WO2017163738A1 - インクセット及び画像記録方法 - Google Patents
インクセット及び画像記録方法 Download PDFInfo
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- WO2017163738A1 WO2017163738A1 PCT/JP2017/006685 JP2017006685W WO2017163738A1 WO 2017163738 A1 WO2017163738 A1 WO 2017163738A1 JP 2017006685 W JP2017006685 W JP 2017006685W WO 2017163738 A1 WO2017163738 A1 WO 2017163738A1
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- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
-
- 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
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
-
- 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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0018—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using ink-fixing material, e.g. mordant, precipitating agent, after printing, e.g. by ink-jet printing, coating or spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
Definitions
- the present invention relates to an ink set and an image recording method.
- a recording method using an inkjet method is widely used in that it can be recorded on an arbitrary material.
- an image can be recorded by ejecting ink droplets from a plurality of nozzles provided in an ink jet head for ejecting ink.
- an image is obtained by using an ink set having an ink containing a colorant and a treatment liquid containing a compound that aggregates the components in the ink, and bringing the ink and the treatment liquid into contact with each other.
- a step of applying an ink containing dispersed pigment to a recording medium, and resin fine particles having at least one selected from a sulfo group and a phosphate group And a step of applying an acidic liquid composition that destabilizes the dispersion state to a recording medium (see, for example, JP-A-2013-18156).
- an image forming method using an ink set comprising an ink composition containing a pigment and water, and a treatment liquid containing a water-soluble polymer compound, an organic acidic compound, silicone oil, water, and the like.
- a water-soluble polymer compound an organic acidic compound, silicone oil, water, and the like.
- the coating solution and the roughness of the image are suppressed by containing a water-soluble polymer compound and silicone oil in the treatment liquid.
- the surface contact angle with respect to water (water contact angle) is 70 ° or more, when recording an image using water-based ink on a substrate having relatively low wettability with water, the water contact angle is Compared to the case where an image is recorded on a low substrate, the ink droplets that have landed tend to be smaller than the desired size due to the water-repellent action of the substrate. Further, as in JP-A-2013-72045, in the recording form in which the components in the ink are aggregated using the treatment liquid and the image is recorded, the treatment liquid has a function of further reducing the diameter of the ink droplet. The ink droplets deposited on the ink may be significantly smaller than the desired droplet size.
- a treatment liquid containing a water-soluble polymer compound is used in the ink set described in JP2013-72045A.
- the water-soluble polymer compound cannot exist in the particle state in the aqueous treatment liquid, and when the treatment liquid is applied to the base material, the water-soluble polymer compound penetrates into the base material, and the base material It is considered that the effect of improving the wettability of the surface is not necessarily sufficient.
- a surfactant may be used, but the effect of improving the wettability by the surfactant may be insufficient.
- the resin fine particles contained in the liquid composition have a sulfo group or a phosphate group, so that an effect of improving the wettability of the surface of the substrate is expected.
- the fine particles swell in the treatment liquid over time and are likely to become coarse.
- the resin of the resin fine particles contains 2-ethylhexyl acrylate, which is a relatively hydrophobic monomer, but is not sufficient as an inhibitory effect on particle swelling. For this reason, the dispersion stability of the resin fine particles in the treatment liquid is low. Therefore, the viscosity increases with time, and uneven coating tends to occur. For this reason, with the technique described in Japanese Patent Application Laid-Open No. 2013-18156, uneven coating tends to occur in an image, which deteriorates with time, and it can be said that it is difficult to stably suppress the occurrence of, for example, streaky unevenness.
- One embodiment of the present invention has been made in view of the above, an ink set in which a solid image portion having a desired density is obtained, and generation of streaky unevenness (hereinafter also referred to as streak unevenness) is suppressed.
- An object is to provide an image recording method, and to achieve this object.
- solid image means a surface image formed by applying ink at a specific halftone dot ratio (density).
- density halftone dot ratio
- smooth unevenness refers to a phenomenon in which the ink composition moves due to the ink droplet landing interference, resulting in the occurrence of streaks.
- a treatment comprising water-insoluble resin particles having a structural unit derived from a second monomer containing at least one structure selected from a ring structure, a compound for aggregating the colorant in the ink composition, and water.
- the structural unit derived from the second monomer is at least one structural unit selected from the group of structural units represented by any one of the following general formulas A to E: ⁇ 1> Ink set.
- R 11 represents a methyl group or a hydrogen atom
- R 12 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.
- n represents an integer of 0 to 5, and when n is 2 or more, the plurality of R 12 may be the same as or different from each other.
- L 11 represents a single bond, a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, —O—, —NH—, —S—, and —C. It represents a divalent linking group in which one or more selected from the group consisting of ( ⁇ O) — are linked.
- the total content of the structural units derived from the second monomer in the water-insoluble resin is 10% by mass to 40% by mass relative to the total mass of the water-insoluble resin ⁇ 1> or The ink set according to ⁇ 2>.
- the structural unit derived from the first monomer is the ink set according to any one of ⁇ 1> to ⁇ 4>, which is a structural unit represented by the following general formula 1.
- R 4 represents a methyl group or a hydrogen atom
- L 4 represents a single bond, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms
- M represents a hydrogen atom or a cation.
- the content ratio of the structural unit derived from the first monomer in the water-insoluble resin is 5% by mass to 25% by mass with respect to the total mass of the water-insoluble resin.
- ⁇ 1> to ⁇ 5> It is an ink set as described in any one of these.
- At least one of the second monomers is any one of ⁇ 1> to ⁇ 6>, wherein the ratio of the mass of oxygen atoms in the monomer to the molecular weight of the monomer is 0.1 or less It is an ink set as described in one.
- ⁇ 8> The ink set according to any one of ⁇ 1> to ⁇ 7>, wherein at least one of the second monomers is styrene.
- ⁇ 9> The ink set according to any one of ⁇ 1> to ⁇ 8>, wherein the glass transition temperature of the water-insoluble resin is 100 ° C. or higher.
- the content ratio of the water-insoluble resin particles to the compound that aggregates the colorant in the ink composition is 0.19 to 0.5 on a mass basis, and any one of ⁇ 1> to ⁇ 9> It is an ink set as described in above.
- ⁇ 11> The ink set according to any one of ⁇ 1> to ⁇ 10>, provided on at least one surface of a base material having a contact angle of 70 ° or more when a water droplet is applied to the surface for 3 seconds.
- the ink composition of the ink set according to any one of ⁇ 1> to ⁇ 10> is ejected by an inkjet method on a pretreatment step for applying the treatment liquid and on one surface to which the treatment liquid is applied. And an image recording process for recording an image.
- ⁇ 12> The image recording method according to ⁇ 11>, wherein the substrate is a paper substrate having a coating layer.
- an ink set and an image recording method in which a solid image portion having a desired density is obtained and generation of streak unevenness (hereinafter also referred to as streak unevenness) is suppressed.
- a numerical range indicated using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the amount of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
- process is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended purpose of the process is achieved. included.
- (meth) acrylate means including both acrylate and methacrylate
- (meth) acryl means including both acrylic and methacrylic.
- the ink set according to the present disclosure has an ink composition containing a colorant and water, and a treatment liquid for pretreating a substrate before application of the ink composition.
- the treatment liquid in the present disclosure includes a structural unit derived from a first monomer containing at least one group selected from a sulfo group and a salt of a sulfo group, and at least one structure selected from an aromatic ring structure and an alicyclic structure Water-insoluble resin particles having a structural unit derived from a second monomer containing, a compound that aggregates the colorant in the ink composition (hereinafter also referred to as “aggregating component”), water, Containing.
- the treatment liquid may further contain water-insoluble resin particles, an aggregating component, and other components other than water, if necessary.
- the ink composition may further include a component other than the colorant and water.
- the structural unit derived from the first monomer containing at least one group selected from a sulfo group and a salt of the sulfo group, and at least one selected from an aromatic ring structure and an alicyclic structure
- the water-insoluble resin particles having a structural unit derived from the second monomer containing the structure are subjected to a pretreatment for applying a treatment liquid to the substrate before image recording.
- the uneven distribution improves the quality of an image recorded on a substrate having a hydrophobic surface.
- the water-insoluble resin particles contained in the treatment liquid have a hydrophilic surface and a hydrophobic interior, the water-insoluble resin particles are present in the treatment liquid. Since the particles themselves are less likely to swell, the dispersion state is stably maintained.
- the surface of the substrate is hydrophilized, This improves the wettability of the ink composition. Thereby, a solid image portion having a desired density is obtained by suppressing the density reduction of the solid image portion, and an image in which the occurrence of streak unevenness is suppressed is obtained.
- the “decrease in the density of the solid image portion” means that when the solid image is formed on the substrate, the size of the droplet of the ink composition deposited on the substrate is small. Influenced by the phenomenon that the numerical value falls below the target color density, or the ink composition moves due to ink droplet landing interference, the image is affected by the color of the substrate, and the target color density It means a phenomenon that the numerical value decreases.
- the water-insoluble resin in the water-insoluble resin particles is hydrophilic because it contains at least one group selected from a sulfo group and a salt of a sulfo group, and the water-insoluble resin particles become hydrophilic. Therefore, when the particles are present on the surface of the substrate, the surface of the substrate is hydrophilized. Further, when the water-insoluble resin particles have a sulfo group or the like, a large amount of anions are present, so that the repulsion between particles is increased and the dispersion stability of the water-insoluble resin particles in the treatment liquid is further improved.
- the water-insoluble resin simply contains a sulfo group or the like in the molecule, it becomes hydrophilic not only on the surface but also inside the particle. Therefore, when the particles are present in the treatment liquid, the water or solvent that is the solvent penetrates into the particles over time and swells, and the particles tend to coalesce and the particles are dispersed in the treatment liquid. The stability is lowered, and the dispersion stability with time in the treatment liquid is also lowered. As a result, the viscosity of the treatment liquid increases with time. As a result, the image quality is lowered as the viscosity increases.
- the water-insoluble resin in the water-insoluble resin particles includes at least one structure selected from an aromatic ring structure and an alicyclic structure as a hydrophobic group.
- Hydrophobic groups tend to be present inside the particles rather than the surface of the particles. For this reason, hydrophobic groups are introduced into the inside of the particles, and the inside of the particles becomes more hydrophobic. Therefore, when the particles are present in an aqueous processing solution, swelling of the particles over time can be suppressed, and in the processing solution Stability over time, prevents the occurrence of muscle irregularities over time.
- the hydrophobic group is not unevenly distributed on the surface of the particle in the aqueous processing solution, but is unevenly distributed inside the particle, so that the surface of the particle can be kept hydrophilic.
- a water-soluble resin is sometimes used as a treatment liquid in an ink set.
- the water-soluble resin cannot exist in a particle state in an aqueous processing solution, and when the particles are applied to the base material, the water-soluble resin easily penetrates into the base material, and the surface wettability of the base material is low. The improved effect is not expected.
- a surfactant may be used to improve the wettability of the surface of the substrate, but the effect of improving the wettability by the surfactant may not be sufficient.
- the ink set of the present disclosure in the water-insoluble resin particles as described above, at least one hydrophobic group selected from an aromatic ring structure and an alicyclic structure (hereinafter also referred to as a specific hydrophobic group), At least one hydrophilic group selected from a sulfo group and a salt of the sulfo group (hereinafter also referred to as a specific hydrophilic group) is present.
- the treatment liquid containing the water-insoluble resin particles is applied to the base material, the water-insoluble resin particles in the treatment liquid are less likely to penetrate into the base material, and the particles are likely to be unevenly distributed on the surface of the base material. It is considered to be.
- the wettability of the surface is remarkably improved in a substrate having a hydrophobic surface (for example, a substrate having a contact angle of 70 ° or more when 3 seconds have passed after applying water droplets on the surface).
- the droplet size of the deposited ink composition becomes too small because the surface of the substrate is hydrophilized. Absent. As a result, the colorant in the ink composition comes into contact with the treatment liquid and aggregation of the ink composition droplets is prevented, and a desired droplet size is obtained. Are placed at the desired position and size of the substrate. As a result, it is considered that an image in which the density reduction of the solid image portion when the solid image is recorded is suppressed and the occurrence of streak unevenness is suppressed can be obtained.
- the water-insoluble resin particles maintain a dispersed state in the processing liquid even when they come into contact with the aggregating component (compound that aggregates the colorant in the ink composition) contained in the processing liquid.
- the treatment liquid in the ink set according to the present disclosure pretreats the substrate before application of an ink composition described later.
- the treatment liquid contains a structural unit derived from a first monomer containing at least one group selected from a sulfo group and a salt of a sulfo group, and a first unit containing at least one structure selected from an aromatic ring structure and an alicyclic structure.
- the wettability with respect to the ink composition of a substrate having a relatively low wettability to water is increased, and a solid having a desired concentration is obtained.
- An image portion can be easily obtained, and the occurrence of streak unevenness can be effectively suppressed.
- the treatment liquid contains at least one kind of water-insoluble resin particles.
- the water-insoluble resin particles By containing the water-insoluble resin particles, most of the water-insoluble resin particles are unevenly distributed on the surface of the substrate after application of the treatment liquid, thereby improving the wettability of the substrate surface.
- the ink composition is deposited on a substrate on which water-insoluble resin particles are unevenly distributed on the surface, the ink droplet spreads on the surface of the substrate, and the aggregation component contained in the treatment liquid is a colorant in the ink composition. Aggregate dispersed components such as This prevents the droplets from being coalesced, and the droplet size becomes the desired size.
- the water-insoluble resin particles themselves are excellent in stability over time in the processing solution, and the coarsening of the particles due to swelling is suppressed, thereby suppressing the occurrence of streak unevenness that tends to occur in a recorded image. It is effective. Furthermore, roughness in the image can also be suppressed.
- “graininess” means that after the ink composition has landed on the substrate, the droplets coalesce, causing minute density unevenness in the image and reducing pixel uniformity. Refers to the phenomenon.
- Water-insoluble of a water-insoluble resin is a volume average particle diameter measurement at a liquid temperature of 25 ° C. using an aqueous dispersion of resin particles adjusted so that the solid content concentration is 1% by mass to 2% by mass. This is the case where the particles can be detected and the volume average particle diameter can be measured. In addition, when particles are not detected and the volume average particle diameter cannot be measured, the resin is dissolved in water, and this state is generally referred to as “water-soluble”.
- solid content refers to the remaining components obtained by removing the solvent from the composition.
- the volume average particle size can be determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.).
- the water-insoluble resin particles may be used in the form of a dispersion in which the particles are dispersed in an aqueous medium (an aqueous dispersion called a latex).
- the water-insoluble resin in the water-insoluble resin particles is selected from a structural unit derived from a first monomer containing at least one group selected from a sulfo group and a salt of a sulfo group, an aromatic ring structure, and an alicyclic structure.
- a structural unit derived from a second monomer containing at least one structure and may further include a structural unit derived from another monomer, if necessary.
- the constitutional unit derived from the first monomer is a copolymer of at least a first monomer containing at least one group selected from a sulfo group and a salt of the sulfo group with at least a second monomer described later. This is a structural unit present in the resin.
- the surface of the water-insoluble resin particles is hydrophilized by copolymerizing the first monomer and including a sulfo group or a salt of the sulfo group.
- the first monomer containing at least one group selected from a sulfo group and a sulfo group salt is particularly a sulfo group or a sulfo group salt or a monomer having a sulfo group and a sulfo group salt.
- the structural unit derived from the first monomer is derived from a structural unit derived from a monomer containing a sulfo group or a salt of a sulfo group, or a structural unit derived from a monomer containing a salt of a sulfo group and a sulfo group. What is necessary is just to select suitably from the group which consists of.
- the 1st monomer may be contained individually by 1 type, and may contain 2 or more types.
- the structural unit derived from the first monomer is preferably a structural unit represented by the following general formula 1.
- R 4 represents a methyl group or a hydrogen atom.
- L 4 in the general formula 1 is a single bond, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, —O—, —NH—, — It represents a divalent linking group in which one or more selected from the group consisting of S—, —C ( ⁇ O) —, and —CH (—OH) — are connected.
- L 4 is one or two selected from the group consisting of a linear, branched or cyclic alkylene group having 1 to 5 carbon atoms, —O—, —NH—, and —C ( ⁇ O) —.
- a divalent linking group in which two or more are linked is preferable, and further, a linear, branched or cyclic alkylene group having 1 to 5 carbon atoms, a linear, branched or cyclic group having 1 to 5 carbon atoms.
- a divalent linking group consisting of C ( ⁇ O) — is preferred.
- L 4 is more preferably at least one linking group selected from the following group a. In the linking group shown in group a, n represents an integer of 1 to 5, and * represents a bonding position.
- M represents a hydrogen atom or a cation.
- examples of the cation in M 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 ions such as ammonium ion.
- Examples of the structural unit represented by the general formula 1 include 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamidopropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, ⁇ -methylstyrenesulfonic acid, and 2-sulfoethyl.
- Examples include structural units derived from monomers having sulfonic acid and salts thereof.
- the salt counter ion includes alkali metal ions such as sodium ion, potassium ion and lithium ion, alkaline earth metal ions such as calcium ion and magnesium ion, and ions such as ammonium ion.
- a monomer having at least one group selected from a sulfo group and a salt of a sulfo group is copolymerized. May be.
- a sulfo group salt is introduced into a water-insoluble resin, a monomer having a sulfo group may be copolymerized to synthesize water-insoluble resin particles, and then neutralized with a base to form a sulfo group salt.
- structural units derived from a monomer having at least one group selected from a sulfo group and a salt of sulfo group 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid salt Or a structural unit derived from 3-sulfopropyl (meth) acrylate.
- a counter ion in the salt sodium ion, potassium ion, lithium ion, and ammonium ion are preferable.
- 2-acrylamido-2-methylpropanesulfonic acid and sodium 2-acrylamido-2-methylpropanesulfonate are more preferable.
- the content ratio in the water-insoluble resin of the structural unit derived from the first monomer having at least one group selected from a sulfo group and a salt of the sulfo group in the water-insoluble resin is the total mass of the water-insoluble resin. On the other hand, 5% by mass to 25% by mass is preferable, 8% by mass to 25% by mass is more preferable, and 10% by mass to 25% by mass is particularly preferable.
- the content ratio of the structural unit derived from the first monomer is 5% by mass or more, it is suitable for hydrophilizing the particle surface, and suitable for hydrophilizing the surface of the substrate.
- the content ratio of the structural unit derived from the first monomer is 25% by mass or less, the balance with the degree of hydrophobicity inside the particles is good, and the particles are hardly swelled, and stable dispersion stability is achieved. Sex is obtained.
- a structural unit derived from the second monomer-- The constitutional unit derived from the second monomer is obtained by copolymerizing at least a second monomer containing at least one structure selected from an aromatic ring structure and an alicyclic structure with at least the first monomer. This is a structural unit present in the resin.
- the hydrophobicity inside the particles of the water-insoluble resin can be compared with the case of having an aliphatic structure such as an alkyl chain, for example. Can be improved.
- the structural unit derived from the second monomer is a hydrophobic structural unit and does not have a sulfo group or a salt of a sulfo group. Therefore, the constitutional unit derived from the second monomer is a first unit having at least one group selected from the above-mentioned sulfo group and sulfo group salt in that it does not have a sulfo group and a sulfo group salt. Distinguished from structural units derived from the mer.
- the second monomer containing at least one structure selected from an aromatic ring structure and an alicyclic structure is an aromatic ring structure or an alicyclic structure, or a monomer having an aromatic ring structure and an alicyclic structure, in particular
- the structural unit derived from the second monomer is derived from a structural unit derived from a monomer containing an aromatic ring structure or an alicyclic structure, or a structural unit derived from a monomer containing an aromatic ring structure and an alicyclic structure. What is necessary is just to select suitably from the group which becomes.
- the 2nd monomer may be contained individually by 1 type, and may contain 2 or more types.
- the structural unit derived from the second monomer is preferably a structural unit selected from the group of structural units represented by any one of the following general formulas A to E.
- R 11 represents a methyl group or a hydrogen atom.
- R 12 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group.
- R 12 is preferably a hydrogen atom or a linear or branched alkyl group having 4 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.
- R 12 may be an unsubstituted group or a group substituted with a substituent.
- substituents include halogen (eg, chlorine atom, bromine atom), alkyl group (eg, methyl group, ethyl group, etc.) and the like.
- n represents an integer of 0 to 5.
- the plurality of R 12 may be the same group or different from each other.
- L 11 represents a single bond, a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, —O—, —NH. It represents a divalent linking group in which one or more selected from the group consisting of —, —S—, and —C ( ⁇ O) — are linked.
- Examples of the linear, branched or cyclic alkylene group having 1 to 18 carbon atoms include a methylene group, an ethylene group, an i-propylene group, a t-butylene group, and an n-propylene group.
- Examples of the arylene group having 6 to 18 carbon atoms include a phenylene group, a naphthylene group, and a tolyl group.
- L 11 is preferably a divalent linking group shown below.
- R 21 each independently represents a methyl group or a hydrogen atom.
- n represents an integer of 1 to 8.
- a structural unit represented by the general formula A is preferable, and styrene is particularly preferable.
- the structural unit represented by the general formula A is included, the proportion of oxygen atoms in the molecule of the water-insoluble resin is decreased, and the effect of suppressing the decrease in the density of the solid image is high.
