin-laminated paper substrates (e.g., polyethylene, polypropylene, polystyrene, etc.), resin substrates, and metal plates (e.g., metal plates such as aluminum, zinc, and copper).
  • resin-laminated paper substrates e.g., polyethylene, polypropylene, polystyrene, etc.
  • resin substrates e.g., aluminum, zinc, and copper
  • metal plates e.g., metal plates such as aluminum, zinc, and copper
  • Textile base materials include natural fibers such as cotton, silk, hemp, and wool; chemical fibers such as viscose rayon and Rheocell; synthetic fibers such as polyester, polyamide, and acrylic; A mixture of at least two selected from the group consisting of As the textile substrate, the textile substrates described in paragraphs [0039] to [0042] of WO2015/158592 may be used.
  • the substrate is preferably a non-permeable substrate.
  • the non-permeable substrate refers to a substrate having a water absorption (% by mass, 24 hr.) of less than 0.2 according to ASTM D570 of the ASTM test method.
  • the impermeable base material is not particularly limited, but a resin base material is preferable.
  • the resin substrate is not particularly limited, and examples thereof include thermoplastic resin substrates. Examples of resin substrates include substrates obtained by forming a thermoplastic resin into a sheet or film. As the resin substrate, a substrate containing polypropylene, polyethylene terephthalate, nylon, polyethylene, or polyimide is preferable.
  • the resin substrate may be a transparent resin substrate.
  • transparent means that the transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more (preferably 90% or more).
  • a transparent resin base material is suitable for the mode in which an image is viewed through the base material from the non-image-recording surface side of the base material, as described above.
  • the shape of the resin base material is not particularly limited, but it is preferably a sheet-like resin base material, and more preferably a sheet-like resin base material that can be wound into a roll.
  • the thickness of the resin substrate is preferably 10 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m.
  • the resin substrate may be surface-treated from the viewpoint of improving the surface energy.
  • surface treatment include, but are not limited to, corona treatment, plasma treatment, flame treatment, heat treatment, abrasion treatment, light irradiation treatment (UV treatment), and flame treatment.
  • the ink of the present disclosure is applied onto a substrate by an inkjet method. That is, the ink of the present disclosure is ejected from an inkjet head and applied onto a substrate.
  • the resolution of the inkjet head is preferably 300 dpi or more, more preferably 600 dpi, still more preferably 800 dpi.
  • dpi is an abbreviation for dot per inch, and 1 inch is 2.54 cm.
  • Methods of ejecting ink from an inkjet head include, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezo element, and an electric signal.
  • Acoustic inkjet method that uses radiation pressure to irradiate ink instead of an acoustic beam to eject ink
  • Thermal inkjet (bubble jet (registered trademark)) method that heats ink to form bubbles and uses the pressure generated etc. can be applied.
  • a method of ejecting ink from an inkjet head for example, in the method described in Japanese Patent Laid-Open No.
  • an inkjet head in which at least a portion of the portions in contact with ink (for example, the nozzle plate and the ink flow path) contain silicon is suitable.
  • the nozzle plate include a silicon nozzle plate having a plurality of ejection holes.
  • the nozzle plate may contain a silicon oxide film.
  • an inkjet head having a plurality of ejection holes and having a liquid-repellent film provided on an ejection surface (for example, an ejection surface of a nozzle plate) can be used.
  • the liquid-repellent film in the inkjet head preferably contains a fluorine compound, more preferably a compound containing a fluorinated alkyl group, and even more preferably a perfluoroalkyl ether.
  • the thickness of the liquid-repellent film is not particularly limited, it is preferably 0.2 nm to 30 nm, more preferably 0.4 nm to 20 nm.
  • a commercially available product may be used as the inkjet head.
  • Commercially available products include an inkjet head “KM1800i” manufactured by Konica Minolta, an inkjet head “KJ4A-AA” manufactured by Kyocera, and an inkjet head “Samba G3L” manufactured by FUJIFILM Dimatix.
  • the amount of ink droplets ejected from the ejection holes of the inkjet head is preferably 1.0 pL (picoliters) or more from the viewpoint of obtaining an image with excellent hiding properties.
  • the ink droplet volume is more preferably 1.5 pL or more.
  • the upper limit of the ink droplet volume is preferably 10 pL, more preferably 6 pL.
  • the diameter of the ejection holes through which the ink is ejected is preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less.
  • the lower limit of the diameter of the ejection hole is not particularly limited, but examples of the lower limit include 10 ⁇ m, 11 ⁇ m, and 12 ⁇ m.
  • the resolution of the inkjet head is preferably 300 dpi or more, more preferably 600 dpi, still more preferably 800 dpi.
  • dpi is an abbreviation for dot per inch, and 1 inch is 2.54 cm.