- styrene is a more hydrophobic compound than a monomer containing an element other than a carbon atom and a hydrogen atom, so that the particle is prevented from swelling and the dispersion stability of the particle is further improved.
- a total of structural units derived from the second monomer containing at least one structure selected from an aromatic ring structure and an alicyclic structure (preferably a structural unit represented by any one of the general formulas A to E)
- the content ratio in the water-insoluble resin can be in the range of 5% by mass to 80% by mass with respect to the total mass of the water-insoluble resin, among which 10% by mass to 40% by mass is preferable, and 20% by mass. More preferred is 40% by mass.
- the total content ratio of the structural units represented by any one of the general formulas A to E is 10% by mass or more, it is suitable for hydrophobizing the inside of the water-insoluble resin particles, and the aqueous treatment It is easy to prevent swelling when particles are present in the liquid, and the dispersion stability of the particles in the treatment liquid becomes better. As a result, the occurrence of streak unevenness in the image is effectively suppressed. Further, when the content ratio of the structural unit represented by any one of the general formulas A to E is 40% by mass or less, it is advantageous in terms of solid image density and stripe unevenness.
- the ratio of the mass of oxygen atoms in the second monomer to the molecular weight of the second monomer is preferably 0.1 or less.
- the ratio of the mass of the oxygen atom to the molecular weight of the second monomer is 0.1 or less, the second monomer is less likely to be unevenly distributed on the surface and is preferable in that it is localized inside.
- the ratio of the mass of the oxygen atom to the molecular weight of the second monomer can be selected from a range of 0 or more.
- the ratio of the mass of the oxygen atom to the molecular weight of the second monomer is preferably as small as possible, and 0 is particularly preferable.
- a structural unit derived from a second monomer containing at least one structure selected from an aromatic ring structure and an alicyclic structure preferably a structural unit represented by any one of the general formulas A to E
- a first monomer containing at least one group selected from a sulfo group and a salt of a sulfo group with respect to the content (the total content when two or more structural units derived from the second monomer are contained)
- the ratio of the content of the structural unit derived from (the total content when two or more structural units derived from the first monomer are included) (the structural unit derived from the first monomer / second
- the structural unit derived from the monomer is preferably from 0.10 to 4.0, more preferably from 0.10 to 2.0, even more preferably from 0.15 to 0.90, and 0.30 on a mass basis.
- the sulfo group and the sulfo group salt are selected.
- the balance between the hydrophilicity due to the hydrophilic group and the hydrophobicity due to the hydrophobic group selected from the aromatic ring structure and the alicyclic structure is good, and both the stability of the particles in the treatment liquid and the image quality can be achieved.
- the water-insoluble resin in the water-insoluble resin particles includes a structural unit derived from the first monomer and a structural unit derived from another monomer other than the structural unit derived from the second monomer. You may go out. Examples of structural units derived from other monomers include, for example, structural units derived from monomers having at least one group selected from carboxy groups and salts of carboxy groups, and other monomers shown below. The structural unit derived from can be mentioned.
- the structural unit derived from another monomer is distinguished from the structural unit derived from the first monomer described above in that it does not have a sulfo group or a salt of a sulfo group.
- the structural unit derived from another monomer is not a hydrophobic structural unit (for example, includes a carboxy group or a salt thereof), or has no aromatic ring structure and alicyclic structure as described above.
- the structural unit derived from the first monomer is distinguished from the structural unit derived from the second monomer.
- the water-insoluble resin contains a structural unit derived from a monomer having at least one group selected from a carboxy group and a salt of a carboxy group, a solid image density reduction can be more effectively suppressed, Concentration is easy to obtain. This is presumably because the interaction with the surface of the substrate (for example, coated paper) has become stronger, and the water-insoluble resin particles are more likely to be unevenly distributed on the surface of the substrate.
- the content ratio of the structural unit derived from the monomer having at least one group selected from a carboxy group and a salt of the carboxy group is preferably 0.01% by mass to 40% by mass with respect to the total mass of the water-insoluble resin. 0.01 mass% to 10 mass% is more preferable.
- Examples of structural units derived from other monomers include acrylic acid esters (for example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate; methyl acrylate, acrylic acid 2 -Hydroxyethyl, etc.), amide monomers (eg, acrylamide, N- (2-hydroxyethyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, isopropylacrylamide, N- (2-hydroxymethyl) ) Acrylamide, methacrylamide, etc.), vinyl cyanide monomers (eg, acrylonitrile, methacrylonitrile, etc.), ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomers (eg, ⁇ -hydroxyethyl acrylate, ⁇ - Hydroxy And tertiary salts such as dimethylaminoethyl (meth) acrylate, die
- Quaternary salts and quaternary salts of dialkylaminoalkyl (meth) acrylamides such as halogenated alkyl adducts (eg methyl chloride adducts) and aryl halide adducts (eg benzyl chloride adducts)), bifunctional Examples include structural units derived from (meth) acrylates (for example, ethylene glycol dimethacrylate, ethylene glycol methacrylate, diethylene glycol dimethacrylate, diethylene glycol methacrylate, etc.). However, examples of structural units derived from other monomers are not limited to the above structural units.
- the structural units derived from other monomers may be included singly or in combination of two or more.
- the content of structural units derived from other monomers can be in the range of 20% by mass to 80% by mass with respect to the total mass of the water-insoluble resin, and more preferably 30% by mass to 75% by mass. 30 mass% to 60 mass% is more preferable.
- the structural unit derived from another monomer is preferably not a structural unit derived from a hydrophobic monomer from the viewpoint of maintaining the hydrophilicity of the water-insoluble resin particles.
- the structural unit derived from another monomer is preferably a structural unit derived from a monomer selected from methyl methacrylate, ethyl methacrylate, and ethyl acrylate, and more preferably methyl methacrylate and methacrylic acid.
- the structural unit derived from the other monomer is introduced into the water-insoluble resin by copolymerizing the other monomer.
- the other monomer is copolymerized. Then, after synthesizing the copolymer, a method of hydrolyzing and further regenerating the carboxy group by adding a strong acid may be applied.
- the glass transition temperature (Tg) of the water-insoluble resin is preferably 100 ° C. or higher. When the Tg is 100 ° C. or higher, the dispersion stability of the water-insoluble resin particles is excellent. Tg is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and 130 ° C. or higher and 200 ° C. or lower from the viewpoint of maintaining good thermal stability of the particles dispersed in the treatment liquid. Is particularly preferred. Tg of water-insoluble resin particles is a value measured by a differential scanning calorimeter (DSC) EXSTAR 6220 manufactured by SII Nano Technology.
- DSC differential scanning calorimeter
- the content ratio of the water-insoluble resin particles to the compound (aggregating component) that aggregates the colorant contained in the ink composition is preferably 0.01 to 2.0, preferably 0.01 to 1.0. Is more preferable, and 0.19 to 0.5 is most preferable.
- the content ratio of the water-insoluble resin particles is 0.19 or more on a mass basis, it is advantageous in terms of the density of the solid image portion. Further, when the content ratio of the water-insoluble resin particles is 0.5 or less on a mass basis, it is advantageous in terms of streak unevenness and image roughness.
- the content ratio of the water-insoluble resin particles is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, and more preferably 3% by mass to 5% by mass with respect to the total mass of the treatment liquid. Further preferred.
- the content of the water-insoluble resin particles is 0.5% by mass or more, the effect of improving the wettability of the substrate is large.
- the content is 20% by mass or less, the viscosity of the treatment liquid is in an appropriate range. To improve the stability of the treatment liquid.
- the weight average molecular weight of the water-insoluble resin is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, still more preferably 10,000 to 300,000, and the viewpoint of the viscosity of the treatment liquid From 20,000 to 70,000 is particularly preferable.
- the weight average molecular weight is a value measured by gel permeation chromatography (GPC).
- GPC uses HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) as a measuring device, and 3 columns of TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as a column. This is carried out using THF (tetrahydrofuran) as an eluent.
- the sample concentration is 0.45 mass%
- the flow rate is 0.35 ml / min
- the sample injection amount is 10 ⁇ l
- the measurement temperature is 40 ° C.
- the suggestive refractometer (RI) detector is used.
- the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It is prepared from 8 samples of “A-2500”, “A-1000” and “n-propylbenzene”.
- the treatment liquid contains at least one compound (aggregating component) that aggregates the colorant in the ink composition.
- the treatment liquid comes into contact with the ink composition, whereby at least the colorant in the ink composition is aggregated and a finer image can be obtained.
- “Aggregating the colorant” refers to increasing the particle diameter of secondary particles formed of the colorant by destabilizing the dispersion state of the colorant dispersed in the ink composition.
- the particle diameter is a value obtained by measuring the volume average particle diameter by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.).
- the aggregating component contributes to aggregation of resin particles and the like in a dispersed state in addition to the colorant (preferably pigment).
- Examples of the aggregating component include acidic compounds such as organic acidic compounds and inorganic acidic compounds, polyvalent metal salts, and cationic compounds. Among these, from the viewpoint of aggregation rate, an acidic compound is preferable, and an organic acidic compound is more preferable.
- Examples of the acidic compound include acidic substances that can lower the pH of the ink composition, and either an organic acidic compound or an inorganic acidic compound may be used. Two or more organic acidic compounds and inorganic acidic compounds may be used in combination.
- the organic acidic compound can aggregate components in the ink composition.
- an organic acidic compound For example, the compound which has a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfo group, a sulfinic acid group, a carboxy group etc. is mentioned.
- the organic acidic compound is preferably a compound having a phosphate group or a carboxy group, and more preferably a compound having a carboxy group.
- Compounds having a carboxy group are polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid. Phthalic acid, 4-methylphthalic acid, lactic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or these (For example, polyvalent metal salts) are preferred. These compounds may be used alone or in combination of two or more.
- the compound having a carboxy group is preferably a divalent or higher carboxylic acid (polyvalent carboxylic acid) from the viewpoint of the aggregation rate of the ink composition, and malonic acid, malic acid, maleic acid, succinic acid, glutaric acid, fumaric acid. More preferred is at least one polyvalent carboxylic acid selected from tartaric acid, 4-methylphthalic acid, and citric acid, and particularly preferred are malonic acid, malic acid, tartaric acid, and citric acid.
- polyvalent carboxylic acid polyvalent carboxylic acid
- More preferred is at least one polyvalent carboxylic acid selected from tartaric acid, 4-methylphthalic acid, and citric acid, and particularly preferred are malonic acid, malic acid, tartaric acid, and citric acid.
- the organic acidic compound preferably has a low pKa. Dispersion stability is reduced by bringing the surface charge of particles such as pigments and polymer particles in the ink composition, which is stabilized by a weakly acidic functional group such as a carboxy group, into contact with an organic acidic compound having a lower pKa. Can be reduced.
- the organic acidic compound is preferably an acidic compound having a low pKa, high solubility in water, and a valence of 2 or more, and a functional group (for example, a carboxy group) that stabilizes the dispersion of particles in the ink composition.
- a divalent or trivalent acidic compound having a high buffering capacity in a pH range lower than the pKa of is more preferable.
- the inorganic acidic compound can agglomerate components in the ink composition.
- an inorganic acidic compound For example, phosphoric acid, a phosphoric acid compound, nitric acid, nitrous acid, a sulfuric acid, hydrochloric acid etc. are mentioned.
- phosphoric acid and a phosphoric acid compound are preferable from the viewpoint of suppressing the roughness of the image and the aggregation speed of the ink.
- Phosphoric acid has a low water solubility (25 ° C.) of 0.0018 g / 100 g of water when calcium salt (calcium phosphate) is used. Therefore, when the inorganic acidic compound contained in the processing liquid is phosphoric acid, the calcium salt is not dissolved but is fixed, and the effect of suppressing the occurrence of roughness on the surface of the image area is high. In particular, when a recording medium having a coating layer containing calcium carbonate is used as the recording medium, phosphoric acid is advantageous as the inorganic acidic compound contained in the treatment liquid.
- phosphoric acid compound for example, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, or a salt thereof can be used.
- polyvalent metal salt examples include alkaline earth metals belonging to Group 2 of the periodic table (eg, magnesium, calcium), Group 3 transition metals (eg, lanthanum) of the periodic table, and cations from Group 13 of the periodic table. (For example, aluminum) and the salt of lanthanides (for example, neodymium) can be mentioned.
- the metal salt carboxylate (formic acid, acetic acid, benzoate, etc.), nitrate, chloride, and thiocyanate are suitable.
- calcium salts or magnesium salts of carboxylic acids (formic acid, acetic acid, benzoates, etc.), calcium salts or magnesium salts of nitric acid, calcium chloride, magnesium chloride, and calcium salts or magnesium salts of thiocyanic acid.
- cationic compound examples include a cationic resin and a cationic surfactant.
- the cationic resin examples include epichlorohydrin / dimethylamine addition polymer, polycondensate of dicyandiamide and formalin or diethylenetriamine, a copolymer of dimethyldiallylammonium chloride and sulfur dioxide (SO 2 ), diallylamine salt and sulfur dioxide ( SO 2 ) copolymer, dimethyldiallylammonium chloride polymer, allylamine salt polymer, dialkylaminoethyl (meth) acrylate quaternary salt polymer, polyallylamine, cationic epoxy, polyethyleneimine, polyacrylamide, poly (meta ) Acrylic acid ester, vinylformamide, cationic resin emulsion, cationic resin polyvalent metal salt and the like.
- a primary, secondary, or tertiary amine salt type compound is preferable.
- amine salt type compounds include hydrochloride or acetate compounds (eg, laurylamine, cocoamine, stearylamine, rosinamine), quaternary ammonium salt type compounds (eg, lauryltrimethylammonium chloride, cetyltrimethyl).
- Ammonium chloride lauryldimethylbenzylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, etc.
- pyridinium salt type compounds eg cetylpyridinium chloride, cetylpyridinium bromide etc.
- imidazoline type cationic compounds eg 2-heptadecenyl- Hydroxyethyl imidazoline, etc.
- ethylene oxide adducts of higher alkylamines eg dihydroxyethyl stearylamine. It is.
- Polyallylamines may also be used.
- amphoteric surfactants that are cationic in a desired pH range can also be used, such as amino acid type amphoteric surfactants, R—NH—CH 2 CH 2 —COOH type compounds (where R is an alkyl group). Group), carboxylate type amphoteric surfactants (for example, stearyldimethylbetaine, lauryldihydroxyethylbetaine, etc.), amphoteric surfactants such as sulfate ester type, sulfonic acid type, or phosphate ester type. It is done.
- amino acid type amphoteric surfactants R—NH—CH 2 CH 2 —COOH type compounds (where R is an alkyl group). Group
- carboxylate type amphoteric surfactants for example, stearyldimethylbetaine, lauryldihydroxyethylbetaine, etc.
- amphoteric surfactants such as sulfate ester type, sulfonic acid type, or phosphate ester type
- the total content of the aggregating component in the total mass of the processing liquid is not particularly limited, but the content of the aggregating component is preferably 5% by mass to 40% by mass with respect to the total mass of the processing liquid. 10% by mass to 30% by mass is more preferable.
- the content of the aggregating component is 5% by mass or more, the roughness of the image can be suppressed. Further, when the content of the aggregating component is 40% by mass or less, the abrasion resistance of the image is improved.
- the content ratio of the organic acidic compound and the inorganic acidic compound is such that the content of the inorganic acidic compound relative to the content of the organic acidic compound is from the viewpoint of suppressing the aggregation rate and roughness.
- the content is preferably 5 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, still more preferably 15 mol% to 35 mol%.
- the mass ratio of the water-insoluble resin particles to the compound (aggregating component) that aggregates the colorant in the ink composition is reduced in the density of the solid image portion.
- the content is from 0.5% by mass to 0.5% by mass, and particularly preferably from 0.1% by mass to 0.4% by mass.
- the treatment liquid contains water and is prepared as an aqueous composition.
- the water content is not particularly limited, but is preferably in the range of 10% by mass to 99% by mass, more preferably 50% by mass to 90% by mass, and still more preferably 60% by mass with respect to the total mass of the treatment liquid. % By mass to 80% by mass.
- the treatment liquid may contain components other than the above components.
- examples of other components include organic solvents, nitrogen-containing heterocyclic compounds, antifoaming agents, and other additives.
- the treatment liquid preferably contains at least one organic solvent.
- the organic solvent is preferably an organic solvent that dissolves 5 g or more in 100 g of water at 20 ° C. (hereinafter also referred to as “water-soluble organic solvent”).
- water-soluble organic solvent the same water-soluble organic solvents as those contained in the ink composition described later can be used.
- these organic solvents from the viewpoint of curling suppression, polyalkylene glycol or a derivative thereof is preferable.
- the content of the organic solvent in the treatment liquid is not particularly limited, but from the viewpoint of curling suppression, it is preferably 1% by mass to 30% by mass with respect to the entire treatment liquid, and 5% by mass to 15% by mass. It is more preferable that
- the treatment liquid may contain a nitrogen-containing heterocyclic compound. Thereby, the abrasion resistance of an image and the conveyance property of a base material further improve.
- a nitrogen-containing 5-membered ring structure or a 6-membered ring structure is preferable, and a nitrogen-containing 5-membered ring structure is particularly preferable.
- a nitrogen-containing 5-membered ring structure and the nitrogen-containing 6-membered ring structure preferably a 5-membered or 6-membered heterocyclic structure containing at least one kind of carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom Is preferred.
- the heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring.
- heterocycle examples include a tetrazole ring, a triazole ring, an imidazole ring, a thiadiazole ring, an oxadiazole ring, a selenodiazole ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a pyrimidine ring, Examples include a triazaindene ring, a tetraazaindene ring, a pentaazaindene ring, and the like.
- the heterocycle may have a substituent.
- Substituents include nitro groups, halogen atoms (eg, chlorine atoms, bromine atoms), mercapto groups, cyano groups, and substituted or unsubstituted alkyl groups (eg, methyl, ethyl, propyl, t-butyl, cyanoethyl groups, respectively) ), Aryl groups (eg phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl groups), alkenyl groups (eg allyl groups), aralkyl groups (eg benzyl, 4- Methylbenzyl and phenethyl groups), sulfonyl groups (eg methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl groups), carbamoyl groups
- nitrogen-containing heterocyclic compounds include imidazole, benzimidazole, benzoindazole, benzotriazole, tetrazole, benzoxazole, benzothiazole, pyridine, quinoline, pyrimidine, piperidine, piperazine, quinoxaline, morpholine and the like.
- the nitrogen-containing heterocyclic compound may have a substituent such as the above alkyl group, carboxy group, or sulfo group.
- Preferred nitrogen-containing 6-membered ring compounds are compounds having a triazine ring, a pyrimidine ring, a pyridine ring, a pyrroline ring, a piperidine ring, a pyridazine ring, or a pyrazine ring, and among them, a compound having a triazine ring or a pyrimidine ring is preferable.
- the nitrogen-containing 6-membered ring compound may have a substituent.
- substituents examples include an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3), an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3), a hydroxyl group, a carboxy group, a mercapto group, and 1 to 6 carbon atoms.
- substituents include (preferably 1 to 3) alkoxyalkyl groups and hydroxyalkyl groups having 1 to 6 carbon atoms (preferably 1 to 3).
- preferable nitrogen-containing 6-membered ring compounds include triazine, methyltriazine, dimethyltriazine, hydroxyethyltriazine ring, pyrimidine, 4-methylpyrimidine, pyridine, pyrroline and the like.
- the treatment liquid may contain an antifoaming agent.
- the antifoaming agent include silicone compounds (silicone defoaming agents) and pluronic compounds (pluronic defoaming agents). Of these, silicone antifoaming agents are preferred.
- a silicone antifoaming agent having a polysiloxane structure is preferable.
- a commercially available product may be used as a defoaming agent.
- a commercially available product may be used.
- BYK-012, 017, 021, 022, 024, 025, 038, 094 above, manufactured by BYK Japan
- KS-537 KS-604, KM-72F manufactured by Shin-Etsu Chemical Co., Ltd.
- TSA-739 manufactured by Momentive Performance Materials Japan Godo Kaisha
- Orphine AF104 manufactured by Nissin Chemical Industry Co., Ltd.
- BYK-017, 021, 022, 024, 025, 094, KS-537, KS-604, KM-72F, and TSA-739 which are silicone-based antifoaming agents, are preferable, from the viewpoint of ink ejection stability.
- the content of the antifoaming agent is preferably 0.0001% by mass to 1% by mass, and 0.001% by mass to 0.1% by mass with respect to the total mass of the treatment liquid. % Is more preferable.
- the amount of silicone oil is 50 ppm to 200 ppm.
- the treatment liquid can contain other additives as required.
- Other additives are the same as other additives in the ink composition described later.
- -Surface tension- There is no restriction
- the surface tension of the treatment liquid is determined by the automatic surface tensiometer. This is a value measured using CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of 25 ° C. by the plate method. The surface tension of the treatment liquid can be adjusted, for example, by adding a surfactant.
- the pH (25 ° C. ⁇ 1 ° C.) of the treatment liquid is preferably in the range of 7.0 or less, more preferably 0.5 to 3.5, and more preferably 0.5 to 2.0 from the viewpoint of the aggregation rate of the ink composition. Is more preferable.
- the pH is a value measured using a pH meter WM-50EG (manufactured by Toa DDK Co., Ltd.) with the treatment liquid adjusted to 25 ° C. in an environment of 25 ° C.
- Viscosity ⁇ The viscosity of the treatment liquid is preferably in the range of 1 mPa ⁇ s to 30 mPa ⁇ s, more preferably in the range of 1 mPa ⁇ s to 20 mPa ⁇ s, from the viewpoint of the aggregation rate of the ink composition. Is more preferable, and the range of 2 mPa ⁇ s to 10 mPa ⁇ s is particularly preferable.
- the viscosity is a value measured under the condition of 25 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
- the ink composition in the ink set contains at least a colorant and water.
- the ink composition can further contain resin particles, a pigment dispersant (polymer dispersant), an organic solvent, a neutralizing agent, and other components as necessary.
- the ink composition contains at least one colorant.
- the colorant is not particularly limited and may be a pigment or a dye.
- the colorant is preferably an anionic colorant, and more preferably a pigment, from the viewpoint of excellent cohesiveness when brought into contact with the aggregating component.
- the “anionic colorant” means an anionic group such as a carboxy group, a sulfo group, or a phosphate group in the structure (in the structure of the dispersant when the colorant is coated with a dispersant described later).
- the coloring agent which has.
- any of an organic pigment and an inorganic pigment may be sufficient.
- the pigment is preferably a pigment that is almost insoluble or hardly soluble in water from the viewpoint of ink colorability.
- Organic pigments include, for example, polycyclic compounds such as azo lakes, azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments.
- pigments examples thereof include pigments, dye lakes such as basic dye lakes and acid dye lakes, nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.
- inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Further, any pigment that is not described in the color index can be used as long as it is dispersible in water. Further, pigments surface-treated with a surfactant, a polymer dispersing agent, etc., graft carbon, etc. can be used.
- azo pigments phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, and carbon black pigments are particularly preferable, and anionic azo pigments, anionic phthalocyanine pigments, and anionic quinacridone pigments are more preferable.
- a form in which the pigment is dispersed by a dispersant is preferable.
- a form in which the pigment is dispersed with the polymer dispersant that is, a form in which at least a part of the pigment is coated with the polymer dispersant is preferable.
- a pigment at least partially coated with a polymer dispersant is referred to as a “resin-coated pigment”.
- the dispersant may be a polymer dispersant or a low molecular surfactant type dispersant.
- the polymer dispersant may be a non-crosslinked polymer dispersant (non-crosslinked polymer dispersant), or a polymer dispersant crosslinked with a crosslinking agent (crosslinked polymer dispersant).
- the non-crosslinked polymer dispersant may be a water-soluble non-crosslinked polymer dispersant or a water-insoluble non-crosslinked polymer dispersant.
- the low molecular surfactant type dispersant the surfactant type dispersants described in paragraphs 0016 to 0020 of JP 2010-188661 A can be used.
- hydrophilic polymer compounds can be used as the water-soluble non-crosslinked polymer dispersant.
- water-soluble non-crosslinked polymer dispersant for example, natural hydrophilic polymer compounds described in paragraphs 0021 to 0022 of JP 2010-188661 A can be used.
- a synthetic hydrophilic polymer compound can also be used as the water-soluble non-crosslinked polymer dispersant.
- Synthetic hydrophilic polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyvinyl methyl ether, polyacrylamide, polyacrylic acid or alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resins, Water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of ⁇ -naphthalene sulfonic acid formalin condensate, cation such as quaternary ammonium and amino group And a high molecular compound having a salt of a functional functional group in the side chain.
- a polymer compound containing a carboxy group is preferable.
- an acrylic resin such as a water-soluble styrene acrylic resin, a water-soluble styrene maleic acid resin, and a water-soluble vinyl naphthalene.
- High molecular compounds containing a carboxy group such as an acrylic resin and a water-soluble vinyl naphthalene maleic resin are particularly preferred.
- a polymer having both a hydrophobic portion and a hydrophilic portion can be used as the water-insoluble dispersant.
- styrene- (meth) acrylic acid copolymer styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, polyethylene glycol ( Examples thereof include a meth) acrylate- (meth) acrylic acid copolymer and a styrene-maleic acid copolymer.
- Styrene- (meth) acrylic acid copolymer (meth) acrylic acid ester- (meth) acrylic acid copolymer, polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymer, styrene-maleic acid copolymer May be a binary copolymer or a ternary or higher copolymer.
- (meth) acrylic acid ester- (meth) acrylic acid copolymer is preferable as the non-crosslinked polymer dispersant, and benzyl (meth) acrylate- (meth) acrylic acid-methyl (meth) acrylate ternary copolymer is preferable.
- Polymers are particularly preferred.
- (meth) acrylic acid refers to acrylic acid or methacrylic acid
- (meth) acrylate refers to acrylate or methacrylate.
- the copolymer may be a random copolymer, a block copolymer, or a graft copolymer.
- the weight average molecular weight of the non-crosslinked polymer dispersant is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, still more preferably 5,000 to 80,000, particularly preferably 10,000. ⁇ 60,000.
- the weight average molecular weight is a value measured by the same method as the measurement of the weight average molecular weight of the water-insoluble resin described above.
- the acid value of the non-crosslinked polymer dispersant is not particularly limited, but from the viewpoint of cohesiveness, the acid value of the non-crosslinked polymer dispersant is based on the acid value of the resin particles (preferably self-dispersing resin particles) described later. Is also preferably large.
- the crosslinked polymer dispersant is formed by crosslinking a polymer (uncrosslinked polymer) with a crosslinking agent.
- the polymer is not particularly limited, and various polymers can be used. Among them, polyvinyls, polyurethanes, polyesters and the like that can function as a water-soluble dispersant are preferable, and polyvinyls are more preferable.
- the polymer is preferably a copolymer obtained using a carboxy group-containing monomer as a copolymerization component.
- the carboxy group-containing monomer include (meth) acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid and the like. Among these, from the viewpoint of the crosslinkability and dispersion stability of the polymer. (Meth) acrylic acid and ⁇ -carboxyethyl acrylate are preferred.
- the polymer Since the polymer is crosslinked by a crosslinking agent, it has a functional group that can be crosslinked by the crosslinking agent.
- the crosslinkable functional group is not particularly limited, and examples thereof include a carboxy group or a salt thereof, an isocyanate group, and an epoxy group, and a carboxy group or a salt thereof is preferable from the viewpoint of improving dispersibility.
- the acid value of the polymer is preferably 90 mgKOH / g or more, and more preferably 95 mgKOH / g or more, from the viewpoint of water solubility of the polymer. Furthermore, from the viewpoint of the dispersibility and dispersion stability of the pigment, it is preferably 100 mgKOH / g to 180 mgKOH / g, more preferably 100 mgKOH / g to 170 mgKOH / g, and 100 mgKOH / g to 160 mgKOH / g. Further preferred.
- the acid value is a value measured by the method described in Japanese Industrial Standard (JIS K0070: 1992).
- the weight average molecular weight (Mw) of the polymer is preferably 50,000 to 120,000, more preferably 60,000 to 120,000, still more preferably 60,000 to 100,000, and 60,000 to 90,000. Particularly preferred.
- the weight average molecular weight is a value measured by the same method as the measurement of the weight average molecular weight of the water-insoluble resin described above.
- the polymer preferably further has at least one hydrophobic monomer as a copolymerization component.
- hydrophobic monomers include alkyl (meth) acrylates having 1 to 20 carbon atoms, (meth) acrylates having an aromatic ring group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and styrene and its Derivatives and the like.
- the copolymerization form of the polymer is not particularly limited, and the polymer may be a random polymer, a block polymer, or a graft polymer.
- the method for synthesizing the polymer is not particularly limited, but random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.
- the cross-linking agent is not particularly limited as long as it is a compound having two or more sites that react with the polymer, but in particular, it has two or more epoxy groups from the viewpoint of excellent reactivity with a carboxy group. (A bifunctional or higher functional epoxy compound) is preferred.
- the crosslinking agent include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and polypropylene glycol.
- Examples thereof include diglycidyl ether and trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether are preferable.
- Examples of the method of coating the pigment with the cross-linked polymer dispersant include a method in which the pigment is dispersed using a water-soluble or water-insoluble polymer and then the polymer is cross-linked with the cross-linking agent to prepare a pigment dispersion. .
- the mass ratio of pigment to dispersant is preferably in the range of 1: 0.06 to 1: 3, more preferably in the range of 1: 0.125 to 1: 2. More preferably, it is 1: 0.125 to 1: 1.5.
- the average particle diameter of the pigment is preferably 10 nm to 200 nm, more preferably 10 nm to 150 nm, and even more preferably 10 nm to 100 nm.
- the particle size distribution of the pigment is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution.
- Two or more pigments having a monodispersed particle size distribution may be mixed and used.
- the average particle size and particle size distribution of the pigment can be determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.). Is.
- the content of the pigment in the ink composition is preferably 1% by mass to 25% by mass with respect to the total mass of the ink composition from the viewpoint of image density, and 2% by mass to 20% by mass. % Is more preferable, and 2% by mass to 10% by mass is particularly preferable. You may use a pigment individually by 1 type or in combination of 2 or more types.
- dye As the dye, known dyes can be used without particular limitation. For example, the dyes described in JP-A-2001-115066, JP-A-2001-335714, JP-A-2002-249677 and the like are used in the present disclosure. It can be used suitably. Moreover, when using dye, what hold
- the carrier holding the dye (water-insoluble colored particles) can be used as an aqueous dispersion using a dispersant.
- the carrier is not particularly limited as long as it is insoluble in water or hardly soluble in water, and inorganic materials, organic materials, and composite materials thereof can be used. Specifically, the carriers described in JP 2001-181549 A, JP 2007-169418 A, and the like can be suitably used in the present disclosure.
- the ink composition preferably contains at least one kind of resin particles. Unlike the polymer dispersant (a polymer dispersant that covers at least a part of the pigment), the resin particles are particles that exist separately from the pigment. When the ink composition contains resin particles, the resin particles are preferably aggregated by contact with the aggregating component described above. In addition, the resin particles are preferably resin particles having an anionic dissociation group other than a sulfo group from the viewpoint of excellent cohesiveness when brought into contact with the aggregating component described above. Details of the resin particles having an anionic dissociation group other than the sulfo group will be described later.
- Resin particles having a sulfo group as an anionic dissociation group are not preferable in that the dispersion stability of the resin particles themselves is greatly improved, so that they do not easily aggregate even if they come into contact with the aggregating component of the treatment liquid.
- the resin particles are preferably water-insoluble or poorly water-soluble resin particles.
- “water-insoluble or poorly water-soluble” means that when the resin is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., the dissolved amount is 15 g or less. That means. From the viewpoint of improving the continuous ejection property and ejection stability of the ink, the dissolved amount is preferably 10 g or less, more preferably 5 g or less, and even more preferably 1 g or less.
- the dissolution amount is the dissolution amount when 100% neutralized with sodium hydroxide or acetic acid according to the type of salt-forming group of the water-insoluble or poorly water-soluble resin particles.
- the resin particles include thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, or fluorine resins, chlorides, and the like.
- Amino resins such as polyvinyl resins such as vinyl, vinyl acetate, polyvinyl alcohol, or polyvinyl butyral, polyester resins such as alkyd resins and phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd co-condensation resins, urea resins, urea resins, etc.
- Examples thereof include particles of a resin having an anionic group such as a system material, a copolymer or a mixture thereof.
- an anionic acrylic resin is, for example, an acrylic monomer having an anionic dissociative group other than a sulfo group (an anionic group-containing acrylic monomer) and, optionally, an anionic dissociative group. It is obtained by polymerizing another monomer copolymerizable with the containing acrylic monomer in a solvent.
- the anionic dissociable group-containing acrylic monomer include an acrylic monomer having one or more selected from the group consisting of a carboxy group and a phosphonic acid group.
- an acrylic monomer having a carboxy group for example, acrylic acid, (Methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, etc.) are preferred, and acrylic acid or methacrylic acid is particularly preferred.
- the resin particles are preferably self-dispersing resin particles (self-dispersing resin particles) from the viewpoint of ejection stability and liquid stability (particularly dispersion stability) of a system containing a colorant.
- self-dispersing resin particles self-dispersing resin particles
- the polymer itself has a functional group (especially a hydrophilic group such as an acidic group or a salt thereof), A water-insoluble polymer that can be dispersed in an aqueous medium.
- the dispersed state refers to an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in an aqueous medium and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in an aqueous medium in a solid state. It includes both states.
- An aqueous medium refers to a medium containing water.
- the aqueous medium may contain a hydrophilic organic solvent as necessary.
- the aqueous medium preferably contains water and 0.2% by mass or less of a hydrophilic organic solvent with respect to water, and more preferably contains only water.
- the self-dispersing resin is preferably self-dispersing resin particles that can be in a dispersed state in which a water-insoluble polymer is dispersed in a solid state from the viewpoint of aggregation rate and fixing property when contained in the ink composition.
- Examples of a method for obtaining an emulsified or dispersed state of the self-dispersing resin that is, a method for preparing an aqueous dispersion of self-dispersing resin particles include a phase inversion emulsification method.
- a phase inversion emulsification method for example, a self-dispersing resin is dissolved or dispersed in a solvent (for example, a water-soluble organic solvent) and then poured into water as it is without adding a surfactant.
- Examples include a method of obtaining an aqueous dispersion in an emulsified or dispersed state after stirring and mixing in a state in which a salt-forming group (for example, acidic group) of the resin is neutralized and mixing, and removing the solvent.
- a salt-forming group for example, acidic group
- the stable emulsification or dispersion state in the self-dispersing resin means a solution obtained by dissolving 30 g of a water-insoluble polymer in 70 g of an organic solvent (for example, methyl ethyl ketone), neutralization capable of neutralizing a salt-forming group of the water-insoluble polymer 100%.
- Agent sodium hydroxide when the salt-forming group is anionic, acetic acid when cationic
- 200 g of water were mixed and stirred (apparatus: stirring device with stirring blades, rotation speed 200 rpm, 30 minutes, 25 ° C.). After that, even after removing the organic solvent from the mixed solution, it means that the emulsified or dispersed state is stably present at 25 ° C. for at least one week (that is, a state in which precipitation cannot be visually confirmed).
- the stability of the emulsified or dispersed state in the self-dispersing resin can also be confirmed by an accelerated sedimentation test by centrifugation.
- the stability of the sedimentation acceleration test by centrifugation is, for example, adjusted by adjusting the aqueous dispersion of resin particles obtained by the above method to a solid content concentration of 25% by mass and then centrifuging at 12000 rpm for 1 hour. It can be evaluated by measuring the solid content concentration of the supernatant after separation. If the ratio of the solid content concentration after centrifugation to the solid content concentration before centrifugation is large (if it is a value close to 1), the resin particles will not settle by centrifugation, that is, the aqueous dispersion of resin particles Means more stable.
- the ratio of the solid content concentration before and after centrifugation is preferably 0.8 or more, more preferably 0.9 or more, and particularly preferably 0.95 or more.
- the self-dispersing resin preferably has a water-soluble component content that exhibits water solubility in a dispersed state of 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. More preferably.
- a water-soluble component content that exhibits water solubility in a dispersed state of 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. More preferably.
- the water-soluble component is a compound contained in the self-dispersing resin and is a compound that dissolves in water when the self-dispersing resin is in a dispersed state.
- the water-soluble component is a water-soluble compound that is by-produced or mixed when the self-dispersing resin is produced.
- the main chain skeleton of the water-insoluble polymer is not particularly limited, and for example, vinyl polymers and condensation polymers (epoxy resins, polyesters, polyurethanes, polyamides, celluloses, polyethers, polyureas, polyimides, polycarbonates, etc.) can be used. . Of these, vinyl polymers are particularly preferred.
- Preferable examples of the vinyl polymer and the monomer constituting the vinyl polymer include those described in JP-A Nos. 2001-181549 and 2002-88294.
- radical transfer of vinyl monomers using dissociable groups (or substituents that can be induced to dissociable groups), polymerization initiators, and iniferters, or dissociable groups on either initiators or terminators A vinyl polymer in which a dissociable group is introduced at the end of a polymer chain by ionic polymerization using a compound having (or a substituent that can be derived from a dissociable group) can also be used.
- preferable examples of the condensation polymer and the monomer constituting the condensation polymer include those described in JP-A-2001-247787.
- the resin particles in the present disclosure preferably include a water-insoluble polymer including a hydrophilic structural unit and a structural unit derived from an aromatic group-containing monomer or a cyclic aliphatic group-containing monomer from the viewpoint of dispersion stability. .
- the “hydrophilic structural unit” is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and two or more hydrophilic groups may be derived from one hydrophilic group-containing monomer. It may be derived from the contained monomer.
- the hydrophilic group is not particularly limited except for a sulfo group, and may be a dissociable group or a nonionic hydrophilic group.
- the hydrophilic group is preferably a dissociable group, more preferably an anionic dissociative group, from the viewpoint of stability of the formed emulsified or dispersed state. That is, the resin particles in the present disclosure are preferably resin particles having an anionic dissociation group. Examples of the dissociable group include a carboxy group and a phosphoric acid group, and among them, a carboxy group is preferable from the viewpoint of fixability when an ink composition is formed.
- the hydrophilic group-containing monomer is preferably a dissociable group-containing monomer from the viewpoint of dispersion stability and aggregability, and is preferably a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond.
- the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.
- the unsaturated carboxylic acid monomer examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.
- Specific examples of the unsaturated phosphoric acid monomer include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloxyethyl phosphate, diphenyl-2-methacryloxyethyl phosphate, dibutyl-2-acryloxy Examples thereof include ethyl phosphate.
- unsaturated carboxylic acid monomers are preferable, and acrylic acid and methacrylic acid are more preferable from the viewpoints of dispersion stability and ejection stability.
- the resin particles preferably contain a polymer having a carboxy group from the viewpoint of dispersion stability and agglomeration speed when in contact with the treatment liquid, and have a carboxy group and an acid value of 25 mgKOH / g to 100 mgKOH / g. More preferably it contains a polymer. Furthermore, the acid value is more preferably from 25 mgKOH / g to 80 mgKOH / g, particularly preferably from 30 mgKOH / g to 65 mgKOH, from the viewpoints of self-dispersibility and aggregation rate when contacted with the treatment liquid.
- the acid value is 25 mgKOH / g or more, the dispersion stability is good, and when it is 100 mgKOH / g or less, the cohesiveness is improved.
- the acid value is a value measured by the method described in Japanese Industrial Standard (JIS K0070: 1992).
- the aromatic group-containing monomer is not particularly limited as long as it is a compound containing an aromatic group and a polymerizable group.
- the aromatic group may be a group derived from an aromatic hydrocarbon or a group derived from an aromatic heterocyclic ring.
- an aromatic group derived from an aromatic hydrocarbon is preferable from the viewpoint of particle shape stability in an aqueous medium.
- the polymerizable group may be a polycondensable polymerizable group or an addition polymerizable polymerizable group.
- an addition-polymerizable polymerizable group is preferable, and a group containing an ethylenically unsaturated bond is more preferable.
- the aromatic group-containing monomer is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond.
- the aromatic group-containing monomer may be used alone or in combination of two or more.
- Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and a styrene monomer.
- aromatic group-containing (meth) acrylate monomers are preferred from the viewpoint of the balance between the hydrophilicity and hydrophobicity of the polymer chain and the ink fixability, and include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth). At least one selected from acrylates is more preferable, and phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are more preferable.
- the cycloaliphatic group-containing monomer is preferably a monomer having a cycloaliphatic group derived from a cycloaliphatic hydrocarbon and an ethylenically unsaturated bond, and a cycloaliphatic group-containing (meth) acrylate monomer (hereinafter referred to as fat). Cyclic (meth) acrylate is sometimes preferred).
- An alicyclic (meth) acrylate includes a component derived from (meth) acrylic acid and a component derived from alcohol, and the component derived from alcohol is unsubstituted or substituted with alicyclic carbonization. It has a structure containing at least one hydrogen group (cycloaliphatic group).
- the alicyclic hydrocarbon group is the structural site itself derived from alcohol, it may be couple
- the alicyclic hydrocarbon group is not particularly limited as long as it contains a cyclic non-aromatic hydrocarbon group, and is a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or more polycyclic group.
- a hydrocarbon group is mentioned.
- the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group.
- the alicyclic hydrocarbon group may further have a substituent.
- substituents include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, a hydroxyl group, a primary amino group, a secondary amino group, a tertiary amino group, an alkyl or arylcarbonyl group, and a cyano group.
- the alicyclic hydrocarbon group may further form a condensed ring.
- the alicyclic hydrocarbon group in the present disclosure preferably has 5 to 20 carbon atoms in the alicyclic hydrocarbon group portion from the viewpoint of viscosity and solubility.
- Monocyclic (meth) acrylates include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl ( Examples thereof include cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in the cycloalkyl group such as (meth) acrylate and cyclodecyl (meth) acrylate.
- bicyclic (meth) acrylate examples include isobornyl (meth) acrylate and norbornyl (meth) acrylate.
- tricyclic (meth) acrylate examples include adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in admixture of two or more.
- At least one kind of bicyclic (meth) acrylate or tricyclic or higher polycyclic (meth) acrylate may be used.
- it is at least one selected from isobornyl (meth) acrylate, adamantyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
- the resin used for forming the resin particles is preferably an acrylic resin containing a structural unit derived from a (meth) acrylate monomer, and a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate.
- An acrylic resin containing is preferable, and further includes a structural unit derived from an aromatic group-containing (meth) acrylate monomer or an alicyclic (meth) acrylate, and the content thereof is 10% by mass to 95% by mass. Is preferred.