  • the single-pass method uses, as an inkjet head, a line head in which ejection holes (nozzles) are arranged corresponding to the entire area of one side of the base material, the line head is fixedly arranged, and the base material is In this method, the ink is applied onto the substrate being transported while the substrate is being transported in a direction that intersects the arrangement direction of the ejection holes of the line head.
  • the scan method is a method in which a short serial head is used as an inkjet head, and ink is applied by scanning the short serial head with respect to the base material.
  • an image may be obtained by heating and drying the ink applied on the substrate.
  • Means for drying by heating include known heating means such as heaters, known air blowing means such as dryers, and means combining these.
  • Methods for drying the ink by heating include, for example, a method of applying heat with a heater or the like from the side opposite to the ink-applied side of the base material, and a method of applying warm air or hot air to the ink-applied side of the base material. , a method of applying heat with an infrared heater from the side opposite to the ink-applied side of the base material or the specific ink-applied side, a combination of these methods, and the like.
  • the heating temperature during heat drying is preferably 55° C. or higher, more preferably 60° C. or higher, and particularly preferably 65° C. or higher.
  • the upper limit of the heating temperature is not particularly limited, but the upper limit is, for example, 100°C, preferably 90°C.
  • the time for heating and drying the ink is not particularly limited, but is preferably 3 seconds to 60 seconds, more preferably 5 seconds to 60 seconds, and particularly preferably 10 seconds to 45 seconds.
  • the substrate may be heated in advance before applying the ink.
  • the heating temperature may be appropriately set, but the temperature of the substrate is preferably 20°C to 50°C, more preferably 25°C to 40°C.
  • the image recording method of the present disclosure may include other steps than the ink applying step.
  • Other steps include a pretreatment liquid application step, which is a step provided before the ink application step, in which a pretreatment liquid containing a coagulant and water is applied onto the substrate.
  • the pretreatment liquid applying step the ink is applied onto the area of the substrate to which the pretreatment liquid has been applied. That is, the image recording method preferably has a pretreatment liquid application step and an ink application step in this order.
  • the pretreatment liquid application step is a step of applying a pretreatment liquid containing water and a coagulant onto the impermeable substrate
  • the ink application step is a pretreatment liquid-applied non-permeable substrate. It is also preferable to apply an inkjet ink onto the area of the base material to which the treatment liquid has been applied.
  • the pretreatment liquid is as described in the section on the ink set above.
  • the flocculant contained in the pretreatment liquid is preferably at least one selected from the group consisting of polyvalent metal compounds, organic acids, metal complexes and cationic polymers, and more preferably contains an organic acid.
  • Application of the pretreatment liquid in the pretreatment liquid application step can be performed by applying a known application method such as a coating method, an inkjet recording method, or an immersion method.
  • a coating method such as a coating method, an inkjet recording method, or an immersion method.
  • the coating method include known coating methods using a bar coater, extrusion die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater and the like.
  • the pretreatment liquid applied onto the substrate may be dried by heating.
  • the preferred method and conditions for heat drying are the same as the preferred method and conditions for heat drying of ink that can be carried out in the ink application step.
  • An image recording method using the ink set of the first embodiment preferably includes: A color ink application step of ejecting color ink from an inkjet head and applying it onto a non-permeable substrate; A white ink application step of ejecting white ink from an inkjet head and applying it onto a region to which the color ink is applied on the non-permeable substrate to which the color ink is applied; including.
  • a color pattern image (characters, figures, etc.) recorded with color ink and a solid image recorded with white ink so as to cover the pattern image are formed on the substrate. It is easy to manufacture an image recorded matter including a multicolor image A in which a white image and a white image are arranged in this order.
  • the image recording method of the above embodiment preferably further includes a pretreatment liquid application step of applying the above-described pretreatment liquid onto the impermeable substrate before the color ink application step.
  • a pretreatment liquid application step of applying the above-described pretreatment liquid onto the impermeable substrate before the color ink application step.
  • water means ion-exchanged water unless otherwise specified.
  • Example 1 ⁇ Preparation of white ink>> A white ink W1 was prepared. Details are shown below.
  • Solution I obtained by dissolving 640 g of benzyl methacrylate, 340 g of methacrylic acid, and 19.94 g of 2-mercaptopropionic acid in 370.28 g of dipropylene glycol;