- the content of the aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate is 10% by mass to 95% by mass, the stability of the emulsified or dispersed state is improved, and the ink viscosity is further increased. Can be suppressed.
- the content of the contained (meth) acrylate monomer or alicyclic (meth) acrylate is more preferably 15% by mass to 90% by mass, more preferably 15% by mass to 80% by mass, and more preferably 25% by mass to It is especially preferable that it is 70 mass%.
- the resin used for forming the resin particles can be configured using, for example, a structural unit derived from an aromatic group-containing monomer or a cyclic aliphatic group-containing monomer and a structural unit derived from a dissociable group-containing monomer. . Furthermore, other structural units may be further included as necessary.
- the monomer forming the other structural unit is not particularly limited as long as it is a monomer copolymerizable with an aromatic group-containing monomer and a dissociable group-containing monomer.
- an alkyl group-containing monomer is preferable from the viewpoint of flexibility of the polymer skeleton and ease of control of the glass transition temperature (Tg).
- alkyl group-containing monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Alkyl (meth) acrylates such as butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Ethylenically unsaturated monomers having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; Dialkylaminoalkyl (
- the molecular weight range of the water-insoluble polymer constituting the resin particles is preferably 3,000 to 200,000, more preferably 5,000 to 150,000 in terms of weight average molecular weight, and 10,000 to 100,000. More preferably, it is 000.
- the weight average molecular weight can be measured by the method described above.
- the water-insoluble polymer constituting the resin particle is a structural unit derived from an aromatic group-containing (meth) acrylate monomer (preferably a structural unit derived from phenoxyethyl (meth) acrylate and / or from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer. Or a structural unit derived from benzyl (meth) acrylate) or a cycloaliphatic group-containing monomer (preferably alicyclic (meth) acrylate) as a copolymerization ratio containing 15% by mass to 80% by mass of the total mass of the resin particles. It is preferable.
- the water-insoluble polymer has a copolymerization ratio of 15% by mass to 80% by mass of a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate monomer from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer.
- % A structural unit derived from a carboxy group-containing monomer, and a structural unit derived from an alkyl group-containing monomer (preferably a structural unit derived from an alkyl ester of (meth) acrylic acid).
- the water-insoluble polymer preferably has an acid value of 25 mgKOH / g to 100 mgKOH / g and a weight average molecular weight of 3,000 to 200,000, and an acid value of 25 mgKOH / g to 95 mgKOH / g.
- the weight average molecular weight is more preferably 5,000 to 150,000. The acid value and the weight average molecular weight can be measured by the method described above.
- B-01 Phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/25)
- B-02 Phenoxyethyl acrylate / benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (30/35/29/6)
- B-03 Phenoxyethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (50/44/6)
- B-04 Phenoxyethyl acrylate / methyl methacrylate / ethyl acrylate / acrylic acid copolymer (30/55/10/5)
- B-05 benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (35/59/6)
- B-06 Styrene / phenoxyethyl acrylate / methyl methacrylate / acrylic acid copo
- the method for producing the water-insoluble polymer contained in the resin particles is not particularly limited.
- a method in which emulsion polymerization is performed in the presence of a polymerizable surfactant to covalently bond the surfactant and the water-insoluble polymer examples thereof include a method in which a monomer mixture containing a hydrophilic group-containing monomer and an aromatic group-containing monomer or an alicyclic group-containing monomer is copolymerized by a known polymerization method such as a solution polymerization method or a bulk polymerization method.
- the solution polymerization method is preferable and the solution polymerization method using an organic solvent is more preferable from the viewpoint of the aggregation rate and droplet ejection stability when the ink composition is used.
- the resin particles include a polymer synthesized in an organic solvent from the viewpoint of aggregation rate, and the polymer has an anionic group (carboxy group) (preferably an acid value of 20 mgKOH / g to 100 mgKOH / g. ) It is preferable that part or all of the anionic group (carboxy group) of the polymer is neutralized and prepared as a polymer dispersion having water as a continuous phase. That is, the production of resin particles is performed by providing a step of synthesizing a polymer in an organic solvent and a dispersion step of forming an aqueous dispersion in which at least a part of the anionic group (carboxy group) of the polymer is neutralized. It is preferable.
- the dispersion step preferably includes the following step (1) and step (2).
- Step (1) Step of stirring a mixture containing a polymer (water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium
- Step (2) Step of removing the organic solvent from the mixture
- Step (1) is preferably a treatment in which a polymer (water-insoluble polymer) is first dissolved in an organic solvent, then a neutralizing agent and an aqueous medium are gradually added, mixed and stirred to obtain a dispersion.
- a neutralizing agent and an aqueous medium are gradually added, mixed and stirred to obtain a dispersion.
- resin particles having a particle size with higher storage stability can be obtained without requiring a strong shearing force. be able to.
- Dispersing machines such as a generally used mixing stirring apparatus and an ultrasonic disperser, a high-pressure homogenizer, can be used as needed.
- step (2) the aqueous dispersion of resin particles is obtained by distilling off the organic solvent from the dispersion obtained in step (1) by a conventional method such as distillation under reduced pressure and phase-inversion into an aqueous system. Obtainable.
- the organic solvent in the obtained aqueous dispersion has been substantially removed, and the amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.
- organic solvent examples include alcohol solvents, ketone solvents, and ether solvents.
- organic solvents exemplified in paragraph 0059 of JP 2010-188661 A can be used.
- the neutralizing agent the neutralizing agents exemplified in paragraphs 0060 to 0061 of JP 2010-188661 A can be used.
- the average particle size of the resin particles (particularly self-dispersing resin particles) in the present disclosure is preferably in the range of 10 nm to 400 nm in volume average particle size, more preferably in the range of 10 nm to 200 nm, and still more preferably in the range of 10 nm to 100 nm. Particularly preferred is a range of 10 nm to 50 nm. Manufacturability is improved when the volume average particle diameter is 10 nm or more. Moreover, storage stability improves that a volume average particle diameter is 400 nm or less. Moreover, there is no restriction
- the average particle size and particle size distribution of the resin particles are determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It is done.
- the ink composition may contain one kind of resin particles (preferably self-dispersing resin particles) or two or more kinds.
- the content (total content) of the resin particles (preferably self-dispersing resin particles) in the ink composition is 1% by mass to 30% by mass with respect to the total amount of the ink composition from the viewpoint of glossiness of the image. %, Preferably 3% by mass to 15% by mass.
- the ink composition contains water and is prepared as an aqueous composition.
- the water content is not particularly limited, but is preferably in the range of 10% by mass to 99% by mass, more preferably 30% by mass to 80% by mass, and still more preferably based on the total mass of the ink composition. 50% by mass to 80% by mass.
- the ink composition may contain components other than the above components.
- the ink composition further contains at least one organic solvent (preferably a water-soluble organic solvent).
- a water-soluble organic solvent By containing an organic solvent, in particular, a water-soluble organic solvent, drying prevention and penetration promotion can be achieved.
- a water-soluble organic solvent is used as an anti-drying agent, when an ink composition is ejected by an ink jet method to record an image, nozzle clogging that may occur due to ink drying at an ink ejection port is effectively prevented. be able to.
- a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
- the water-soluble organic solvent suitable for preventing drying include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2 , 6-hexanetriol, acetylene glycol derivatives, glycerin, polyhydric alcohols typified by trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ) Lower alkyl ethers of polyhydric alcohols such as ether, tripropylene glycol monomethyl (or ethyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl- - imidazolid
- N- ethylmorpholine, sulfolane, dimethyl sulfoxide, sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives are preferable. Moreover, these may be used individually by 1 type, or may use 2 or more types together. These water-soluble organic solvents are preferably contained in the ink composition in an amount of 10% by mass to 50% by mass.
- a water-soluble organic solvent is preferably used from the viewpoint of allowing the ink composition to penetrate better into the substrate.
- water-soluble organic solvents suitable for promoting penetration include ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, tripropylene glycol monomethyl (or ethyl) ether, and 1,2-hexanediol. Examples include alcohol. When these are contained in the ink composition in an amount of 5 to 30% by mass, good effects can be obtained. Further, these water-soluble organic solvents are preferably used within a range of addition amounts that do not cause printing / image bleeding and paper loss (print-through).
- the water-soluble organic solvent can be used for adjusting the viscosity.
- water-soluble organic solvents that can be used to adjust the viscosity include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, Cyclohexanol, benzyl alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, Thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) Ter, ethylene glycol monobuty
- the ink composition may contain at least one surfactant.
- the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants and the like. From the viewpoint of the aggregation rate, an anionic surfactant or a nonionic surfactant is preferable.
- the surfactant preferably contains an amount capable of adjusting the surface tension of the ink composition to 25 mN / m or more and 40 mN / m or less in order to deposit ink well by the ink jet method.
- the content of the surfactant is preferably an amount capable of adjusting the surface tension to 27 mN / m to 37 mN / m.
- surfactants can also be used as an antifoaming agent.
- fluorine compounds fluorine compounds, silicone compounds, chelating agents represented by ethylenediaminetetraacetic acid (EDTA), and the like can also be used.
- EDTA ethylenediaminetetraacetic acid
- the ink composition can further contain other additives in addition to the above components.
- Other additives include, for example, antifading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, antiseptics, antifungal agents, pH adjusters, antifoaming agents, viscosity modifiers, dispersion stabilizers, and rust inhibitors.
- Known additives such as agents and chelating agents are included. These various additives may be added directly after the ink composition is prepared, or may be added when the ink composition is prepared.
- a neutralizer (organic base, inorganic alkali) can be used as the pH adjuster.
- the pH adjuster is preferably added so that the pH of the ink composition is 6 to 10, and is preferably added so that the pH is 7 to 10. More preferred.
- the viscosity of the ink composition is preferably in the range of 1 mPa ⁇ s to 30 mPa ⁇ s, from the viewpoint of ejection stability when ejected by the ink jet method, and the aggregation rate when using the treatment liquid described later.
- the range of 20 mPa ⁇ s is more preferable, the range of 2 mPa ⁇ s to 15 mPa ⁇ s is still more preferable, and the range of 2 mPa ⁇ s to 10 mPa ⁇ s is particularly preferable.
- the viscosity is measured using a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD) under the condition of 25 ° C.
- the ink set according to the present disclosure has been described above.
- the ink set of the present invention is not particularly limited to a specific configuration as long as it includes a combination of at least one ink composition and a treatment liquid. Absent.
- a preferred embodiment of the ink set is a configuration (three-color configuration) comprising a combination of cyan ink as an ink composition, magenta ink as an ink composition, yellow ink as an ink composition, and a treatment liquid.
- a black ink that is an ink composition a cyan ink that is an ink composition, a cyan ink that is an ink composition, a magenta ink that is an ink composition, a yellow ink that is an ink composition, and a treatment liquid.
- the structure (4 color structure) which consists of a combination of these is mentioned.
- the ink set may be a one-color or two-color ink set composed of one or two ink compositions and a treatment liquid, as necessary.
- the ink set includes, in addition to the above ink composition, other ink compositions such as at least one selected from light cyan ink, light magenta ink, and light yellow ink, if necessary. Also good.
- other ink compositions such as at least one selected from light cyan ink, light magenta ink, and light yellow ink, if necessary. Also good.
- a known ink composition can be applied to the other ink composition.
- the ink set may contain two or more kinds of treatment liquids as necessary.
- the ink set includes two or more ink compositions
- at least one of the ink compositions may be an ink composition including a colorant (preferably a pigment).
- at least one of the treatment liquids has a structural unit derived from the first monomer and a water-insoluble resin having a structural unit derived from the second monomer.
- the treatment liquid may contain any of the above particles, an aggregating component (a compound that aggregates the colorant in the ink composition) and water.
- Image recording method In the image recording method according to the present disclosure, the treatment of the ink set according to the present disclosure described above is performed on at least one surface of a base material having a contact angle of 70 ° or more when 3 seconds have passed since a water droplet was applied to the surface.
- a pre-processing step of applying a liquid, and an image recording step of recording an image by ejecting the ink composition of the ink set according to the present disclosure described above on one side to which the processing liquid is applied by an inkjet method. Have.
- the image recording method according to the present disclosure since the ink set described above is used when recording an image, a decrease in density in the solid image is suppressed, a desired density is obtained, and streaky unevenness is generated. It is possible to record an image in which the image is suppressed.
- a base material having a contact angle (water contact angle) of 70 ° or more when 3 seconds have passed after applying a water droplet to the surface is used.
- Specific examples include paper base materials such as coated paper and synthetic paper, and polymer base materials such as polyethylene terephthalate (PET) films.
- PET polyethylene terephthalate
- a paper base material is preferable and a paper base material (coated paper) having a coating layer is more preferable in that the effect of suppressing a decrease in density and streaky unevenness (and roughness in some cases) of the solid image portion appears remarkably. preferable.
- the contact angle with water on the surface of the base material is measured at normal temperature and humidity in accordance with the method described in Japanese Industrial Standard (JIS R3257) using a contact angle meter Dropmaster DM700 (manufactured by Kyowa Interface Science Co., Ltd.). Measured.
- the coated paper is one in which a coating layer containing an inorganic pigment or the like is provided on the surface of high-quality paper or neutral paper, which is generally not surface-treated, mainly composed of cellulose as a support.
- the coated paper tends to cause uneven gloss in the image area, but when the treatment liquid contains phosphoric acid or a phosphoric acid compound, the occurrence of uneven gloss in the image area can be effectively suppressed.
- art paper, coated paper, lightweight coated paper, or finely coated paper is preferable.
- the inorganic pigment contained in the coating layer is not particularly limited, but silica, kaolin, clay, calcined clay, zinc oxide, tin oxide, magnesium sulfate, aluminum oxide, aluminum hydroxide, pseudoboehmite, calcium carbonate, satin white , Aluminum silicate, smectite, zeolite, magnesium silicate, magnesium carbonate, magnesium oxide, and diatomaceous earth are preferable, and calcium carbonate, silica, and kaolin are more preferable.
- the substrate commercially available materials can be used.
- “MagnoStarGloss” manufactured by Sappi “Carolina C2S” manufactured by International, “CartaIntegra” manufactured by Metsaboard, and “VJFP series” manufactured by YUPO. Or the like.
- the application amount of the treatment liquid and the application amount of the ink composition may be changed depending on the substrate in order to adjust the physical properties such as the viscoelasticity of the aggregate formed by mixing the treatment liquid and the ink composition.
- the treatment liquid of the ink set described above is applied to at least one surface of the base material having a contact angle of 70 ° or more when 3 seconds have passed after applying water droplets to the surface.
- the treatment liquid can be applied by a known method such as a coating method, an ink jet method, or an immersion method.
- a coating method a known coating method using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater or the like can be used. Details of the inkjet method will be described later.
- the pretreatment step is provided before the image recording step using the ink composition. That is, before applying the ink composition onto the base material, a processing liquid for aggregating the dispersion components (colorants, etc.) in the ink composition is applied in advance, and the processing liquid applied onto the base material An ink composition is applied so as to come into contact with the film, and an image is formed. Thereby, inkjet recording can be speeded up and a fine image with high density and resolution can be obtained even at high speed recording.
- the treatment liquid on the substrate is dried by heating after the treatment liquid is applied on the substrate and before the ink composition is applied.
- ink coloring properties such as bleeding prevention are improved, and a visible image with good color density and hue can be recorded.
- Heating and drying can be performed by a known heating means such as a heater, a blowing means using air blowing such as a dryer, or a combination of a known heating means and a blowing means.
- a heating method for example, a method of applying heat with a heater or the like from the side opposite to the side to which the substrate processing liquid is applied, a method of applying warm air or hot air to the side of the substrate processing liquid applied, or infrared rays The method of heating using a heater is mentioned. Heating may be performed by combining a plurality of these.
- image recording process an image is recorded by ejecting the ink composition of the ink set described above onto one surface of the base material to which the treatment liquid has been applied in the pretreatment step, by an inkjet method.
- the inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method
- An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. ))
- Any method may be used.
- an ink jet method in particular, the method described in Japanese Patent Laid-Open No.
- Sho 54-59936 causes a sudden change in volume of the ink subjected to the action of thermal energy, and the ink is ejected from the nozzle by the action force caused by this state change.
- Ink jet method can be used effectively.
- the inkjet method uses a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method used is included.
- an ink jet head used in the ink jet method may be an on-demand method or a continuous method.
- Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), and electro-thermal conversion methods (eg, thermal Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.) and a discharge type (for example, a spark jet type).
- any discharge method may be used.
- the ink nozzles used when recording by the ink jet method there are no particular restrictions on the ink nozzles used when recording by the ink jet method, and they can be appropriately selected according to the purpose.
- an inkjet head As an inkjet head, a single serial head is used, and a shuttle system that performs recording while scanning the head in the width direction of the substrate, and a line in which recording elements are arranged corresponding to the entire area of one side of the substrate.
- a line system using a head.
- the substrate In the line system, the substrate can be scanned in the direction orthogonal to the arrangement direction of the recording elements, whereby image recording can be performed on the entire surface of the substrate, and a transport system such as a carriage for scanning the short head is not necessary.
- complicated scanning control between the carriage and the base material is not necessary, and only the base material moves, so that the recording speed can be increased as compared with the shuttle system.
- the image recording step is preferably started within 10 seconds after the pretreatment step, and more preferably within 0.1 seconds to 10 seconds. Thereby, an image can be formed at high speed. “Start within 10 seconds after the pretreatment step” means that the time from application of the treatment liquid and completion of drying until the first ink droplets are deposited on the substrate is within 10 seconds.
- the amount of ink droplets to be applied is preferably 1.5 pL (picoliter) to 3.0 pL, more preferably 1.5 pL to 2 More preferably, it is 5 pL.
- the amount of ink droplets can be adjusted by appropriately selecting the ejection conditions in the ink jet method according to the ink composition to be ejected.
- a heat fixing step of heat fixing the image recorded through the preprocessing step and the image recording step may be further provided.
- the image on the base material is fixed, and the abrasion resistance of the image is further improved.
- the heating in the heat fixing step is preferably performed at a temperature equal to or higher than the minimum film-forming temperature (MFT) of the resin particles in the image.
- MFT minimum film-forming temperature
- the pressure during pressurization is preferably in the range of 0.1 MPa to 3.0 MPa, more preferably in the range of 0.1 MPa to 1.0 MPa, and still more preferably in terms of surface smoothing. Is in the range of 0.1 MPa to 0.5 MPa.
- the heating method is not particularly limited, but a non-contact drying method such as a method of heating with a heating element such as a nichrome wire heater, a method of supplying warm air or hot air, a method of heating with a halogen lamp, an infrared lamp or the like is suitable. Can be listed.
- the heating and pressing method is not particularly limited.
- a method of pressing a hot plate against the image recording surface of the substrate, a pair of heating and pressing rollers, a pair of heating and pressing belts, or a substrate Using a heating and pressing device equipped with a heating and pressing belt arranged on the image recording surface side and a holding roller arranged on the opposite side, heat fixing by bringing them into contact, such as a method of passing a pair of rollers, etc.
- the method of performing is mentioned suitably.
- a preferable nip time is 1 to 10 seconds, more preferably 2 to 1 second, and further preferably 4 to 100 milliseconds.
- the preferable nip width is 0.1 mm to 100 mm, more preferably 0.5 mm to 50 mm, and still more preferably 1 mm to 10 mm.
- the heat and pressure roller may be a metal metal roller, or a metal core bar provided with a coating layer made of an elastic body and, if necessary, a surface layer (also referred to as a release layer).
- the latter metal core can be formed of a cylindrical body made of, for example, iron, aluminum, or stainless steel (SUS), and the surface of the metal core is preferably at least partially covered with a coating layer.
- the coating layer is particularly preferably formed of a silicone resin or fluororesin having releasability.
- a heating element is built in one core metal of the heat and pressure roller, and the heat treatment and the pressure treatment are simultaneously performed or necessary by passing the base material between the rollers.
- the substrate may be sandwiched and heated using two heating rollers.
- the heating element for example, a halogen lamp heater, a ceramic heater, a nichrome wire or the like is preferable.
- the thickness of the base material is preferably 10 ⁇ m to 100 ⁇ m.
- the material of the belt base material aluminum, iron, polyethylene or the like can be used in addition to nickel.
- the thickness of the layer formed using these resins is preferably 1 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 30 ⁇ m.
- nip pressure for example, elastic members such as springs having tension are provided at both ends of a roller such as a heating and pressure roller so that a desired nip pressure can be obtained in consideration of the nip gap. Select and install.
- the conveyance speed of the substrate is preferably 200 mm / second to 700 mm / second, more preferably 300 mm / second to 650 mm / second, and still more preferably 400 mm / second. ⁇ 600 mm / sec.
- Solution A prepared by dissolving 4.14 g of a 50% by mass aqueous solution of sodium 2-acrylamido-2-methylpropanesulfonate (AMPSANa) (manufactured by Aldrich) in 20 g of water in a mixed solution in a heated three-necked flask, and methyl methacrylate (MMA: manufactured by Wako Pure Chemical Industries, Ltd.) 26.89 g and styrene (St: manufactured by Wako Pure Chemical Industries, Ltd.) 12.41 g mixed with solution B and 40 g of water in sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 6 Solution C in which 0.0 g was dissolved was added dropwise simultaneously over 3 hours.