  • Solution II obtained by dissolving 17.69 g of t-butyl peroxy-2-ethylhexanoate (product name “Perbutyl O”, manufactured by NOF Chemical) in 221.17 g of dipropylene glycol; were prepared respectively.
  • Solution I was added dropwise to the three-necked flask over 4 hours, and solution II was added dropwise over 5 hours. After the dropwise addition was completed, the reaction was further continued for 2 hours. Disappearance of the monomer was confirmed by 1 H-NMR.
  • the resulting reaction solution was heated to 70° C., 248.02 g of a 50% by mass potassium hydroxide aqueous solution was added, and then 107.48 g of dipropylene glycol and 75.52 g of pure water were added and stirred to obtain 37 masses of random polymer. % solution was obtained.
  • This random polymer was designated as uncrosslinked polymer dispersant N1.
  • Structural units constituting the resulting random polymer ie, uncrosslinked polymer dispersant N1 were confirmed by 1 H-NMR.
  • the weight average molecular weight (Mw) was determined by GPC.
  • the obtained uncrosslinked polymer dispersant N1 had a weight average molecular weight (Mw) of 8400 and an acid value of 221.7 mgKOH/g.
  • a white pigment dispersion liquid N (uncrosslinked dispersion liquid) in which the white pigment is dispersed by the uncrosslinked polymer dispersant N1 was obtained.
  • the uncrosslinked dispersion had a pigment concentration of 45% by weight and an uncrosslinked polymer dispersant N1 concentration of 3.6% by weight.
  • Trimethylolpropane polyglycidyl ether (product name “Denacol EX-321”) is added as a cross-linking agent to 136 parts by mass of white pigment dispersion N (uncross-linked dispersion) in which white pigment is dispersed by non-cross-linked polymer dispersant N1.
  • white pigment dispersion N uncross-linked dispersion
  • N1 non-cross-linked polymer dispersant N1.
  • boric acid aqueous solution boric acid concentration: 4% by mass
  • the uncrosslinked polymer dispersant N1 in the dispersion is crosslinked to form the crosslinked polymer dispersant L1, thereby obtaining a white pigment dispersion (crosslinked dispersion) in which the white pigment is dispersed by the crosslinked polymer dispersant L1.
  • rice field. Ion-exchanged water was added to the resulting crosslinked dispersion so that the concentration of the pigment was 15% by mass.
  • the cross-linked dispersion to which ion-exchanged water was added was subjected to an ultrafiltration device (cross-flow type ultra filter (UF), manufactured by Sartorius) equipped with a polyethersulfone (PESU) membrane (pore size: 0.1 ⁇ m).
  • UF cross-flow type ultra filter
  • PESU polyethersulfone
  • Crosslinked polymer dispersant L1 is a crosslinked polymer obtained by crosslinking uncrosslinked polymer dispersant N1 with polyethylene glycol diglycidyl ether as a crosslinking agent.
  • a white ink which will be described later, was prepared using a white pigment dispersion CL containing this crosslinked polymer dispersant L1.
  • a dispersion of resin particles P1 which is one of the components in the ink, was prepared. Details are shown below.
  • a 2-liter three-necked flask (reaction vessel) equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 560.0 g of methyl ethyl ketone and heated to 87°C.
  • Step (1) A solution of 1.16 g of "V-601" and 6.4 g of methyl ethyl ketone was added and stirred for 2 hours. Subsequently, the operation of the above step (1) was repeated four times, and then a solution consisting of 1.16 g of "V-601" and 6.4 g of methyl ethyl ketone was added and stirring was continued for 3 hours (the operation up to this point was “reaction”).
  • ⁇ Preparation of white ink W1> Using the white pigment dispersion CL containing the crosslinked polymer dispersant L1, the dispersion of the resin particles P1, and the materials in the following composition, a white ink W1 having the following composition was prepared.
  • "dispersion method” column in Tables 1 and 2 below “crosslinked” means that the white pigment dispersion CL containing the crosslinked polymer dispersant L1 was used in the preparation of the white ink.
  • a pretreatment liquid was obtained by mixing components having the following composition.
  • pretreatment liquid - Malonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; flocculant (organic acid)) ... 5.0% by mass ⁇ Sodium dodecylbenzenesulfonate (surfactant) (manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.0% by mass ⁇ Water: Remaining amount of 100% by mass in total
  • Image recording>> Using the above ink, using a biaxially oriented polypropylene (OPP) film (thickness: 40 ⁇ m, surface treatment: corona discharge treatment, manufactured by Futamura Chemical Co., Ltd.) (impermeable substrate) as a substrate, the following procedure was performed. Image recording was performed.
  • OPP biaxially oriented polypropylene
  • the above ink is ejected from the inkjet head to deposit the ink onto the corona discharge-treated surface of the substrate. It was applied in the form of a solid image. By drying the ink applied on the substrate at 80° C.
  • a liquid-repellent film (SAM (Self-Assembled Monolayer) film) was formed using a fluorinated alkylsilane compound, and an inkjet head (hereinafter also referred to as an “IJ head”) was evaluated.
  • a specimen was obtained.
  • the white ink W1 (30 mL) prepared above was placed in a polypropylene 50 mL wide-mouth bottle (eyeboy wide-mouth bottle 50 mL (manufactured by AS ONE)), the test piece was immersed therein, and the ink temperature was 60 ° C. for 72 hours. aged.