- AMPSANa sodium 2-acrylamido-2-methylpropanesulfonate
- the reaction was further continued for 3 hours to synthesize 410 g of an aqueous dispersion of water-insoluble resin particles A-1 (solid content of water-insoluble resin particles: 10.2% by mass).
- the volume average particle diameter of the water-insoluble resin particles A-1 in the aqueous dispersion was 30 nm.
- the weight average molecular weight of the water-insoluble resin of the water-insoluble resin particles A-1 was 32000.
- the volume average particle size is determined dynamically using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) with respect to an aqueous dispersion of water-insoluble resin particles adjusted so that the solid content concentration is 10% by mass. It was determined by measuring at a liquid temperature of 25 ° C. by a light scattering method.
- the weight average molecular weight was measured by gel permeation chromatography (GPC). Specifically, GPC uses HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) as a measuring device, and 3 columns of TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as a column. This was carried out using THF (tetrahydrofuran) as an eluent. As the conditions, the sample concentration was 0.45% by mass, the flow rate was 0.35 ml / min, the sample injection amount was 10 ⁇ l, the measurement temperature was 40 ° C., and the suggested refractometer (RI) detector was used. .
- HLC registered trademark
- TSKgel tetrahydrofuran
- the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It was prepared from 8 samples of “A-2500”, “A-1000” and “n-propylbenzene”.
- a solution A obtained by dissolving 8.27 g of a 50% by mass aqueous solution of sodium 2-acrylamido-2-methylpropanesulfonate (AMPSANa) (manufactured by Aldrich) in 20 g of water and methyl methacrylate (MMA; manufactured by Wako Pure Chemical Industries, Ltd.) 22.75 g, methacrylic acid (produced by Wako Pure Chemical Industries, Ltd.) 2.07 g, styrene 12.41 g, dodecanethiol (chain transfer agent) 0.708 g mixed with water
- B Solution C in which 6.0 g of sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 40 g was simultaneously added dropwise over 3 hours.
- aqueous solution of water-soluble resin X-1 having the following structure.
- the solid content of the water-soluble resin in the aqueous solution was 16.2% by mass.
- the weight average molecular weight of the water-soluble resin X-1 in the aqueous solution was 27000.
- the weight average molecular weight was measured in the same manner as in the aqueous dispersion of water-insoluble resin particles A-1. Note that the particle diameter of the water-soluble resin X-1 was not detected by measuring the volume average particle diameter.
- the structures of the water-insoluble resin particles X-1 to X-4 are shown below.
- the numerical value in a structure represents the mass part of each structural unit.
- ⁇ Preparation of treatment solution> (Preparation of treatment liquids A1 to A27, AX1 to AX4) The components were mixed so as to have the following composition to prepare treatment liquids A1 to A27 and comparative treatment liquids AX1 to AX4.
- ⁇ Compositions of treatment liquids A1 to A27 and AX1 to AX4> Diethylene glycol monoethyl ether: 6.0% by mass ⁇ 1,4-butanediol: 2.5% by mass Malonic acid (aggregating component: organic acidic compound) ...
- Propanetricarboxylic acid 4.3% by mass (Aggregating component: organic acidic compound) ⁇ Phosphoric acid (aggregation component: inorganic acidic compound): 4.3% by mass -Aqueous dispersion or water-soluble resin of water-insoluble resin particles described in Tables 5 to 7 below-Amount described in Tables 5-7-Benzotriazole-1% by mass ⁇ Antifoaming agent ⁇ ⁇ ⁇ Silicon oil amount of 100 ppm (TSA-739 (solid content 15% by mass), manufactured by Momentive Performance Materials Japan GK; emulsion type silicone antifoaming agent) ⁇ Ion-exchanged water: remaining amount of 100% by mass in total
- Treatment liquid C Each component was mixed so that it might become the following composition, and the processing liquid C was prepared.
- ⁇ Composition of treatment liquid C> ⁇ Calcium chloride (aggregation component: polyvalent metal salt): 10% by mass ⁇ 3-Methoxy-3-methyl-1-butanol: 5% by mass ⁇ Glycerin ... 30% by mass ⁇ Emulgen 108 ⁇ ⁇ ⁇ 1% by mass (Polyoxyethylene lauryl ether, manufactured by Kao Corporation; surfactant) Proxel xl-2 (s) (Lonza; preservative) ... 0.2% by mass -Aqueous dispersion of water-insoluble resin particles shown in Table 7 ... Amounts shown in Table 7-Ion-exchanged water ... Remaining amount of 100% by mass in total
- Treatment liquid D Each component was mixed so that it might become the following composition, and the processing liquid D was prepared.
- ⁇ Composition of treatment liquid D> Diethylene glycol monoethyl ether: 6.0% by mass ⁇ 1,4-butanediol: 2.5% by mass -Malonic acid (aggregation component: organic acidic compound) ... 10% by mass ⁇ Benzotriazole: 1% by mass ⁇ Antifoaming agent ⁇ ⁇ ⁇ Silicon oil amount of 100 ppm (TSA-739 (solid content: 15 mass%), manufactured by Momentive Performance Materials Japan GK; emulsion type silicone antifoaming agent) -Aqueous dispersion of water-insoluble resin particles described in Table 7 ... Amount described in Table 7-Ion-exchanged water-Remaining amount of 100% by mass in total
- Treatment liquid E Each component was mixed so that it might become the following composition, and the processing liquid E was prepared.
- ⁇ Composition of treatment liquid E> Diethylene glycol monoethyl ether: 6.0% by mass ⁇ 1,4-butanediol: 2.5% by mass -Malonic acid (aggregation component: organic acidic compound) ... 5% by mass ⁇ Benzotriazole: 1% by mass ⁇
- Antifoaming agent The amount of silicone oil is 100 ppm (TSA-739 (solid content 15% by mass), manufactured by Momentive Performance Materials Japan GK; emulsion type silicone antifoaming agent) -Aqueous dispersion of water-insoluble resin particles described in Table 7 ... Amount described in Table 7-Ion-exchanged water-Remaining amount of 100% by mass in total
- Treatment liquid F Each component was mixed so that it might become the following composition, and the processing liquid F was prepared.
- ⁇ Composition of treatment liquid F> Diethylene glycol monoethyl ether: 6.0% by mass ⁇ 1,4-butanediol: 2.5% by mass -Malonic acid (aggregation component: organic acidic compound) ... 3% by mass ⁇ Benzotriazole: 1% by mass ⁇
- Antifoaming agent The amount of silicone oil is 100 ppm (TSA-739 (solid content 15% by mass), manufactured by Momentive Performance Materials Japan GK; emulsion type silicone antifoaming agent) -Aqueous dispersion of water-insoluble resin particles described in Table 7 ... Amount described in Table 7-Ion-exchanged water-Remaining amount of 100% by mass in total
- the pH, surface tension, and viscosity of the treatment liquids A1 to A27 and AX1 to AX4 and the treatment liquids B to F are as follows.
- the pH was measured with a pH meter WM-50EG (manufactured by Toa DDK) with each treatment solution adjusted to 25 ° C. in an environment of 25 ° C., and the surface tension was Automatic Surface Tensiometer CBVP-Z (Kyowa Interface Science). Measured at 25 ° C. by the plate method.
- the viscosity was measured using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD) with each treatment solution adjusted to 25 ° C.
- composition of the obtained polymer dispersant P-1 was confirmed by proton nuclear magnetic resonance spectroscopy ( 1 H-NMR), and the weight average molecular weight (Mw) determined by GPC was 44,600. Furthermore, it was 65.2 mgKOH / g when the acid value was calculated
- the volume average particle size is adjusted using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) for a dispersion of water-insoluble resin particles adjusted so that the solid content concentration is 10% by mass. It was determined by measuring at a liquid temperature of 25 ° C. by a dynamic light scattering method.
- magenta dispersion M a dispersion of resin-coated pigment particles (pigment coated with a polymer dispersant) was prepared in the same manner as in the preparation of the cyan dispersion.
- the volume average particle diameter of the resin-coated pigment particles of the magenta dispersion M was 85 nm.
- the volume average particle size was measured by the same method as the measurement of the volume average particle size of the resin-coated pigment particles of cyan dispersion C.
- Pigment Yellow 74 (chromofine yellow, manufactured by Dainichi Chemical Co., Ltd.), which is a yellow pigment, was used instead of Pigment Blue 15: 3 (Phthalocyanine-A220, manufactured by Dainichi Chemical Co., Ltd.). Except for this, a dispersion (yellow dispersion Y) of resin-coated pigment particles (pigment coated with a polymer dispersant) was prepared in the same manner. The volume average particle diameter of the resin-coated pigment particles of the yellow dispersion Y was 82 nm. The volume average particle size was measured by the same method as the measurement of the volume average particle size of the resin-coated pigment particles of cyan dispersion C.
- ink 1 (Preparation of ink 1) Using the pigment dispersions (cyan dispersion C, magenta dispersion M, yellow dispersion Y, black dispersion K) and resin particles (B-01) obtained above, the compositions shown in Table 4 below are obtained. In this way, the respective components are mixed to prepare four types of ink compositions (magenta ink composition M1, cyan ink composition C1, yellow ink composition Y1, and black ink composition K1). Ink 1 was produced. The pH (25 ° C.) of the magenta ink M1, the cyan ink C1, the yellow ink Y1, and the black ink K1 measured by the same method as the pH of the treatment liquid is 8.1, 8.3, 8.0, 8.2.
- Examples 1 to 32, Comparative Examples 1 to 4 ⁇ Ink set> The ink 1 (magenta ink M1, black ink K1, cyan ink C1, yellow ink Y1) and the respective processing liquids (processing liquids A1 to A27, processing liquids B to F, and comparative processing liquids AX1 to AX4) Ink sets 1 to 25 and ink sets X1 to X4 were prepared. Using each ink set, an image was recorded by the following procedure, and the recorded image was evaluated by the following method.
- coated paper (CartaIntegra, Metasaboard, Inc .; water contact angle 74 ° when 3 seconds passed after applying water droplets on the surface) was recorded under the following conditions.
- ink droplets were started within 10 seconds after applying the treatment liquid.
- the water contact angle of the base material was measured using a contact angle meter drop master DM700 (manufactured by Kyowa Interface Science Co., Ltd.) according to the method described in Japanese Industrial Standard (JIS R3257).
- JIS R3257 Japanese Industrial Standard
- applying the treatment liquid immediately before applying ink means applying the treatment liquid every time an image is recorded in the image recording step.
- the treatment liquid applied on the substrate was dried under the following conditions.
- Density of solid image area The density of the black solid image portion in the image sample was measured at a visual (V) density using a spectrophotometer Spectroeye (manufactured by Sakata Inx Corporation). When the droplet size of the ink droplet (ink dot) forming the image is small, the density of the solid image portion appears low due to the influence of the white background of the substrate. Further, when the cohesiveness of the dispersed component in the ink by the treatment liquid is low, adjacent ink dots cause interference so that the white background of the substrate is easily seen and the density appears low. The evaluation was performed assuming that ranks 3 to 6 are practically acceptable. ⁇ Evaluation criteria> 6: The density of the solid image portion in the image sample exceeds 2.0.
- the density of the solid image portion in the image sample is more than 1.9 and not more than 2.0.
- the density of the solid image portion in the image sample is more than 1.7 and 1.9 or less.
- 3 The density of the solid image portion in the image sample is more than 1.5 and 1.7 or less.
- 2 The density of the solid image portion in the image sample is more than 1.3 and 1.5 or less.
- 1 The density of the solid image portion in the image sample is 1.3 or less.
- the secondary color image portion in the image sample obtained in the image recording step was visually observed, and the roughness of the image was evaluated according to the following criteria.
- the secondary color image portion forms a magenta solid image by applying magenta ink M1 in a solid form on the coated processing liquid, and further forms a magenta solid image on the magenta solid image.
- the cyan ink C1 was obtained by applying a heat fixing process in the heat fixing step after applying the cyan ink C1 in a halftone dot shape so that the dot area ratio is 50% to 80%.
- Muscle irregularity over time 25 g of the treatment liquid corresponding to each of the above Examples and Comparative Examples was accommodated in a 30 ml polyethylene bottle. Each bottle containing the treatment liquid was placed in a thermocell set at 40 ° C. and stored for 2 weeks. Using the processing solution after storage, in the image recording step, the cyan ink C1 is applied in a solid form on the coated processing solution to form a cyan solid image, and this image is visually observed. The presence or absence of streak unevenness in the conveying direction was confirmed, and the degree of streak unevenness was evaluated according to the following evaluation criteria. The stripe unevenness appears because the ink dots adjacent to each other interfere with each other so that the white background of the substrate can be easily seen.
- ⁇ viscosity is more than 0.4 mPa ⁇ s and 1.0 mPa ⁇ s or less.
- ⁇ viscosity is more than 1.0 mPa ⁇ s and not more than 2.0 mPa ⁇ s.
- ⁇ viscosity exceeds 2.0 mPa ⁇ s.
- Example 7 and Examples 11 to 12 and Examples 8 to 10 the structural unit derived from the second monomer containing an aromatic ring structure or an alicyclic structure
- Examples 7 to 10 in which the content ratio is 40% by mass or less with respect to the total mass of the water-insoluble resin examples 10 and 11 in which the content ratio of the structural unit derived from the second monomer exceeds 40% by mass.
- density reduction and streak unevenness in the solid image portion are more effectively suppressed.
- the content ratio of the structural unit derived from the 2nd monomer containing an aromatic ring structure or an alicyclic structure is adjusted to 10 mass% or more with respect to the total mass of water-insoluble resin, 2nd
- the content ratio of the structural unit derived from the monomer is less than 10% by mass, the occurrence of streak unevenness occurring over time can be more effectively suppressed. ing.
- Example 3 using a treatment liquid containing particles of a water-insoluble resin having an oxygen atom content of 0.1% by mass or less, a water-insoluble resin having an oxygen atom content in the molecule exceeding 0.1% by mass Compared with Examples 13 to 15 using the treatment liquid containing the above particles, the effect of suppressing the decrease in density in the solid image portion was greatly exhibited.
- L 4 in the general formula 1 is —C ( Compared to the structure having ⁇ O) —O—, the structure having —C ( ⁇ O) —NH— was superior in terms of storage stability with time in the treatment liquid.
- the structure of —C ( ⁇ O) —O— is susceptible to hydrolysis.
- Tg glass transition temperature of the water-insoluble resin
- the effect of suppressing the unevenness of the stripes is lowered, and the stability over time of the treatment solution is also lowered.
- the Tg of the water-insoluble resin is desirably 100 ° C. or higher.
- the water-insoluble resin contains MA as a monomer component and Tg is 100 ° C. or more, as shown in Examples 21 to 22, the effect of suppressing density reduction in the solid image portion is remarkably desired. A solid image portion of density was obtained.
- Example 33 Each component was mixed so as to have the composition shown in Table 8 below, and 18 types of ink compositions (3 types for each of magenta ink, cyan ink, yellow ink, black ink, orange ink, green ink, and violet ink) Was prepared. Then, any one of 18 kinds of ink compositions and any one of the processing liquids A-3, A-9, A-14, A-16, and A-22 described above are arbitrarily selected. An ink set was prepared by combining them.
- Example 2 An image was recorded using the prepared ink set in the same procedure as in Example 1, and the density of the solid image, the occurrence of streaks, and the roughness of the image were evaluated for the recorded image. Note that the solid image density and streak unevenness were evaluated by forming solid images of each color and in the same manner as in Example 1 above.
- arbitrary two types were selected from the 18 types of ink compositions shown in Table 8 below, and evaluated as follows. That is, An image sample was obtained using the two ink compositions selected from Table 8 in the image recording step, and the secondary color image portion in the obtained image sample was visually observed, and the above-mentioned “ ⁇ 2. Evaluation was performed in the same manner as “Roughness of image”.
- the secondary color image portion forms a solid image by applying one of the two ink compositions in a solid form on the coated processing liquid, and the other halftone dot area on the solid image. It is obtained by applying a halftone dot shape so that the rate is 50% to 80% and performing heat fixing treatment.
- Pro-Jet Cyan APD3000 Pigment dispersion containing pigment blue 15: 3 (pigment concentration: 12.0% by mass, nonvolatile content concentration: 21.8% by mass), manufactured by FUJIFILM Imaging Colorants, Inc.