  • the test piece was taken out from the white ink W1 and washed with ultrapure water, and the water contact angle of the surface on the liquid-repellent film side of the washed test piece was measured.
  • the water contact angle was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.) and ultrapure water in an environment of 25° C. and 50 RH% according to a conventional method.
  • DM-500 manufactured by Kyowa Interface Science Co., Ltd.
  • ultrapure water in an environment of 25° C. and 50 RH% according to a conventional method.
  • the dissolution deterioration of the IJ head was evaluated according to the following evaluation criteria.
  • the water contact angle of the surface on the liquid-repellent film side of the test piece before being immersed in the white ink W1 was 80° or more.
  • AA is the rank for which dissolution deterioration of the inkjet head is most suppressed.
  • the water contact angle was 80° or more.
  • A The water contact angle was 60° or more and less than 80°.
  • B The water contact angle was 40° or more and less than 60°.
  • C The water contact angle was 20° or more and less than 40°.
  • D The water contact angle was less than 20°.
  • a test piece for IJ head evaluation similar to the test piece used for evaluation of dissolution deterioration of the IJ head was prepared.
  • Diethylene glycol monobutyl ether (20 parts by mass), diethylene glycol (10 parts by mass), and water (70 parts by mass) were mixed to obtain cleaning liquid 1.
  • the resulting cleaning liquid 1 (97 parts by mass) and white ink W1 (3 parts by mass) were mixed to obtain diluted ink.
  • a cloth (Toraysee manufactured by Toray Industries, Inc.) was wound around a ⁇ 40 mm rubber roller having a rotating mechanism, and the wound cloth was impregnated with the diluted ink.
  • the roller was rotated to perform a rubbing operation in which the surface of the test piece on the liquid-repellent film side was rubbed with the cloth impregnated with the diluted ink.
  • the rubbing operation (that is, rotation of the roller) was interrupted as appropriate, and the water contact angle of the surface of the test piece on the liquid-repellent film side was measured.
  • the water contact angle was measured in the same manner as the water contact angle in the evaluation of dissolution deterioration of the IJ head.
  • the rubbing operation and the measurement of the water contact angle were repeated, and based on the measurement results, the number of roller rotations at which the water contact angle was less than 60° was determined.
  • the wear deterioration of the IJ head was evaluated according to the following evaluation criteria.
  • A is the rank at which abrasion deterioration of the inkjet head is most suppressed.
  • A The number of roller rotations at which the water contact angle is less than 60° is 1500 or more.
  • B The number of roller rotations at which the water contact angle is less than 60° is 1000 or more and less than 1500.
  • C The number of roller rotations at which the water contact angle is less than 60° is 800 or more and less than 1000.
  • D Less than 800 roller rotations at which the water contact angle is less than 60°.
  • the solid image concealability of the image record was evaluated as follows. Separately from the image recording material, a character image of each size of 2pt (point), 4pt, 6pt and 8pt was printed on the substrate using a black inkjet ink (“C-WP-QK” manufactured by Fuji Film Co., Ltd.). (4 pieces in total) were recorded to obtain a substrate with a character image. All four character images were character images shown in FIG. The image-recorded product and the character-image-bearing substrate were laminated so that their non-image-recorded surfaces (surfaces on which no image was recorded) were in contact with each other to form a laminate.
  • C-WP-QK black inkjet ink
  • the resulting laminate was held over a 30 W fluorescent lamp with the solid image facing the side of the evaluator, and it was confirmed whether or not the details of each character image could be visually recognized through the solid image.
  • Image concealability was evaluated. At this time, the distance between the evaluator's eyes and the laminate was 20 cm, and the distance from the laminate to the fluorescent lamp was 2 m. In the following evaluation criteria, "A" is the highest rank in solid image concealability.
  • Examples 2 to 13, Comparative Examples 1 to 5 in white ink, particle size of titanium dioxide, content of titanium dioxide relative to the total amount of white ink (% by mass), types of silicon compounds, particle size when the silicon compound is colloidal silica, The same operation as in Example 1 was performed except that the combination of the content (% by mass) of the silicon compound relative to the total amount of the white ink and the dispersion method were changed as shown in Tables 1 and 2. The results are shown in Tables 1 and 2. Tables 1 and 2 also show the white ink number in each example and each comparative example.
  • block means that the following block polymer 1 was used as a polymer dispersant for dispersing titanium dioxide particles.
  • the preparation of the white pigment dispersion in the case where the column of dispersion method is "block” was carried out as follows.
  • Block polymer 1 as a polymer dispersant was synthesized with reference to Synthesis Example 8 of JP-A-2015-83688. Details are given below.