- Pro-Jet Magenta APD3000 Pigment dispersion containing Pigment Red 122 (pigment concentration: 15.0 mass%, nonvolatile content concentration: 21.6 mass%), manufactured by FUJIFILM Imaging Colorants
- Pro-Jet Yellow APD3000 Pigment Yellow 74 Pigment dispersion (pigment concentration: 13.6% by mass, nonvolatile content concentration: 24.6% by mass), manufactured by FUJIFILM Imaging Colorants, Pro-Jet Black APD3000; Pigment Bra Pigment dispersion containing pigment 7 (pigment concentration: 10.0% by mass, nonvolatile content concentration: 18.9% by mass), FUJIFILM Imaging Colorants, FUJI SP ORANGE 651: Pigment dispersion
- Latex A The above resin particles (B-01) and water are mixed. Aqueous dispersion of adjusting the resin particles in the solid content 23.20 wt%, PE-108: New Pole (R) PE-108, polyoxyethylene-polyoxypropylene block polymer (manufactured by Sanyo Chemical Industries, Ltd.) -GP250: Sannix GP-250, polyoxypropylene glyceryl ether (manufactured by Sanyo Chemical Industries) ⁇ PEG-200: Polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd.) MFTG: Tripropylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) ⁇ PVP K15: Polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ⁇ Orphine E1010: Acetylene glycol surfactant (manufactured by Nissin Chemical Industry Co., Ltd.) ⁇ Orphin
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Abstract
Description
具体的な例として、分散している顔料を含有するインクを記録媒体に付与する工程と、スルホ基及びリン酸基から選択される少なくとも1種を有する樹脂微粒子を含有し、インク中の顔料の分散状態を不安定化させる酸性の液体組成物を記録媒体に付与する工程と、を有する画像記録方法が開示されている(例えば、特開2013-18156号公報参照)。
また、「筋ムラ」とは、インク組成物の着滴干渉によりインク組成物が移動し、筋状に濃淡が発生する現象をいう。
<1> 着色剤及び水を含むインク組成物、並びに、スルホ基及びスルホ基の塩から選ばれる少なくとも一つの基を含む第1の単量体に由来の構成単位、及び、芳香環構造及び脂環構造から選ばれる少なくとも一つの構造を含む第2の単量体に由来の構成単位を有する水不溶性樹脂の粒子と、インク組成物中の着色剤を凝集させる化合物と、水と、を含む処理液、を有するインクセットである。
<2> 第2の単量体に由来の構成単位は、下記一般式A~一般式Eのいずれかで表される構成単位の群より選ばれる少なくとも一つの構成単位である<1>に記載のインクセットである。
<4> 第2の単量体に由来の構成単位に対する、第1の単量体に由来の構成単位の質量比率が、0.15~0.90である<1>~<3>のいずれか1項に記載のインクセットである。
<5> 第1の単量体に由来の構成単位は、下記一般式1で表される構成単位である<1>~<4>のいずれか1つに記載のインクセットである。
<7> 第2の単量体の少なくとも一つは、単量体の分子量に対する単量体中の酸素原子の質量の比率が、0.1以下である<1>~<6>のいずれか1つに記載のインクセットである。
<8> 第2の単量体の少なくとも一つが、スチレンである<1>~<7>のいずれか1つに記載のインクセットである。
<9> 水不溶性樹脂のガラス転移温度が、100℃以上である<1>~<8>のいずれか1つに記載のインクセットである。
<10> インク組成物中の着色剤を凝集させる化合物に対する、水不溶性樹脂の粒子の含有比率が、質量基準で0.19~0.5である<1>~<9>のいずれか1つに記載のインクセットである。
<11> 表面に水滴を付与して3秒経過したときの接触角が70°以上である基材の少なくとも一方の面に、<1>~<10>のいずれか1つに記載のインクセットの処理液を付与する前処理工程と、処理液が付与された一方の面に、<1>~<10>のいずれか1つに記載のインクセットのインク組成物をインクジェット法により吐出して画像を記録する画像記録工程と、を有する画像記録方法である。
<12> 基材は、塗工層を有する紙基材である<11>に記載の画像記録方法である。
また、本明細書において、組成物中の各成分の量は、組成物中に各成分に相当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。
本開示に係るインクセットは、着色剤及び水を含むインク組成物と、インク組成物の付与前に基材を前処理するための処理液と、を有している。本開示における処理液は、スルホ基及びスルホ基の塩から選ばれる少なくとも一つの基を含む第1の単量体に由来の構成単位、並びに芳香環構造及び脂環構造から選ばれる少なくとも一つの構造を含む第2の単量体に由来の構成単位を有する水不溶性樹脂の粒子と、インク組成物中の着色剤を凝集させる化合物(以下、「凝集化成分」ともいう。)と、水と、を含有する。
処理液は、必要に応じて、更に、水不溶性樹脂の粒子、凝集化成分、及び水以外の他の成分を含んでもよい。また、インク組成物は、着色剤及び水以外の他の成分を更に含んでもよい。
本開示においては、粒子によって、基材の表面の親水化と処理液の安定化との向上を図る点が重要である。
具体的には、処理液中に含まれる水不溶性樹脂の粒子は、表面が親水的であり、かつ、内部が疎水的であるので、水不溶性樹脂の粒子が処理液中に存在している際は、粒子自体の膨潤が生じにくいために分散状態が安定的に保たれ、水不溶性樹脂の粒子が基材に付与された際は、基材の表面(処理液付与面)を親水化し、水性のインク組成物の濡れ性を改善する。これにより、ベタ画像部の濃度低下が抑制されることで、所望濃度のベタ画像部が得られ、かつ、筋ムラの発生が抑制された画像が得られる。
水不溶性樹脂の粒子における水不溶性樹脂は、スルホ基及びスルホ基の塩から選ばれる少なくとも一つの基を含むため、親水的であり、水不溶性樹脂の粒子は親水化する。したがって、粒子を基材の表面に存在させると、基材の表面は親水化される。また、水不溶性樹脂の粒子がスルホ基等を有していると、アニオンが多く存在するため、粒子間反発が増大し、水不溶性樹脂粒子の処理液中における分散安定性がより向上する。一方、水不溶性樹脂は、分子内に単にスルホ基等を含ませると、粒子とした場合の表面のみならず内部まで親水的になる。そのため、粒子を処理液中に存在させた場合、溶媒である水又は溶剤が経時で粒子中に浸透して膨潤し、粒子同士の合一などが発生しやすくなり、処理液中における粒子の分散安定性が低下し、処理液中における経時での分散安定性も低下する。これにより、処理液は、経時で粘度上昇を来たす。結果、粘度上昇に伴って画像品質の低下を招来することになる。
したがって、水不溶性樹脂の粒子における水不溶性樹脂に、疎水基として、芳香環構造及び脂環構造から選ばれる少なくとも一つの構造を含める。疎水基は、粒子の表面よりむしろ粒子の内部に存在しやすい。そのため、粒子の内部に疎水基が導入され、粒子の内部がより疎水的になるため、粒子を水系の処理液中に存在させた場合、経時での粒子の膨潤が抑えられ、処理液中での経時安定性、経時での筋ムラの発生を防ぐ。しかも、疎水基は、水系の処理液中では粒子の表面に偏在せず、粒子の内部に偏在するため、粒子の表面は親水性を保つことができる。
これに対して、本開示のインクセットでは、上記のように水不溶性樹脂の粒子において、芳香環構造及び脂環構造から選ばれる少なくとも一つの疎水性基(以下、特定疎水基ともいう)と、スルホ基及びスルホ基の塩から選ばれる少なくとも一つの親水性基(以下、特定親水基ともいう)と、を存在させる。この水不溶性樹脂の粒子を含有する処理液が基材に付与されると、処理液中の水不溶性樹脂の粒子は、基材の内部に浸透しにくく、粒子が基材の表面に偏在しやすくなると考えられる。その一方、粒子の表面には、親水的なスルホ基又はスルホ基の塩が存在するため、粒子が基材の表面に偏在することで、基材の表面に対する親水化作用が期待される。
なお、水不溶性樹脂の粒子は、処理液中に含まれる凝集化成分(インク組成物中の着色剤を凝集させる化合物)と接触した際にも、処理液中で分散状態を維持する。
本開示に係るインクセットにおける処理液は、後述するインク組成物の付与前に基材を前処理するものである。処理液は、スルホ基及びスルホ基の塩から選ばれる少なくとも一つの基を含む第1の単量体に由来の構成単位と、芳香環構造及び脂環構造から選ばれる少なくとも一つの構造を含む第2の単量体に由来の構成単位と、を有する水不溶性樹脂の粒子、インク組成物中の着色剤を凝集させる化合物(凝集化成分)、及び水を少なくとも含有し、基材の親水化作用に優れる。すなわち、水に対する濡れ性が比較的低い基材(例えば、表面の水に対する接触角(水接触角)が70°以上の基材)のインク組成物に対する濡れ性を高め、所望とする濃度のベタ画像部が得られやすく、筋状ムラの発生を効果的に抑制することができる。
処理液は、水不溶性樹脂の粒子の少なくとも一種を含有する。
水不溶性樹脂の粒子が含有されることで、処理液付与後の基材の表面に水不溶性樹脂の粒子の大部分が偏在し、基材の表面の濡れ性を改善する。
水不溶性樹脂の粒子が表面に偏在した基材にインク組成物が着滴すると、インク滴が基材の表面で濡れ広がり、かつ、処理液に含まれる凝集化成分がインク組成物中の着色剤等の分散成分を凝集させる。これにより、液滴同士の合一を防止し、かつ、液滴サイズが所望とする大きさになる。結果、ベタ画像部の濃度低下が抑制され、所望とする濃度を有するベタ画像部が得られる。
また、上記のように、水不溶性樹脂の粒子自体の処理液中での経時安定性に優れ、膨潤による粒子の粗大化が抑えられており、記録画像中に生じやすい筋ムラの発生を抑えるのに効果的である。更に、画像中のざらつきも抑制することができる。
なお、「ざらつき(graininess)」とは、インク組成物が基材に着滴した後、液滴同士が合一することで、画像中に微小な濃度ムラが発生し、画素の均一性が低下する現象をいう。
なお、本開示において、「固形分」とは、組成物から溶媒を除いた残りの成分をいう。
体積平均粒子径は、ナノトラック粒度分布測定装置UPA-EX150(日機装(株)製)を用いて、動的光散乱法により体積平均粒子径を測定することで求められる。
第1の単量体に由来の構成単位は、スルホ基及びスルホ基の塩から選ばれる少なくとも一つの基を含む第1の単量体を、少なくとも後述の第2の単量体と共重合させることにより樹脂中に存在する構成単位である。第1の単量体を共重合させてスルホ基又はスルホ基の塩を含めることで、水不溶性樹脂の粒子の表面を親水化する。
中でも、第1の単量体に由来の構成単位としては、下記一般式1で表される構成単位が好ましい。
また、一般式1におけるL4は、単結合、炭素数1~10の直鎖状、分岐鎖状若しくは環状のアルキレン基、炭素数6~10のアリーレン基、-O-、-NH-、-S-、-C(=O)-、及び-CH(-OH)-からなる群より選ばれる1つ又は2つ以上を連結した2価の連結基を表す。
L4としては、炭素数1~5の直鎖状、分岐鎖状若しくは環状のアルキレン基、-O-、-NH-、及び-C(=O)-からなる群より選ばれる1つ又は2つ以上を連結した2価の連結基が好ましく、更には、炭素数1~5の直鎖状、分岐鎖状若しくは環状のアルキレン基、炭素数1~5の直鎖状、分岐鎖状若しくは環状のアルキレン基と-O-と-C(=O)-とからなる2価の連結基、又は、炭素数1~5の直鎖状、分岐鎖状若しくは環状のアルキレン基と-NH-と-C(=O)-とからなる2価の連結基が好ましい。
L4は、更に好ましくは、下記群aから選ばれる少なくとも一つの連結基である。群aに示す連結基において、nは1から5までの整数を表し、*は結合位置を表す。
Mにおける陽イオンとしては、ナトリウムイオン、カリウムイオン、及びリチウムイオンなどのアルカリ金属イオン、カルシウムイオン及びマグネシウムイオンなどのアルカリ土類金属イオン、並びに、アンモニウムイオンなどのイオンが挙げられる。
上記の中でも、2-アクリルアミド-2-メチルプロパンスルホン酸及び2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウムがより好ましい。
第1の単量体に由来の構成単位の含有比率が5質量%以上であると、粒子表面の親水化に適しており、基材の表面を親水化処理するのに好適である。また、第1の単量体に由来の構成単位の含有比率が25質量%以下であると、粒子の内部の疎水の程度とのバランスがよく、粒子の膨潤が起こり難く、安定的な分散安定性が得られる。
第2の単量体に由来の構成単位は、芳香環構造及び脂環構造から選ばれる少なくとも一つの構造を含む第2の単量体を、少なくとも上記の第1の単量体と共重合させることにより樹脂中に存在する構成単位である。第2の単量体を共重合させて、分子中に芳香環構造又は脂環構造を含めることで、例えばアルキル鎖等の脂肪族構造を有する場合に比べ、水不溶性樹脂の粒子の内部の疎水化を高めることができる。
中でも、第2の単量体に由来の構成単位としては、下記一般式A~一般式Eのいずれかで表される構成単位の群より選ばれる構成単位が好ましい。
また、一般式A~一般式CにおけるR12は、水素原子又は炭素数1~10の直鎖状若しくは分岐鎖状のアルキル基を表す。炭素数1~10の直鎖状若しくは分岐鎖状のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、t-ブチル基などを挙げることができる。R12は、水素原子又は炭素数4~10の直鎖状若しくは分岐鎖状のアルキル基が好ましく、水素原子又はメチル基がより好ましい。また、R12は、無置換の基でもよいし、置換基で置換された基でもよい。R12が置換基で置換されている場合、置換基としては、例えば、ハロゲン(例:塩素原子、臭素原子)、アルキル基(例えば、メチル基、エチル基等)などが挙げられる。
一般式A~一般式Cにおけるnは、0~5の整数を表す。nが2以上である場合、複数のR12は互いに同一の基であってもよいし、互いに異なる基であってもよい。
炭素数1~18の直鎖状、分岐鎖状若しくは環状のアルキレン基としては、例えば、メチレン基、エチレン基、i-プロピレン基、t-ブチレン基、n-プロピレン基などを挙げることができる。
炭素数6~18のアリーレン基としては、フェニレン基、ナフチレン基、トリル基などを挙げることができる。
中でも、L11は、以下に示す2価の連結基が好ましい。下記の2価の連結基において、R21は、それぞれ独立に、メチル基又は水素原子を表す。nは、1~8の整数を表す。
特に、一般式A~一般式Eのいずれかで表される構成単位の合計の含有比率が10質量%以上であると、水不溶性樹脂の粒子の内部の疎水化に好適であり、水系の処理液中に粒子を存在させた場合の膨潤を防ぎやすく、処理液中における粒子の分散安定性がより良好になる。結果、画像中の筋ムラの発生が効果的に抑制される。また、一般式A~一般式Eのいずれかで表される構成単位の含有比率が40質量%以下であると、ベタ画像濃度、筋ムラの点で有利である。
第2の単量体に由来する構成単位の含有量に対する第1の単量体に由来の構成単位の含有量の比率が上記の範囲内であると、スルホ基及びスルホ基の塩から選ばれる親水性基による親水性と、芳香環構造及び脂環構造から選ばれる疎水性基による疎水性と、のバランスがよく、処理液中での粒子の安定性と画質を両立することができる。
水不溶性樹脂の粒子における水不溶性樹脂は、上記の第1の単量体に由来の構成単位及び第2の単量体に由来の構成単位以外の他の単量体に由来の構成単位を含んでいてもよい。他の単量体に由来の構成単位としては、例えば、カルボキシ基及びカルボキシ基の塩から選ばれる少なくとも一つの基を有する単量体に由来の構成単位、並びに、以下に示すその他の単量体に由来する構成単位を挙げることができる。
また、他の単量体に由来の構成単位は、疎水性の構成単位でない(例えば、カルボキシ基又はその塩を含む)か、又は、芳香環構造及び脂環構造を有しない点において、既述の第1の単量体に由来の構成単位第2の単量体に由来の構成単位とは区別される。
カルボキシ基及びカルボキシ基の塩から選ばれる少なくとも一つの基を有する単量体に由来する構成単位の含有比率は、水不溶性樹脂の全質量に対して、0.01質量%~40質量%が好ましく、0.01質量%~10質量%がより好ましい。
他の単量体に由来の構成単位の含有量は、水不溶性樹脂の全質量に対して、20質量%~80質量%の範囲とすることができ、30質量%~75質量%がより好ましく、30質量%~60質量%がさらに好ましい。
他の単量体に由来する構成単位としては、水不溶性樹脂の粒子の親水性を維持する観点から、疎水性の単量体に由来の構成単位ではないことが好ましい。他の単量体に由来の構成単位としては、好ましくは、メタクリル酸メチル、メタクリル酸エチル、及びエチルアクリレートから選ばれる単量体に由来の構成単位であり、より好ましくは、メタクリル酸メチル及びメタクリル酸エチルの少なくとも一方に由来の構成単位であり、更に好ましくは、メタクリル酸メチルに由来の構成単位である。
他の単量体として、例えば、カルボキシ基及びカルボキシ基の塩から選ばれる少なくとも一つの基を有する単量体に由来の構成単位を水不溶性樹脂に導入する場合、他の単量体を共重合して共重合体を合成した後、加水分解し、さらに強酸を添加することによってカルボキシ基を再生させる方法を適用してもよい。
水不溶性樹脂粒子のTgは、エスアイアイ・ナノテクノロジー社製の示差走査熱量計(DSC)EXSTAR6220により測定される値である。
水不溶性樹脂の粒子の含有比率としては、処理液の全質量に対して0.5質量%~20質量%が好ましく、1質量%~10質量%がより好ましく、3質量%~5質量%がさらに好ましい。水不溶性樹脂粒子の含有量が0.5質量%以上であると、基材の濡れ性改善の効果が大きく、一方、含有量が20質量%以下であると、処理液の粘度が適正な範囲に維持され、処理液の安定性が向上する。
具体的には、GPCは、測定装置として、HLC(登録商標)-8220GPC(東ソー社製)を用い、カラムとして、TSKgel、Super Multipore HZ-H(東ソー社製、4.6mmID×15cm)を3本用い、溶離液として、THF(テトラヒドロフラン)を用いて行う。また、条件としては、試料濃度を0.45質量%とし、流速を0.35ml/minとし、サンプル注入量を10μlとし、測定温度を40℃として、示唆屈折計(RI)検出器を用いる。また、検量線は、東ソー社製の「標準試料TSK standard,polystyrene」:「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、「n-プロピルベンゼン」の8サンプルから作製する。
処理液は、インク組成物中の着色剤を凝集させる化合物(凝集化成分)の少なくとも一種を含有する。画像を記録するに際して処理液がインク組成物と接触することで、インク組成物中の少なくとも着色剤が凝集し、より精細な画像を得ることができる。
凝集化成分は、着色剤(好ましくは顔料)のほか、分散状態にある樹脂粒子等の凝集にも寄与する。
酸性化合物としては、インク組成物のpHを低下させ得る酸性物質を挙げることができ、有機酸性化合物及び無機酸性化合物のいずれを用いてもよい。また、有機酸性化合物及び無機酸性化合物は、2種以上を併用してもよい。
処理液に有機酸性化合物が含まれる場合、有機酸性化合物は、インク組成物中の成分を凝集させることができる。
有機酸性化合物としては、特に制限はなく、例えば、リン酸基、ホスホン酸基、ホスフィン酸基、硫酸基、スルホ基、スルフィン酸基、及びカルボキシ基等を有する化合物が挙げられる。有機酸性化合物は、インク組成物の凝集速度の観点から、リン酸基又はカルボキシ基を有する化合物が好ましく、カルボキシ基を有する化合物がより好ましい。
処理液に無機酸性化合物が含まれる場合、無機酸性化合物は、インク組成物中の成分を凝集させることができる。
無機酸性化合物としては、特に制限はなく、例えば、リン酸、リン酸化合物、硝酸、亜硝酸、硫酸、塩酸などが挙げられる。無機酸性化合物としては、画像のざらつき抑制とインクの凝集速度の観点から、リン酸及びリン酸化合物が好ましい。
多価金属塩としては、周期表の第2属のアルカリ土類金属(例えば、マグネシウム、カルシウム)、周期表の第3族の遷移金属(例えば、ランタン)、周期表の第13族からのカチオン(例えば、アルミニウム)、ランタニド類(例えば、ネオジム)の塩を挙げることができる。
金属塩としては、カルボン酸塩(蟻酸、酢酸、安息香酸塩など)、硝酸塩、塩化物、及びチオシアン酸塩が好適である。中でも、好ましくは、カルボン酸(蟻酸、酢酸、安息香酸塩など)のカルシウム塩又はマグネシウム塩、硝酸のカルシウム塩又はマグネシウム塩、塩化カルシウム、塩化マグネシウム、及びチオシアン酸のカルシウム塩又はマグネシウム塩である。
カチオン性化合物としては、カチオン性樹脂及びカチオン性界面活性剤が挙げられる。
カチオン性樹脂としては、例えば、エピクロルヒドリン・ジメチルアミン付加重合物、ジシアンジアミドとホルマリンもしくはジエチレントリアミンとの重縮合物、ジメチルジアリルアンモニウムクロライドと二酸化硫黄(SO2)との共重合物、ジアリルアミン塩と二酸化硫黄(SO2)との共重合物、ジメチルジアリルアンモニウムクロライド重合物、アリルアミン塩の重合物、ジアルキルアミノエチル(メタ)アクリレート4級塩重合物、ポリアリルアミン、カチオンエポキシ、ポリエチレンイミン、ポリアクリルアミド、ポリ(メタ)アクリル酸エステル、ビニルホルムアミド、カチオン性樹脂エマルジョン、カチオン性樹脂多価金属塩などが挙げられる。
また、ポリアリルアミン類を用いてもよい。これらのほか、所望のpH領域でカチオン性を示す両性界面活性剤も使用可能であり、例えば、アミノ酸型の両性界面活性剤、R-NH-CH2CH2-COOH型の化合物(Rはアルキル基等を表す)、カルボン酸塩型両性界面活性剤(例えば、ステアリルジメチルベタイン、ラウリルジヒドロキシエチルベタインなど)、硫酸エステル型、スルホン酸型、又はリン酸エステル型等の両性界面活性剤等が挙げられる。
処理液は、水を含有し、水性組成物として調製されている。
水の含有量は、特に制限はないが、処理液の全質量に対して、10質量%~99質量%の範囲が好ましく、より好ましくは50質量%~90質量%であり、更に好ましくは60質量%~80質量%である。
処理液は、上記の成分以外の他の成分を含んでいてもよい。他の成分としては、有機溶剤、含窒素ヘテロ環化合物、消泡剤、及びその他の添加剤等を挙げることができる。
処理液は、有機溶剤の少なくとも1種を含むことが好ましい。