  • Diethylene glycol dimethyl ether (266 parts by mass; polymerization solvent), 2-iodo-2-cyanopropane (6.2 parts by mass; polymerization initiator compound), Methyl methacrylate (MMA) (120 parts by weight; monomer), acrylic acid (AA) (28.8 parts by weight; monomer), cyclohexyl methacrylate (CHMA) (67.2 parts by weight; monomer), Azobisdimethylisovaleronitrile (7.9 parts by mass) and 2-t-butyl-4,6-dimethylphenol (0.7 parts by mass; catalyst) were added and stirred while flowing nitrogen.
  • reaction temperature the temperature (reaction temperature) of the mixture in the reactor was raised to 70° C. and polymerization was performed for 3 hours to obtain a polymerization solution A containing an MMA/AA/CHMA copolymer. After 3 hours, a part of the polymerization solution A was sampled and the solid content was measured. Further, when the molecular weight of the MMA/AA/CHMA copolymer was measured by GPC, the weight average molecular weight (Mn) was 7,500. The acid value of this MMA/AA/CHMA copolymer was 101.0 mgKOH/g.
  • polymerization solution A a mixture of benzyl methacrylate (BzMA) (35.2 parts by mass; monomer) and V-65 (0.3 parts by mass; radical generator) was added and heated at 70°C.
  • Polymerization solution B containing block polymer 1 as a polymer dispersant was obtained by polymerizing for 3 hours.
  • the block polymer 1 is a block polymer containing an A block that is an MMA/AA/CHMA copolymer and a B block that is a BzMA homopolymer.
  • the solid content of the resulting polymerization solution B was measured, it was found to be 43.2% by mass, confirming that most of the monomers were polymerized.
  • the block polymer 1 had an Mw of 8,500 and an acid value of 89.3 mgKOH/g.
  • ⁇ Preparation of white pigment dispersion (“block”)> The above block polymer 1 (136.4 parts by mass), butyl carbitol (163.6 parts by mass), and C.I. I. Pigment White 6 (trade name “JR-405”, titanium dioxide particles, manufactured by Tayca) (450 parts by mass) was blended and stirred with a disper. Next, a horizontal media dispersing machine was used to sufficiently disperse the white pigment to obtain an oil-based pigment dispersion. The average particle size of the white pigment dispersed in the oil pigment dispersion was 290 nm. The oil pigment dispersion had a viscosity of 86.3 m3 Pa ⁇ s.
  • random means that the following random polymer 1 was used as a polymer dispersant for dispersing titanium dioxide particles.
  • the preparation of the white pigment dispersion liquid when the column of dispersion method is "random” was carried out as follows.
  • a three-necked flask equipped with a stirrer and condenser was charged with 605 g of dipropylene glycol and heated to 85° C. under a nitrogen atmosphere.
  • the solution I was added dropwise over 4 hours, and the solution II was added dropwise over 5 hours. After the dropwise addition was completed, the mixture was further reacted for 2 hours, then heated to 95° C. and heated and stirred for 3 hours to react all the unreacted monomers. Disappearance of the monomer was confirmed by 1 H-NMR.
  • the resulting reaction solution is heated to 70° C., 74 g of dimethylaminoethanol is added as an amine compound, and then 764 g of propylene glycol is added and stirred to obtain a mixture having a weight average molecular weight (Mw) of 30000 and an acid value of 112 mgKOH/g.
  • Mw weight average molecular weight
  • a solution of random polymer 1 (solid content: 30% by mass) was obtained.
  • the constituent components of the obtained polymer were confirmed by 1 H-NMR.
  • Each component was mixed according to the composition of the white pigment dispersion below, and the resulting mixture was added with Labo Star Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd., bead diameter: 0.1 mm ⁇ , zirconia beads, rotation speed: 10 m / sec), and subjected to dispersion treatment for 1.5 hours to obtain a white pigment dispersion (white pigment concentration: 48% by mass, solid content concentration: 50% by mass).
  • Labo Star Mini LMZ015 manufactured by Ashizawa Finetech Co., Ltd., bead diameter: 0.1 mm ⁇ , zirconia beads, rotation speed: 10 m / sec
  • self-dispersion means that a white pigment dispersion of self-dispersing titanium dioxide particles (“self-dispersion”) was used as the white pigment dispersion.
  • Preparation of the white pigment dispersion liquid when the column of dispersion method is "self-dispersion” was carried out as follows.
  • ultrafiltration with a dialysis membrane is performed using ion-exchanged water, and then ultrasonic dispersion is performed using an ultrasonic dispersing machine to obtain a white pigment dispersion having a pigment concentration of 45% by mass (“self-dispersion ”).
  • the average primary particle diameter of the titanium dioxide particles is 100 nm or more
  • the silicon compound is silicate and colloidal silica. is at least one selected from the group consisting of, the content of the silicon compound relative to the total amount of the titanium dioxide particles is 0.0020% by mass or more, and the particle size ratio [colloidal silica/titanium dioxide particles] (i.e., the dioxide In each example using the ink in which the ratio of the average primary particle size of the colloidal silica to the average primary particle size of the titanium particles) is 0.04 or less, an image with excellent hiding properties can be recorded and the IJ head can be used. Suppressed wear deterioration. Furthermore, in each example, the dissolution deterioration of the IJ head could be suppressed.