有機溶剤としては、20℃で100gの水に5g以上溶解する有機溶剤(以下、「水溶性有機溶剤」ともいう。)であることが好ましい。
水溶性有機溶剤としては、後述するインク組成物に含まれる水溶性有機溶剤と同様のものを用いることができる。これらの有機溶剤の中でも、カール抑制の観点から、ポリアルキレングリコール又はその誘導体であることが好ましく、ジエチレングリコールモノアルキルエーテル、トリエチレングリコールモノアルキルエーテル、ジプロピレングリコール、トリプロピレングリコールモノアルキルエーテル、ポリオキシプロピレングリセリルエーテル、及びポリオキシエチレンポリオキシプロピレングリコールから選ばれる少なくとも1種であることがより好ましい。
有機溶剤の処理液中における含有量としては、特に制限はされないが、カール抑制の観点から、処理液全体に対して1質量%~30質量%であることが好ましく、5質量%~15質量%であることがより好ましい。
処理液は、含窒素ヘテロ環化合物を含有してもよい。これにより、画像の耐擦性及び基材の搬送性がさらに向上する。
含窒素5員環構造及び含窒素6員環構造の中で好ましくは、炭素原子、窒素原子、酸素原子、硫黄原子及びセレン原子の少なくとも一種の原子を含む5員もしくは6員のヘテロ環の構造が好ましい。なお、ヘテロ環は、炭素芳香環又は複素芳香環で縮合していてもよい。
ヘテロ環としては、例えば、テトラゾール環、トリアゾール環、イミダゾール環、チアジアゾール環、オキサジアゾール環、セレナジアゾール環、オキサゾール環、チアゾール環、ベンゾオキサゾール環、ベンゾチアゾール環、ベンゾイミダゾール環、ピリミジン環、トリアザインデン環、テトラアザインデン環、ペンタアザインデン環等が挙げられる。
好ましい含窒素6員環化合物の具体例としては、トリアジン、メチルトリアジン、ジメチルトリアジン、ヒドロキシエチルトリアジン環、ピリミジン、4-メチルピリミジン、ピリジン、ピロリン等が挙げられる。
処理液は、消泡剤を含有していてもよい。消泡剤としては、例えば、シリコーン系化合物(シリコーン系消泡剤)、プルロニック系化合物(プルロニック系消泡剤)等が挙げられる。中でも、シリコーン系消泡剤が好ましい。
シリコーン系消泡剤としては、ポリシロキサン構造を有するシリコーン系消泡剤が好ましい。
消泡剤としてシリコーン系消泡剤を用いる場合には、シリコーンオイル量が50ppm~200ppmとなる量を含有することが好ましい。
処理液は、必要に応じて、その他の添加剤を含むことができる。その他の添加剤としては、後述のインク組成物中におけるその他の添加剤と同様である。
処理液の表面張力としては、特に制限はなく、例えば、20mN/m以上とすることができる。基材に対する塗布性の観点から、20mN/m~60mN/mがより好ましく、25mN/m~45mN/mがさらに好ましい。
処理液の表面張力は、Automatic Surface Tensiometer
CBVP-Z(協和界面科学株式会社製)を用い、プレート法により25℃の条件下で測定される値である。
処理液の表面張力は、例えば、界面活性剤を添加することで調整することができる。
処理液のpH(25℃±1℃)は、インク組成物の凝集速度の観点から、7.0以下の範囲が好ましく、0.5~3.5がより好ましく、0.5~2.0がさらに好ましい。
pHは、25℃環境下において、処理液を25℃に調温した状態でpHメータWM-50EG(東亜DDK社製)を用いて測定される値である。
処理液の粘度は、インク組成物の凝集速度の観点から、1mPa・s~30mPa・sの範囲が好ましく、1mPa・s~20mPa・sの範囲がより好ましく、2mPa・s~15mPa・sの範囲がさらに好ましく、2mPa・s~10mPa・sの範囲が特に好ましい。
粘度は、VISCOMETER TV-22(TOKI SANGYO CO.LTD製)を用いて25℃の条件下で測定される値である。
インクセットにおけるインク組成物は、少なくとも着色剤及び水を含有する。インク組成物は、必要に応じて、更に、樹脂粒子、顔料分散剤(ポリマー分散剤)、有機溶剤、中和剤、及びその他の成分を含有することができる。
インク組成物は、着色剤の少なくとも一種を含有する。着色剤としては、特に制限されず、顔料であっても染料であってもよい。また、着色剤は、前述の凝集化成分と接触した際の凝集性に優れる点から、アニオン性着色剤が好ましく、更には顔料が好ましい。
なお、「アニオン性着色剤」とは、構造中(着色剤が後述の分散剤で被覆される場合は分散剤の構造中)に、カルボキシ基、スルホ基、リン酸基等のアニオン性基を有する着色剤をいう。
顔料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、有機顔料、無機顔料のいずれであってもよい。顔料は、水に殆ど不溶であるか又は難溶である顔料であることが、インク着色性の点で好ましい。
有機顔料としては、例えば、アゾレーキ、アゾ顔料、フタロシアニン顔料、ペリレン及びペリノン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、ジケトピロロピロール顔料、チオインジゴ顔料、イソインドリノン顔料、キノフタロン顔料等の多環式顔料や、塩基性染料型レーキ、酸性染料型レーキ等の染料レーキや、ニトロ顔料、ニトロソ顔料、アニリンブラック、昼光蛍光顔料等が挙げられる。
無機顔料としては、例えば、酸化チタン、酸化鉄、炭酸カルシウム、硫酸バリウム、水酸化アルミニウム、バリウムイエロー、カドミウムレッド、クロムイエロー、カーボンブラック等が挙げられる。
また、カラーインデックスに記載されていない顔料であっても、水に分散可能であればいずれも使用できる。更に、顔料を界面活性剤や高分子分散剤等で表面処理したものや、グラフトカーボン等も使用可能である。
これら顔料のうち、特に、アゾ顔料、フタロシアニン顔料、アントラキノン顔料、キナクリドン顔料、カーボンブラック顔料が好ましく、アニオン性のアゾ顔料、アニオン性のフタロシアニン顔料、アニオン性のキナクリドン顔料がより好ましい。
インク組成物では、顔料が分散剤によって分散されている形態が好ましい。中でも、特に顔料がポリマー分散剤によって分散されている形態、すなわち顔料の少なくとも一部がポリマー分散剤により被覆されている形態が好ましい。
以下、少なくとも一部がポリマー分散剤により被覆されている顔料を「樹脂被覆顔料」という。
低分子の界面活性剤型分散剤としては、特開2010-188661号公報の段落0016~0020に記載の界面活性剤型分散剤を用いることができる
水溶性の非架橋ポリマー分散剤としては、例えば、特開2010-188661号公報の段落0021~0022に記載の天然の親水性高分子化合物を用いることができる。
合成系の親水性高分子化合物としては、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル等のビニル系高分子、ポリアクリルアミド、ポリアクリル酸又はそのアルカリ金属塩、水溶性スチレンアクリル樹脂等のアクリル系樹脂、水溶性スチレンマレイン酸樹脂、水溶性ビニルナフタレンアクリル樹脂、水溶性ビニルナフタレンマレイン酸樹脂、ポリビニルピロリドン、ポリビニルアルコール、β-ナフタレンスルホン酸ホルマリン縮合物のアルカリ金属塩、四級アンモニウムやアミノ基等のカチオン性官能基の塩を側鎖に有する高分子化合物等が挙げられる。
スチレン-(メタ)アクリル酸共重合体、(メタ)アクリル酸エステル-(メタ)アクリル酸共重合体、ポリエチレングリコール(メタ)アクリレート-(メタ)アクリル酸共重合体、スチレン-マレイン酸共重合体は、2元共重合体であっても3元以上の共重合体であってもよい。
非架橋ポリマー分散剤としては、これらのうち、(メタ)アクリル酸エステル-(メタ)アクリル酸共重合体が好ましく、ベンジル(メタ)アクリレート-(メタ)アクリル酸-メチル(メタ)アクリレート3元共重合体が特に好ましい。
ここで、(メタ)アクリル酸は、アクリル酸又はメタクリル酸を指し、(メタ)アクリレートは、アクリレート又はメタクリレートを指す。
なお、共重合体は、ランダム共重合体でも、ブロック共重合体でも、グラフト共重合体でもよい。
なお、重量平均分子量は、既述の水不溶性樹脂の重量平均分子量の測定と同様の方法により測定される値である。
ポリマーとしては、特に制限されず、種々のポリマーを用いることができるが、中でも、水溶性分散剤として機能し得るポリビニル類、ポリウレタン類、ポリエステル類等が好ましく、ポリビニル類がより好ましい。
ポリマーは、共重合成分としてカルボキシ基含有モノマーを用いて得られる共重合体であることが好ましい。カルボキシ基含有モノマーとしては、例えば、(メタ)アクリル酸、β-カルボキシエチルアクリレート、フマル酸、イタコン酸、マレイン酸、クロトン酸等が挙げられ、中でも、ポリマーの架橋性及び分散安定性の観点から、(メタ)アクリル酸やβ-カルボキシエチルアクリレートが好ましい。
さらには、顔料の分散性、分散安定性の観点から、100mgKOH/g~180mgKOH/gであることが好ましく、100mgKOH/g~170mgKOH/gであることがより好ましく、100mgKOH/g~160mgKOH/gがさらに好ましい。
なお、酸価は、日本工業規格(JIS K0070:1992)に記載の方法により測定される値である。
なお、重量平均分子量は、既述の水不溶性樹脂の重量平均分子量の測定と同様の方法により測定される値である。
ポリマーの共重合形態は特に制限されず、ポリマーは、ランダムポリマーでも、ブロックポリマーでも、グラフトポリマーでもよい。
架橋剤としては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、1,6-へキサンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等が挙げられ、ポリエチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルが好ましい。
なお、顔料の平均粒子径及び粒径分布は、ナノトラック粒度分布測定装置UPA-EX150(日機装(株)製)を用いて、動的光散乱法により体積平均粒子径を測定することにより求められるものである。
顔料は、1種単独で又は2種以上を組合せて使用してもよい。
染料としては公知の染料を特に制限なく用いることができ、例えば、特開2001-115066号公報、特開2001-335714号公報、特開2002-249677号公報等に記載の染料を本開示においても好適に用いることができる。
また、染料を用いる場合には、染料を水不溶性の担体に保持したものを用いてもよい。染料を保持した担体(水不溶性着色粒子)は、分散剤を用いて水系分散物として用いることができる。担体としては、水に不溶又は水に難溶であれば特に制限なく、無機材料、有機材料及びこれらの複合材料を用いることができる。具体的には、特開2001-181549号公報、特開2007-169418号公報等に記載の担体を本開示においても好適に用いることができる。
インク組成物は、樹脂粒子の少なくとも一種を含有することが好ましい。
樹脂粒子は、前述のポリマー分散剤(顔料の少なくとも一部を覆うポリマー分散剤)とは異なり、顔料とは別に存在している粒子である。
インク組成物が樹脂粒子を含む場合、樹脂粒子は、前述の凝集化成分と接触することで凝集するものであることが好ましい。
また、樹脂粒子は、前述の凝集化成分と接触した際の凝集性に優れる点から、スルホ基以外のアニオン性の解離基を有する樹脂粒子が好ましい。スルホ基以外のアニオン性の解離基を有する樹脂粒子の詳細は後述する。
アニオン性解離基としてスルホ基を有する樹脂粒子は、樹脂粒子自体の分散安定性が大きく向上するため、処理液の凝集化成分と接触しても凝集しにくい点で好ましくない。
ここで、「非水溶性又は難水溶性」であるとは、樹脂を105℃で2時間乾燥させた後、25℃の水100g中に溶解させた場合に、その溶解量が15g以下であることをいう。インクの連続吐出性及び吐出安定性が向上する観点から、溶解量は好ましくは10g以下、より好ましくは5g以下であり、更に好ましくは1g以下である。溶解量は、非水溶性又は難水溶性の樹脂粒子の塩生成基の種類に応じて、水酸化ナトリウム又は酢酸で100%中和した時の溶解量である。
ここで、分散状態とは、水性媒体中に水不溶性ポリマーが液体状態で分散された乳化状態(エマルジョン)、及び、水性媒体中に水不溶性ポリマーが固体状態で分散された分散状態(サスペンジョン)の両方の状態を含むものである。
また、水性媒体は水を含む媒体を指す。水性媒体は、必要に応じて親水性有機溶剤を含んでいてもよい。水性媒体は、水と水に対して0.2質量%以下の親水性有機溶剤とが含まれることが好ましく、水のみであることがより好ましい。
自己分散性樹脂としては、インク組成物に含有された場合の凝集速度と定着性の観点から、水不溶性ポリマーが固体状態で分散された分散状態となりうる自己分散性樹脂粒子であることが好ましい。
転相乳化法としては、例えば、自己分散性樹脂を溶媒(例えば、水溶性有機溶剤等)中に溶解又は分散させた後、界面活性剤を添加せずにそのまま水中に投入し、自己分散性樹脂が有する塩生成基(例えば、酸性基)を中和した状態で、撹拌、混合し、溶媒を除去した後、乳化又は分散状態となった水性分散物を得る方法が挙げられる。
遠心分離前の固形分濃度に対する遠心分離後の固形分濃度の比が大きければ(1に近い数値であれば)、遠心分離による樹脂粒子の沈降が生じない、すなわち、樹脂粒子の水性分散物がより安定であることを意味する。本開示においては、遠心分離前後での固形分濃度の比が0.8以上であることが好ましく、0.9以上であることがより好ましく、0.95以上であることが特に好ましい。
ここで水溶性成分とは、自己分散性樹脂に含有される化合物であって、自己分散性樹脂を分散状態にした場合に水に溶解する化合物をいう。水溶性成分は自己分散性樹脂を製造する際に、副生又は混入する水溶性の化合物である。
また、縮合系ポリマーと縮合系ポリマーを構成するモノマーの好適な例としては、特開2001-247787号公報に記載されているものを挙げることができる。
親水性基は、形成された乳化又は分散状態の安定性の観点から、解離性基であることが好ましく、アニオン性の解離基であることがより好ましい。
すなわち、本開示における樹脂粒子としては、アニオン性の解離基を有する樹脂粒子であることが好ましい。
解離性基としては、カルボキシ基、リン酸基などが挙げられ、中でも、インク組成物を構成した場合の定着性の観点から、カルボキシ基が好ましい。
解離性基含有モノマーとしては、例えば、不飽和カルボン酸モノマー、不飽和スルホン酸モノマー、不飽和リン酸モノマー等が挙げられる。
不飽和リン酸モノマーとして具体的には、ビニルホスホン酸、ビニルホスフェート、ビス(メタクリロキシエチル)ホスフェート、ジフェニル-2-アクリルオキシエチルホスフェート、ジフェニル-2-メタクリルオキシエチルホスフェート、ジブチル-2-アクリルオキシエチルホスフェート等が挙げられる。
解離性基含有モノマーの中では、分散安定性、吐出安定性の観点から、不飽和カルボン酸モノマーが好ましく、アクリル酸及びメタクリル酸がより好ましい。
特に、酸価は、25mgKOH/g以上であると分散安定性が良好になり、100mgKOH/g以下であると凝集性が向上する。
なお、酸価は、日本工業規格(JIS K0070:1992)に記載の方法により測定される値である。
また重合性基は、縮重合性の重合性基であっても、付加重合性の重合性基であってもよい。本開示においては水性媒体中での粒子形状安定性の観点から、付加重合性の重合性基であることが好ましく、エチレン性不飽和結合を含む基であることがより好ましい。
芳香族基含有モノマーとしては、例えば、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェニル(メタ)アクリレート、スチレン系モノマー等が挙げられる。中でも、ポリマー鎖の親水性と疎水性のバランスとインク定着性の観点から、芳香族基含有(メタ)アクリレートモノマーが好ましく、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、及びフェニル(メタ)アクリレートから選ばれる少なくとも1種がより好ましく、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレートが更に好ましい。
脂環式(メタ)アクリレートとは、(メタ)アクリル酸に由来する構成部位と、アルコールに由来する構成部位とを含み、アルコールに由来する構成部位に、無置換又は置換された脂環式炭化水素基(環状脂肪族基)を少なくとも1つ含む構造を有しているものである。尚、脂環式炭化水素基は、アルコールに由来する構成部位そのものであっても、連結基を介してアルコールに由来する構成部位に結合していてもよい。
脂環式炭化水素基は、更に置換基を有してもよい。置換基としては、例えば、アルキル基、アルケニル基、アリール基、アラルキル基、アルコキシ基、水酸基、1級アミノ基、2級アミノ基、3級アミノ基、アルキル又はアリールカルボニル基、及びシアノ基等が挙げられる。また、脂環式炭化水素基は、さらに縮合環を形成していてもよい。本開示における脂環式炭化水素基としては、粘度や溶解性の観点から、脂環式炭化水素基部分の炭素数が5~20であることが好ましい。
単環式(メタ)アクリレートとしては、シクロプロピル(メタ)アクリレート、シクロブチル(メタ)アクリレート、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、シクロヘブチル(メタ)アクリレート、シクロオクチル(メタ)アクリレート、シクロノニル(メタ)アクリレート、シクロデシル(メタ)アクリレート等のシクロアルキル基の炭素数が3~10のシクロアルキル(メタ)アクリレート等が挙げられる。
2環式(メタ)アクリレートとしては、イソボルニル(メタ)アクリレート、ノルボルニル(メタ)アクリレート等が挙げられる。
3環式(メタ)アクリレートとしては、アダマンチル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート等が挙げられる。
これらは、それぞれ単独で又は2種以上を混合して用いることができる。
分散状態の安定性、芳香環同士又は脂環同士の疎水性相互作用による水性媒体中での粒子形状の安定化、粒子の適度な疎水化による水溶性成分量の低下の観点から、芳香族基含有(メタ)アクリレートモノマー又は脂環式(メタ)アクリレートの含有量が15質量%~90質量%であることがより好ましく、15質量%~80質量%であることがより好ましく、25質量%~70質量%であることが特に好ましい。
アルキル基含有モノマーとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、エチルヘキシル(メタ)アクリレート等のアルキル(メタ)アクリレート;ヒドロキシメチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、ヒドロキシペンチル(メタ)アクリレート、ヒドロキシヘキシル(メタ)アクリレート等の水酸基を有するエチレン性不飽和モノマー;ジメチルアミノエチル(メタ)アクリレート等のジアルキルアミノアルキル(メタ)アクリレート;N-ヒドロキシメチル(メタ)アクリルアミド、Nーヒドロキシエチル(メタ)アクリルアミド、N-ヒドロキシブチル(メタ)アクリルアミド等のN-ヒドロキシアルキル(メタ)アクリルアミド;N-メトキシメチル(メタ)アクリルアミド、N-エトキシメチル(メタ)アクリルアミド、N-(n-,イソ)ブトキシメチル(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、N-エトキシエチル(メタ)アクリルアミド、N-(n-、イソ)ブトキシエチル(メタ)アクリルアミド等のN-アルコキシアルキル(メタ)アクリルアミド等の(メタ)アクリルアミド等が挙げられる。
なお、重量平均分子量は、既述の方法で測定することができる。
また、水不溶性ポリマーは、ポリマーの親疎水性制御の観点から、芳香族基含有(メタ)アクリレートモノマー又は脂環式(メタ)アクリレートモノマーに由来する構成単位を共重合比率として15質量%~80質量%と、カルボキシ基含有モノマーに由来する構成単位と、アルキル基含有モノマーに由来する構成単位(好ましくは、(メタ)アクリル酸のアルキルエステルに由来する構成単位)とを含むことが好ましく、フェノキシエチル(メタ)アクリレートに由来する構成単位及び/又はベンジル(メタ)アクリレートに由来する構成単位を共重合比率として15質量%~80質量%と、カルボキシ基含有モノマーに由来する構成単位と、アルキル基含有モノマーに由来する構成単位(好ましくは、(メタ)アクリル酸の炭素数1~4のアルキルエステルに由来する構成単位)とを含むことがより好ましい。
また、水不溶性ポリマーは、酸価が25mgKOH/g~100mgKOH/gであって重量平均分子量が3,000~200,000であることが好ましく、酸価が25mgKOH/g~95mgKOH/gであって重量平均分子量が5,000~150,000であることがより好ましい。酸価及び重量平均分子量は、既述の方法で測定することができる。
B-02:フェノキシエチルアクリレート/ベンジルメタクリレート/イソブチルメタクリレート/メタクリル酸共重合体(30/35/29/6)
B-03:フェノキシエチルメタクリレート/イソブチルメタクリレート/メタクリル酸共重合体(50/44/6)
B-04:フェノキシエチルアクリレート/メチルメタクリレート/エチルアクリレート/アクリル酸共重合体(30/55/10/5)
B-05:ベンジルメタクリレート/イソブチルメタクリレート/メタクリル酸共重合体(35/59/6)
B-06:スチレン/フェノキシエチルアクリレート/メチルメタクリレート/アクリル酸共重合体(10/50/35/5)
B-07:ベンジルアクリレート/メチルメタクリレート/アクリル酸共重合体(55/40/5)
B-08:フェノキシエチルメタクリレート/ベンジルアクリレート/メタクリル酸共重合体(45/47/8)
B-09:スチレン/フェノキシエチルアクリレート/ブチルメタクリレート/アクリル酸共重合体(5/48/40/7)
B-10:ベンジルメタクリレート/イソブチルメタクリレート/シクロヘキシルメタクリレート/メタクリル酸共重合体(35/30/30/5)
B-11:フェノキシエチルアクリレート/メチルメタクリレート/ブチルアクリレート/メタクリル酸共重合体(12/50/30/8)
B-12:ベンジルアクリレート/イソブチルメタクリレート/アクリル酸共重合体(93/2/5)
B-13:スチレン/フェノキシエチルメタクリレート/ブチルアクリレート/アクリル酸共重合体(50/5/20/25)
B-14:スチレン/ブチルアクリレート/アクリル酸共重合体(62/35/3)
B-15:メチルメタクリレート/フェノキシエチルアクリレート/アクリル酸共重合体(45/51/4)
B-16:メチルメタクリレート/フェノキシエチルアクリレート/アクリル酸共重合体(45/49/6)
B-17:メチルメタクリレート/フェノキシエチルアクリレート/アクリル酸共重合体(45/48/7)
B-18:メチルメタクリレート/フェノキシエチルアクリレート/アクリル酸共重合体(45/47/8)
B-19:メチルメタクリレート/フェノキシエチルアクリレート/アクリル酸共重合体(45/45/10)
B-20:メチルメタクリレート/イソボルニルメタクリレート/メタクリル酸共重合体(20/72/8)
B-21:メチルメタクリレート/イソボルニルメタクリレート/メタクリル酸共重合体(40/52/8)
B-22:メチルメタクリレート/イソボルニルメタクリレート/ジシクロペンタニルメタクリレート/メタクリル酸共重合体(20/62/10/8)
B-23:メチルメタクリレート/ジシクロペンタニルメタクリレート/メタクリル酸共重合体(20/72/8)
すなわち、樹脂粒子の製造は、有機溶剤中でポリマーを合成する工程と、ポリマーのアニオン性基(カルボキシ基)の少なくとも一部が中和された水性分散物とする分散工程と、を設けて行なうことが好ましい。