  • the results of each comparative example were as follows.
  • Comparative Example 1 in which the ink does not contain a silicon compound, the abrasion deterioration of the IJ head could not be suppressed.
  • Comparative Examples 2 and 3 in which the content of the silicon compound relative to the total amount of titanium dioxide particles in the ink is less than 0.0020% by mass, the abrasion deterioration of the IJ head could not be suppressed.
  • Comparative Example 4 in which the particle size ratio [colloidal silica/titanium dioxide particles] in the ink was more than 0.04, wear deterioration of the IJ head could not be suppressed.
  • Comparative Example 5 in which the average primary particle size of the titanium dioxide particles in the ink was less than 100 nm, the image concealability was lowered and the abrasion deterioration of the IJ head could not be suppressed.
  • the silicon compound in the ink comprises a silicate, and the silicate is selected from the group consisting of alkali metal silicate and ammonium silicate.
  • the silicate is selected from the group consisting of alkali metal silicate and ammonium silicate.
  • Example 7 to 10 when the ink contains a polymer dispersant and the polymer dispersant contains a block polymer or a polymer having a crosslinked structure (Examples 7 to 10), abrasion deterioration of the IJ head is further suppressed. I know you can. The reason for this is that the titanium dioxide particles can be densely coated with the polymer dispersant, as compared with the case where the polymer dispersant is a random polymer, and as a result, polishing of the IJ head by the titanium dioxide particles can be further suppressed. Conceivable.
  • Example 101 to 111 ⁇ Preparing the ink set>>> Each No. shown in Table 3. , the following color ink (common), and the following pretreatment liquid (common) were combined to prepare an ink set. Each No. is the white ink used in Examples 1-10.
  • a color ink (specifically, a cyan ink) having the following composition was prepared using the white pigment dispersion CL containing the crosslinked polymer dispersant L1, the dispersion of the resin particles P1, and the materials in the following composition.
  • Table 3 shows the types and contents of silicon compounds in the following color inks.
  • a pretreatment liquid was obtained by mixing components having the following composition.
  • pretreatment liquid - Malonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; flocculant (organic acid)) ... 5% by mass ⁇ Sodium dodecylbenzenesulfonate (surfactant) (manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.0% by mass ⁇ Water: Remaining amount of 100% by mass in total
  • image recording was carried out as follows.
  • An image was recorded using an inkjet recording apparatus equipped with a conveying system for conveying the base material, a wire bar coater (coating amount: 1.5 g/m 2 ) for applying the pretreatment liquid, and a plurality of IJ heads. Recorded.
  • the plurality of IJ heads the same IJ heads as the IJ heads used in Example 1 were used.
  • a plurality of IJ heads were arranged in the conveying direction of the substrate. Specifically, first, while the substrate was being transported, the pretreatment liquid was applied onto the corona discharge-treated surface of the substrate and dried at 80° C.
  • the color ink (specifically, cyan ink) was ejected from the IJ head on the upstream side in the conveying direction of the substrate onto the area of the substrate coated with the pretreatment liquid to obtain a cyan character image.
  • the cyan character images here are the same as the four character images used for the evaluation of concealability in Example 1 (that is, the character images shown in FIG. 1 with sizes of 2pt, 4pt, 6pt and 8pt). It is a character image.
  • the white ink is ejected from the IJ head on the downstream side in the substrate conveying direction to form a solid image so as to cover the entire four cyan character images. White ink was applied.
  • Example 111 The same operation as in Example 101 was performed except that the type of silicon compound in the color ink was changed as shown in Table 3. Table 3 shows the results.
  • the silicon compound contained in the white ink is the first silicon compound
  • the silicon compound contained in the color ink is the second silicon compound
  • the first silicon compound relative to the total amount of the white ink When the content of the second silicon compound is X1% by mass and the content of the second silicon compound with respect to the total amount of the color ink is X2% by mass, the X1/X2 ratio is less than 1.0 (Examples 102 to 104, 107 ⁇ 110), which is superior in image definition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
PCT/JP2022/018651 2021-05-14 2022-04-25 インクジェットインク、インクセット、及び画像記録方法 Ceased WO2022239625A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202280034377.1A CN117295798A (zh) 2021-05-14 2022-04-25 喷墨油墨、油墨组以及图像记录方法
EP22807328.4A EP4338961A4 (en) 2021-05-14 2022-04-25 INKJET INK, INK SET AND IMAGE RECORDING METHODS
JP2023520952A JPWO2022239625A1 (https=) 2021-05-14 2022-04-25
US18/505,741 US20240067837A1 (en) 2021-05-14 2023-11-09 Ink-jet ink, ink set, and image-recording method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021082581 2021-05-14
JP2021-082581 2021-05-14

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/505,741 Continuation US20240067837A1 (en) 2021-05-14 2023-11-09 Ink-jet ink, ink set, and image-recording method

Publications (1)

Publication Number Publication Date
WO2022239625A1 true WO2022239625A1 (ja) 2022-11-17

Family

ID=84029539

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/018651 Ceased WO2022239625A1 (ja) 2021-05-14 2022-04-25 インクジェットインク、インクセット、及び画像記録方法

Country Status (5)

Country Link
US (1) US20240067837A1 (https=)
EP (1) EP4338961A4 (https=)
JP (1) JPWO2022239625A1 (https=)
CN (1) CN117295798A (https=)
WO (1) WO2022239625A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4411062A1 (en) * 2023-01-31 2024-08-07 Brother Kogyo Kabushiki Kaisha Image forming method and image forming system

Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5459936A (en) 1977-10-03 1979-05-15 Canon Inc Recording method and device therefor
JPS59157636A (ja) 1983-02-25 1984-09-07 Fuji Photo Film Co Ltd カラ−画像形成方法
JP2002012607A (ja) 2000-06-28 2002-01-15 Mitsubishi Chemicals Corp 光重合性組成物、光重合性着色組成物およびカラーフィルター
JP2002188025A (ja) 2000-10-10 2002-07-05 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化型インクジェットインキ
JP2003026978A (ja) 1998-09-08 2003-01-29 Ricoh Co Ltd 記録液体
JP2003306623A (ja) 2002-04-16 2003-10-31 Fuji Photo Film Co Ltd 水性インク
JP2003322926A (ja) 2002-05-02 2003-11-14 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JP2003342503A (ja) 2002-05-28 2003-12-03 Konica Minolta Holdings Inc インクジェット記録用ブラックインクおよび画像形成方法
JP2004309806A (ja) 2003-04-08 2004-11-04 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JP2004325707A (ja) 2003-04-24 2004-11-18 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料および水性塗布組成物
JP2013001854A (ja) 2011-06-17 2013-01-07 Fujifilm Corp インクセット及び画像形成方法
WO2013180074A1 (ja) 2012-05-29 2013-12-05 富士フイルム株式会社 インクジェット記録用メンテナンス液、インクジェット記録用インクセット、画像形成方法、及びメンテナンス方法
JP5430316B2 (ja) 2009-09-18 2014-02-26 富士フイルム株式会社 画像形成方法
JP2015083688A (ja) 2008-07-28 2015-04-30 大日精化工業株式会社 水性顔料分散液、および使用
WO2015158592A1 (en) 2014-04-15 2015-10-22 Agfa Graphics Nv Methods for manufacturing printed textiles
JP2016145312A (ja) 2015-01-29 2016-08-12 富士フイルム株式会社 インクセット及び画像形成方法
JP2016188345A (ja) 2015-03-30 2016-11-04 富士フイルム株式会社 インクジェット用顔料分散体及びその製造方法、インクセット、並びに画像形成方法
JP2017031354A (ja) * 2015-08-04 2017-02-09 株式会社リコー インク、インクカートリッジ、インクジェット記録装置、インクジェット記録方法、及び記録物
WO2017149917A1 (ja) 2016-02-29 2017-09-08 富士フイルム株式会社 インク組成物、インクセット、画像形成方法、及び印刷物
JP2018009260A (ja) * 2016-07-15 2018-01-18 大日精化工業株式会社 捺染印刷方法
JP2018528876A (ja) * 2015-07-15 2018-10-04 フジフィルム・イメイジング・カラランツ，インコーポレーテッド 水溶性材料上での印刷方法
WO2019004485A1 (ja) 2017-06-30 2019-01-03 富士フイルム株式会社 非浸透媒体印刷用前処理液、印刷用基材、印刷用基材の製造方法、画像記録方法及びインクセット
JP2019112600A (ja) 2017-12-26 2019-07-11 セイコーエプソン株式会社 白色顔料組成物及びその乾燥体、塗布方法、塗布物、インクジェット記録方法、記録物、並びにインクジェットプリンター
JP2019112601A (ja) * 2017-12-26 2019-07-11 セイコーエプソン株式会社 白色顔料組成物及びその乾燥体、塗布方法、塗布物、インクジェット記録方法、記録物、並びにインクジェットプリンター
JP2019116598A (ja) * 2017-12-27 2019-07-18 花王株式会社 水系インク
WO2019163581A1 (ja) 2018-02-26 2019-08-29 富士フイルム株式会社 インクセット、画像記録方法、ラミネート体の製造方法、画像記録物、及びラミネート体
WO2019188855A1 (ja) * 2018-03-30 2019-10-03 富士フイルム株式会社 インクジェットインク組成物、画像記録方法、及び、画像記録物
WO2019188856A1 (ja) * 2018-03-30 2019-10-03 富士フイルム株式会社 インクジェットインク組成物、メンテナンス方法、画像記録方法、及び、画像記録物
WO2019187665A1 (ja) * 2018-03-30 2019-10-03 富士フイルム株式会社 インクジェット記録用インク組成物、インクセット及び画像記録方法
JP2020044724A (ja) 2018-09-19 2020-03-26 セイコーエプソン株式会社 記録方法、及び記録装置
WO2020174940A1 (ja) * 2019-02-28 2020-09-03 株式会社 資生堂 インク組成物、インク組成物を収容しているインクジェットカートリッジ、及びインクジェットカートリッジを搭載したインクジェット装置
WO2020195211A1 (ja) * 2019-03-28 2020-10-01 富士フイルム株式会社 インクセット、画像記録方法、及び、画像記録物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001096902A (ja) * 1999-09-29 2001-04-10 Seiko Epson Corp インクジェット用記録媒体、それを用いた記録方法および記録物
JP5068502B2 (ja) * 2006-09-28 2012-11-07 富士フイルム株式会社 インク組成物、インクジェット記録方法、印刷物、平版印刷版の製造方法及び平版印刷版
JP5490474B2 (ja) * 2009-09-18 2014-05-14 富士フイルム株式会社 画像形成方法及びインク組成物
JP2013181055A (ja) * 2012-02-29 2013-09-12 Seiko Epson Corp インクジェット記録用インク組成物及び記録物
US8956450B2 (en) * 2012-07-25 2015-02-17 Funai Electric Co., Ltd. Formulation for silicon-doped ink used to prevent chip etching
WO2016175743A1 (en) * 2015-04-27 2016-11-03 Hewlett-Packard Development Company, L.P. Fluid sets for inkjet imaging
CN105482552A (zh) * 2015-12-29 2016-04-13 武汉理工大学 一种喷墨打印用白色玻璃墨水及其制备方法
JP2022081707A (ja) * 2019-03-29 2022-06-01 富士フイルム株式会社 画像記録方法及びインクセット
WO2021084960A1 (ja) * 2019-10-29 2021-05-06 富士フイルム株式会社 画像記録物及びその製造方法
US20230365824A1 (en) * 2020-07-29 2023-11-16 Landa Corporation Ltd Inkjet ink formulations and uses thereof
CN118434573A (zh) * 2021-12-21 2024-08-02 富士胶片株式会社 图像记录方法及层压体的制造方法

Patent Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5459936A (en) 1977-10-03 1979-05-15 Canon Inc Recording method and device therefor
JPS59157636A (ja) 1983-02-25 1984-09-07 Fuji Photo Film Co Ltd カラ−画像形成方法
JP2003026978A (ja) 1998-09-08 2003-01-29 Ricoh Co Ltd 記録液体
JP2002012607A (ja) 2000-06-28 2002-01-15 Mitsubishi Chemicals Corp 光重合性組成物、光重合性着色組成物およびカラーフィルター
JP2002188025A (ja) 2000-10-10 2002-07-05 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化型インクジェットインキ
JP2003306623A (ja) 2002-04-16 2003-10-31 Fuji Photo Film Co Ltd 水性インク
JP2003322926A (ja) 2002-05-02 2003-11-14 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JP2003342503A (ja) 2002-05-28 2003-12-03 Konica Minolta Holdings Inc インクジェット記録用ブラックインクおよび画像形成方法
JP2004309806A (ja) 2003-04-08 2004-11-04 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JP2004325707A (ja) 2003-04-24 2004-11-18 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料および水性塗布組成物
JP2015083688A (ja) 2008-07-28 2015-04-30 大日精化工業株式会社 水性顔料分散液、および使用
JP5430316B2 (ja) 2009-09-18 2014-02-26 富士フイルム株式会社 画像形成方法
JP2013001854A (ja) 2011-06-17 2013-01-07 Fujifilm Corp インクセット及び画像形成方法
WO2013180074A1 (ja) 2012-05-29 2013-12-05 富士フイルム株式会社 インクジェット記録用メンテナンス液、インクジェット記録用インクセット、画像形成方法、及びメンテナンス方法
WO2015158592A1 (en) 2014-04-15 2015-10-22 Agfa Graphics Nv Methods for manufacturing printed textiles
JP2016145312A (ja) 2015-01-29 2016-08-12 富士フイルム株式会社 インクセット及び画像形成方法
JP2016188345A (ja) 2015-03-30 2016-11-04 富士フイルム株式会社 インクジェット用顔料分散体及びその製造方法、インクセット、並びに画像形成方法
JP2018528876A (ja) * 2015-07-15 2018-10-04 フジフィルム・イメイジング・カラランツ，インコーポレーテッド 水溶性材料上での印刷方法
JP2017031354A (ja) * 2015-08-04 2017-02-09 株式会社リコー インク、インクカートリッジ、インクジェット記録装置、インクジェット記録方法、及び記録物
WO2017149917A1 (ja) 2016-02-29 2017-09-08 富士フイルム株式会社 インク組成物、インクセット、画像形成方法、及び印刷物
JP2018009260A (ja) * 2016-07-15 2018-01-18 大日精化工業株式会社 捺染印刷方法
WO2019004485A1 (ja) 2017-06-30 2019-01-03 富士フイルム株式会社 非浸透媒体印刷用前処理液、印刷用基材、印刷用基材の製造方法、画像記録方法及びインクセット
JP2019112601A (ja) * 2017-12-26 2019-07-11 セイコーエプソン株式会社 白色顔料組成物及びその乾燥体、塗布方法、塗布物、インクジェット記録方法、記録物、並びにインクジェットプリンター
JP2019112600A (ja) 2017-12-26 2019-07-11 セイコーエプソン株式会社 白色顔料組成物及びその乾燥体、塗布方法、塗布物、インクジェット記録方法、記録物、並びにインクジェットプリンター
JP2019116598A (ja) * 2017-12-27 2019-07-18 花王株式会社 水系インク
WO2019163581A1 (ja) 2018-02-26 2019-08-29 富士フイルム株式会社 インクセット、画像記録方法、ラミネート体の製造方法、画像記録物、及びラミネート体
WO2019188855A1 (ja) * 2018-03-30 2019-10-03 富士フイルム株式会社 インクジェットインク組成物、画像記録方法、及び、画像記録物
WO2019188856A1 (ja) * 2018-03-30 2019-10-03 富士フイルム株式会社 インクジェットインク組成物、メンテナンス方法、画像記録方法、及び、画像記録物
WO2019187665A1 (ja) * 2018-03-30 2019-10-03 富士フイルム株式会社 インクジェット記録用インク組成物、インクセット及び画像記録方法
JP2020044724A (ja) 2018-09-19 2020-03-26 セイコーエプソン株式会社 記録方法、及び記録装置
WO2020174940A1 (ja) * 2019-02-28 2020-09-03 株式会社 資生堂 インク組成物、インク組成物を収容しているインクジェットカートリッジ、及びインクジェットカートリッジを搭載したインクジェット装置
WO2020195211A1 (ja) * 2019-03-28 2020-10-01 富士フイルム株式会社 インクセット、画像記録方法、及び、画像記録物

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Pigment Dictionary", INDUSTRIAL ORGANIC PIGMENTS, 2000
FIBER AND INDUSTRY, vol. 60, no. 7, 2004, pages 376
See also references of EP4338961A4
W. HERBSTK. HUNGER: "Handbook of Organic Pigments", 2006

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4411062A1 (en) * 2023-01-31 2024-08-07 Brother Kogyo Kabushiki Kaisha Image forming method and image forming system

Also Published As

Publication number Publication date
CN117295798A (zh) 2023-12-26
EP4338961A1 (en) 2024-03-20
JPWO2022239625A1 (https=) 2022-11-17
US20240067837A1 (en) 2024-02-29
EP4338961A4 (en) 2024-10-23

Similar Documents

Publication Publication Date Title
JP7179964B2 (ja) 非浸透性基材用インクジェットインク、画像記録方法、及びラミネート体の製造方法
JP7459236B2 (ja) 画像記録方法
JP7755001B2 (ja) 画像記録物及びその製造方法、並びに、ラミネート体及びその製造方法
JP7047108B2 (ja) 非浸透性基材印刷用インク組成物及び画像記録方法
WO2019163581A1 (ja) インクセット、画像記録方法、ラミネート体の製造方法、画像記録物、及びラミネート体
JP6964760B2 (ja) インクジェットインク組成物、画像記録方法、及び、画像記録物
JP7163410B2 (ja) インクジェットインク組成物及び画像記録方法
JPWO2020195211A1 (ja) インクセット、画像記録方法、及び、画像記録物
JP7408689B2 (ja) 画像記録方法
JP7413409B2 (ja) 画像記録方法
JP7130114B2 (ja) 画像形成方法
WO2022239625A1 (ja) インクジェットインク、インクセット、及び画像記録方法
WO2022190722A1 (ja) 画像記録方法、画像記録物、及びインクセット、並びに、ラミネート体及びその製造方法
WO2023095710A1 (ja) インクジェット記録方法
WO2023120320A1 (ja) 画像記録方法及びラミネート体の製造方法
WO2020179313A1 (ja) インク組成物、インクセット、及び画像形成方法
WO2025100162A1 (ja) 加熱成形物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22807328

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023520952

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280034377.1

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2022807328

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022807328

Country of ref document: EP

Effective date: 20231214