工程(1):ポリマー(水不溶性ポリマー)、有機溶剤、中和剤、及び水性媒体を含有する混合物を、撹拌する工程
工程(2):混合物から有機溶剤を除去する工程
混合物の撹拌方法に特に制限はなく、一般に用いられる混合撹拌装置や、必要に応じて超音波分散機や高圧ホモジナイザー等の分散機を用いることができる。
また、工程(2)においては、工程(1)で得られた分散体から、減圧蒸留等の常法により有機溶剤を留去して水系へと転相することで樹脂粒子の水性分散物を得ることができる。得られた水性分散物中の有機溶剤は実質的に除去されており、有機溶剤の量は、好ましくは0.2質量%以下、更に好ましくは0.1質量%以下である。
中和剤としては、特開2010-188661号公報の段落0060~0061に例示された中和剤を用いることができる。
なお、樹脂粒子の平均粒子径及び粒径分布は、ナノトラック粒度分布測定装置UPA-EX150(日機装(株)製)を用いて、動的光散乱法により体積平均粒径を測定することにより求められる。
樹脂粒子(好ましくは自己分散性樹脂粒子)のインク組成物中における含有量(総含有量)としては、画像の光沢性などの観点から、インク組成物全量に対して、1質量%~30質量%であることが好ましく、3質量%~15質量%であることがより好ましい。
インク組成物は、水を含有し、水性組成物として調製されている。
水の含有量は、特に制限はないが、インク組成物の全質量に対して、10質量%~99質量%の範囲が好ましく、より好ましくは30質量%~80質量%であり、更に好ましくは50質量%~80質量%である。
インク組成物は、上記の成分以外の他の成分を含んでいてもよい。
[有機溶剤]
インク組成物は、有機溶剤(好ましくは、水溶性有機溶剤)の少なくとも1種を更に含有することがより好ましい。有機溶剤、特に、水溶性有機溶剤を含有することで、乾燥防止、浸透促進を図ることができる。
水溶性有機溶剤を乾燥防止剤として用いる場合、インク組成物をインクジェット法で吐出して画像を記録する際、インク吐出口でのインクの乾燥によって発生し得るノズルの目詰まりを効果的に防止することができる。
これらの水溶性有機溶剤の中でも、グリセリン、ジエチレングリコール等の多価アルコールが好ましい。また、これらは、1種単独で用いても、2種以上を併用してもよい。これらの水溶性有機溶剤は、インク組成物中に10質量%~50質量%含有されることが好ましい。
なお、水溶性有機溶剤は、1種単独で又は2種以上を混合して用いてもよい。
インク組成物は、界面活性剤の少なくとも1種を含有していてもよい。
界面活性剤としては、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤、ベタイン界面活性剤等が挙げられる。凝集速度の観点からは、アニオン性界面活性剤又はノニオン性界面活性剤であることが好ましい。
インク組成物は、上記成分以外にその他の添加剤を更に含有することができる。その他の添加剤としては、例えば、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤、pH調整剤、消泡剤、粘度調整剤、分散安定剤、防錆剤、キレート剤等の公知の添加剤が挙げられる。これらの各種添加剤は、インク組成物を調製後に直接添加してもよく、インク組成物の調製時に添加してもよい。
粘度は、VISCOMETER TV-22(TOKI SANGYO CO.LTD製)を用い、インク組成物を25℃の条件下で測定されるものである。
インクセットは、必要に応じて、1種又は2種のインク組成物と処理液とからなる1色構成又は2色構成のインクセットであってもよい。
また、インクセットは、上述のインク組成物に加え、必要に応じて、ライトシアンインク、ライトマゼンタインク、及びライトイエローインクから選択される少なくとも1つ等、他のインク組成物を含む形態であってもよい。他のインク組成物には、公知のインク組成物を適用することができる。
また、インクセットには、必要に応じて2種以上の処理液が含まれてもよい。
また、インクセットが2種以上の処理液を含む場合、処理液の少なくとも1つが、第1の単量体に由来の構成単位及び第2の単量体に由来の構成単位を有する水不溶性樹脂の粒子と凝集化成分(インク組成物中の着色剤を凝集させる化合物)と水とを含む処理液であればよい。
本開示に係る画像記録方法は、表面に水滴を付与して3秒経過したときの接触角が70°以上である基材の少なくとも一方の面に、既述の本開示に係るインクセットの処理液を付与する前処理工程と、処理液が付与された一方の面に、既述の本開示に係るインクセットのインク組成物をインクジェット法により吐出して画像を記録する画像記録工程と、を有している。
本開示に係る画像記録方法では、画像記録する場合に既述のインクセットが用いられるので、ベタ画像中の濃度低下が抑えられ、所望とする濃度を有し、かつ、筋状のムラの発生が抑制された画像の記録が可能である。
前処理工程は、表面に水滴を付与して3秒経過したときの接触角が70°以上である基材の少なくとも一方の面に、既述のインクセットの処理液を付与する。
処理液の付与は、塗布法、インクジェット法、浸漬法などの公知の方法により行うことができる。塗布法としては、バーコーター、エクストルージョンダイコーター、エアードクターコーター、ブレードコーター、ロッドコーター、ナイフコーター、スクイズコーター、リバースロールコーター、バーコーター等を用いた公知の塗布方法によって行うことができる。インクジェット法の詳細については後述する。
加熱方法としては、例えば、基材の処理液が付与された側と反対側からヒーター等で熱を与える方法、基材の処理液が付与された側に温風又は熱風をあてる方法、又は赤外線ヒーターを用いて加熱する方法などが挙げられる。加熱は、これらの複数を組み合わせて行ってもよい。
画像記録工程は、前処理工程で処理液が付与された基材の一方の面に、既述のインクセットのインク組成物をインクジェット法により吐出して画像を記録する。
なお、インクジェット法には、フォトインクと称する濃度の低いインクを小さい体積で多数射出する方式、実質的に同じ色相で濃度の異なる複数のインクを用いて画質を改良する方式や無色透明のインクを用いる方式が含まれる。
なお、インクジェット法により記録を行う際に使用するインクノズル等については特に制限はなく、目的に応じて、適宜選択することができる。
なお、インク滴の液滴量は、打滴するインク組成物に応じて、インクジェット法における吐出条件を適宜選択することで調整することができる。
画像記録方法において、前処理工程及び画像記録工程を経て記録された画像を加熱定着する加熱定着工程を更に設けてもよい。加熱定着を行うことにより、基材上の画像の定着が施され、画像の耐擦性がより向上する。
加熱しかつ加圧する場合、加圧時における圧力は、表面平滑化の点で、0.1MPa~3.0MPaの範囲が好ましく、より好ましくは0.1MPa~1.0MPaの範囲であり、更に好ましくは0.1MPa~0.5MPaの範囲である。
また、加熱加圧の方法は、特に制限はないが、例えば、熱板を基材の画像記録面に押圧する方法や、一対の加熱加圧ローラ、一対の加熱加圧ベルト、あるいは基材の画像記録面側に配された加熱加圧ベルトとその反対側に配された保持ローラとを備えた加熱加圧装置を用い、対をなすローラ等を通過させる方法など、接触させて加熱定着を行なう方法が好適に挙げられる。
なお、表1中の「-」の表記は、その成分を含有していないことを示す。
撹拌機、冷却管を備えた1000mlの三口フラスコに、ドデシルベンゼンスルホン酸ナトリウム(62質量%水溶液、東京化成工業社製)1.5gと水310gを加え、窒素雰囲気下で90℃に加熱した。加熱された三口フラスコ中の混合溶液に、水20gに2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウム(AMPSANa)の50質量%水溶液(Aldrich社製)4.14gを溶解した溶液Aと、メチルメタクリレート(MMA;和光純薬工業社製)26.89g及びスチレン(St;和光純薬工業社製)12.41gを混合した溶液Bと、水40gに過硫酸ナトリウム(和光純薬工業社製)6.0gを溶解した溶液Cと、を3時間かけて同時に滴下した。滴下終了後、さらに3時間反応させることにより、水不溶性樹脂粒子A-1の水分散液(水不溶性樹脂粒子の固形分量:10.2質量%)410gを合成した。
水分散液中の水不溶性樹脂粒子A-1の体積平均粒子径は30nmであった。また、水不溶性樹脂粒子A-1の水不溶性樹脂の重量平均分子量は、32000であった。
具体的には、GPCは、測定装置として、HLC(登録商標)-8220GPC(東ソー社製)を用い、カラムとして、TSKgel、Super Multipore HZ-H(東ソー社製、4.6mmID×15cm)を3本用い、溶離液として、THF(テトラヒドロフラン)を用いて行った。また、条件としては、試料濃度を0.45質量%とし、流速を0.35ml/minとし、サンプル注入量を10μlとし、測定温度を40℃として、示唆屈折計(RI)検出器を用いた。また、検量線は、東ソー社製の「標準試料TSK standard,polystyrene」:「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、「n-プロピルベンゼン」の8サンプルから作製した。
水不溶性樹脂粒子A-1の水分散液の合成において、原料モノマーを下記表1に示すように変更したこと以外は、水不溶性樹脂粒子A-1の水分散液の合成と同様にして、水不溶性樹脂粒子A-2~A-20及びA-23の水分散液を合成し、体積平均粒子径及び重量平均分子量の測定を行った。測定結果を表5~表7に示す。
なお、水分散液中における水不溶性樹脂粒子A-2~A-20、A-23の固形分量は、いずれも9.5質量%~10.5質量%とした。
撹拌機、冷却管を備えた500mlの三口フラスコに、ドデシルベンゼンスルホン酸ナトリウム(62質量%水溶液、東京化成工業社製)1.5gと水130gを加え、窒素雰囲気下で90℃に加熱した。加熱された三口フラスコ中の混合溶液に、水20gに2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウム(AMPSANa)の50質量%水溶液(Aldrich製)8.27gを溶解した溶液Aと、メチルメタクリレート(MMA;和光純薬工業社製)22.75g、メタクリル酸(和光純薬工業社製)2.07g、スチレン12.41g、ドデカンチオール(連鎖移動剤)0.708gを混合した溶液Bと、水40gに過硫酸ナトリウム(和光純薬工業社製)6.0gを溶解した溶液Cと、を3時間かけて同時に滴下した。滴下終了後、さらに3時間反応させることにより、水不溶性樹脂粒子A-22の水分散液(水不溶性樹脂粒子の固形分量:19.6質量%)239gを合成した。体積平均粒子径及び重量平均分子量の測定結果は、表6に示す。なお、体積平均粒子径及び重量平均分子量の測定は、水不溶性樹脂粒子A-1の水分散液における場合と同様の方法で行った。
水不溶性樹脂粒子A-21の水分散液の合成において、原料モノマーの量を下記表1に示すように変更したこと以外は、水不溶性樹脂粒子A-21の水分散液の合成と同様にして、水不溶性樹脂粒子A-22の水分散液(水不溶性樹脂粒子の固形分量:19.8質量%)を合成し、体積平均粒子径及び重量平均分子量の測定を行った。測定結果を表6に示す。
撹拌機、冷却管を備えた500mlの三口フラスコに、水150gを加えて窒素雰囲気下で80℃に加熱した。加熱された水に、水45gに過硫酸ナトリウム3.60g及び2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウム(AMPSANa)の50質量%水溶液57.91gを混合した溶液Aと、メタクリル酸メチル(MMA;和光純薬工業社製)12.41g(溶液B)と、を2時間かけて同時に滴下した。滴下終了後、過硫酸ナトリウム1.3gを加え、さらに3時間反応させることにより、下記構造を有する水溶性樹脂X-1の水溶液を得た。なお、水溶液中の水溶性樹脂の固形分量は、16.2質量%とした。
水溶液中の水溶性樹脂X-1の重量平均分子量は、27000であった。重量平均分子量の測定は、水不溶性樹脂粒子A-1の水分散液における場合と同様の方法で行った。
なお、水溶性樹脂X-1は、体積平均粒子径の測定にて粒子径が検出されなかった。
水不溶性樹脂粒子A-1の水分散液の調製において、原料モノマーを下記表1に示すように変更したこと以外は、水不溶性樹脂粒子A-1の水分散液の調製と同様にして、水不溶性樹脂粒子X-2~X-4の水分散液を調製し、体積平均粒子径及び重量平均分子量の測定を行った。測定結果を表7に示す。
なお、水分散液中における水不溶性樹脂粒子X-2~X-4の固形分量は、いずれも15.0~17.0質量%とした。
(処理液A1~A27、AX1~AX4の調製)
下記組成となるように各成分を混合し、処理液A1~A27及び比較用の処理液AX1~AX4を調製した。
<処理液A1~A27、AX1~AX4の組成>
・ジエチレングリコールモノエチルエーテル・・・6.0質量%
・1,4-ブタンジオール・・・2.5質量%
・マロン酸(凝集化成分:有機酸性化合物)・・・17.3質量%
・プロパントリカルボン酸・・・4.3質量%
(凝集化成分:有機酸性化合物)
・リン酸(凝集化成分:無機酸性化合物)・・・4.3質量%
・下記表5~表7に記載の、水不溶性樹脂粒子の水分散液又は水溶性樹脂・・・表5~表7に記載の量
・ベンゾトリアゾール・・・1質量%
・消泡剤 ・・・シリコーンオイル量が100ppmとなる量
(TSA-739(固形分15質量%)、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製;エマルジョン型シリコーン消泡剤)
・イオン交換水・・・合計で100質量%となる残量
下記組成となるように各成分を混合し、処理液Bを調製した。
<処理液Bの組成>
・ジシアンジアミド・ホルマリン重縮合物・・・10質量%
(重合平均分子量3000、凝集化成分:カチオン性化合物)
・グリセリン・・・5質量%
・エチレングリコール・・・15質量%
・イオネットD46・・・1質量%
(三洋化成工業社製 4級アンモニウム型カチオン界面活性剤)
・安息香酸ナトリウム・・・1質量%
・トリエタノールアミン・・・0.7質量%
・表7に記載の水不溶性樹脂粒子の水分散液・・・表7に記載の量
・イオン交換水・・・合計で100質量%となる残量
下記組成となるように各成分を混合し、処理液Cを調製した。
<処理液Cの組成>
・塩化カルシウム(凝集化成分:多価金属塩)・・・10質量%
・3-メトキシ-3-メチル-1-ブタノール・・・5質量%
・グリセリン・・・30質量%
・エマルゲン108・・・1質量%
(ポリオキシエチレンラウリルエーテル、花王社製;界面活性剤)
・プロキセルxl-2(s)(Lonza社製;防腐剤)・・・0.2質量%
・表7に示す水不溶性樹脂粒子の水分散液・・・表7に記載の量
・イオン交換水・・・合計で100質量%となる残量
下記組成となるように各成分を混合し、処理液Dを調製した。
<処理液Dの組成>
・ジエチレングリコールモノエチルエーテル・・・6.0質量%
・1,4-ブタンジオール・・・2.5質量%
・マロン酸(凝集化成分:有機酸性化合物)・・・10質量%
・ベンゾトリアゾール・・・1質量%
・消泡剤 ・・・シリコーンオイル量が100ppmとなる量
(TSA-739(固形分:15質量%)、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製;エマルジョン型シリコーン消泡剤)
・表7に記載の水不溶性樹脂粒子の水分散液・・・表7に記載の量
・イオン交換水・・・合計で100質量%となる残量
下記組成となるように各成分を混合し、処理液Eを調製した。
<処理液Eの組成>
・ジエチレングリコールモノエチルエーテル・・・6.0質量%
・1,4-ブタンジオール・・・2.5質量%
・マロン酸(凝集化成分:有機酸性化合物)・・・5質量%
・ベンゾトリアゾール・・・1質量%
・消泡剤・・・シリコーンオイル量が100ppmとなる量
(TSA-739(固形分15質量%)、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製;エマルジョン型シリコーン消泡剤)
・表7に記載の水不溶性樹脂粒子の水分散液・・・表7に記載の量
・イオン交換水・・・合計で100質量%となる残量
下記組成となるように各成分を混合し、処理液Fを調製した。
<処理液Fの組成>
・ジエチレングリコールモノエチルエーテル・・・6.0質量%
・1,4-ブタンジオール・・・2.5質量%
・マロン酸(凝集化成分:有機酸性化合物)・・・3質量%
・ベンゾトリアゾール・・・1質量%
・消泡剤・・・シリコーンオイル量が100ppmとなる量
(TSA-739(固形分15質量%)、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製;エマルジョン型シリコーン消泡剤)
・表7に記載の水不溶性樹脂粒子の水分散液・・・表7に記載の量
・イオン交換水・・・合計で100質量%となる残量
なお、pHは25℃環境下、各処理液を25℃に調温した状態でpHメータWM-50EG(東亜DDK社製)にて測定し、表面張力はAutomatic Surface Tensiometer CBVP-Z(協和界面科学社製)にてプレート法により25℃の条件下で測定した。また、粘度は、VISCOMETER TV-22(TOKI SANGYO CO.LTD製)を用い、各処理液を25℃に調温した状態で測定した。
(ポリマー分散剤P-1の合成)
下記スキームにしたがって、以下に示すようにしてポリマー分散剤P-1を合成した。ポリマー分散剤P-1の構造式中の数値は、質量比を表す。
得られたポリマー分散剤P-1の組成は、プロトン核磁気共鳴分光法(1H-NMR)で確認し、GPCにより求めた重量平均分子量(Mw)は44,600であった。さらに、日本工業規格(JIS K0070:1992)に記載の方法により酸価を求めたところ、65.2mgKOH/gであった。
-シアン分散液の調製-
シアン顔料であるピグメント・ブルー15:3(フタロシアニンブル-A220、大日精化社製)10質量部と、ポリマー分散剤P-1を5質量部と、メチルエチルケトン42質量部と、1×103mol/L NaOH水溶液5.5質量部と、イオン交換水87.2質量部と、を混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて2時間~6時間分散した。
得られた分散物を減圧下、55℃でメチルエチルケトンを除去し、更に一部の水を除去した後、更に、高速遠心冷却機7550(久保田製作所製)を用いて、50ml遠心管を使用し、8000rpmで30分間遠心処理を行なった。延伸処理後、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、顔料濃度が10.2質量%の樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(シアン分散液C)を得た。
シアン分散液Cの樹脂被覆顔料粒子の体積平均粒子径は105nmであった。なお、体積平均粒子径は、固形分濃度が10質量%になるように調整した水不溶性樹脂粒子の分散物に対して、ナノトラック粒度分布測定装置UPA-EX150(日機装社製)を用いて動的光散乱法により液温25℃で測定して求めた。
シアン分散液の調製において、ピグメント・ブルー15:3(フタロシアニンブル-A220、大日精化社製)の代わりに、マゼンタ顔料であるピグメント・レッド122(クロモファインレッド、大日精化社製)を用いたこと以外はシアン分散液の調製と同様にして、樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(マゼンタ分散液M)を調製した。
マゼンタ分散液Mの樹脂被覆顔料粒子の体積平均粒子径は85nmであった。なお、体積平均粒子径は、シアン分散液Cの樹脂被覆顔料粒子の体積平均粒子径の測定と同様の方法で測定した。
シアン分散液の調製において、ピグメント・ブルー15:3(フタロシアニンブル-A220、大日精化社製)の代わりに、イエロー顔料であるピグメントイエロー74(クロモファインイエロー、大日精化社製)を用いたこと以外は、同様の方法で樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(イエロー分散液Y)を調製した。
イエロー分散液Yの樹脂被覆顔料粒子の体積平均粒子径は82nmであった。なお、体積平均粒子径は、シアン分散液Cの樹脂被覆顔料粒子の体積平均粒子径の測定と同様の方法で測定した。
シアン分散液の調製において、ピグメント・ブルー15:3(フタロシアニンブル-A220、大日精化社製)の代わりに、ブラック顔料であるカーボンブラック(NIPEX160-IQ、デグッサ社製)を用いたこと以外は、同様の方法で樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(ブラック分散液K)を調製した。
ブラック分散液Kの樹脂被覆顔料粒子の体積平均粒子径は130nmであった。なお、体積平均粒子径は、シアン分散液Cの樹脂被覆顔料粒子の体積平均粒子径の測定と同様の方法で測定した。
撹拌機、温度計、還流冷却管、及び窒素ガス導入管を備えた2リットル三口フラスコに、メチルエチルケトン293gを仕込んで、80℃まで昇温した。反応容器内温度を80℃に保ちながら、メチルメタクリレート(三菱ガス化学社製)165.7g、イソボロニルメタクリレート(共栄社化学社製)63.7g メタクリル酸(三菱ガス化学社製)25.5g、メチルエチルケトン48g、及び「V-601」(和光純薬工業社製、重合開始剤)1.25gからなる混合溶液を、2時間で滴下が完了するように等速で滴下した。滴下完了後、(1)「V-601」0.60g及びメチルエチルケトン5.0gを混合した溶液を加え、さらに2時間撹拌する。その後、(1)の工程を4回繰り返し、さらに「V-601」0.60g及びメチルエチルケトン5.0gを混合した溶液を加え、3時間撹拌した。その後、このようにして、重合体溶液を調製した。
重合体溶液中の共重合体の重量平均分子量(Mw)は72,000であり、酸価は62.9mgKOH/gであった。
なお、酸価は、日本工業規格(JIS K0070:1992)に記載の方法に準拠して測定した。重量平均分子量は、GPCにより既述の方法で測定した。
なお、以下に示す樹脂粒子(B-01)の各構成単位の数字は、質量比を表す。
上記で得られた各顔料分散液(シアン分散液C、マゼンタ分散液M、イエロー分散液Y、ブラック分散液K)、及び樹脂粒子(B-01)を用い、下記表4に示す組成となるように各成分を混合し、4種のインク組成物(マゼンタインク組成物M1、シアンインク組成物C1、イエローインク組成物Y1、ブラックインク組成物K1)を調製し、4種のインク組成物からなるインク1を作製した。
マゼンタインクM1、シアンインクC1、イエローインクY1、及びブラックインクK1の、上記処理液のpHと同様の方法で測定したpH(25℃)は、それぞれ8.1、8.3、8.0、8.2であった。
・サンニックスGP-250 ・・・三洋化成工業社製の有機溶剤
・オルフィンE1010 ・・・日信化学工業社製のノニオン性界面活性剤
<インクセット>
上記のインク1(マゼンタインクM1、ブラックインクK1、シアンインクC1、イエローインクY1)と、各処理液(処理液A1~A27、処理液B~F、及び比較用の処理液AX1~AX4)と、を組み合わせたインクセット1~インクセット25及びインクセットX1~X4を準備した。
各インクセットを用い、以下の手順で画像を記録し、以下に示す方法により記録画像の評価を行った。
基材として、コート紙(CartaIntegra、Metsaboard社;表面に水滴を付与して3秒経過したときの水接触角74°)を用い、下記条件で画像を記録した。なお、画像を記録する際、処理液を付与した後、10秒以内にインクの打滴が開始されるようにした。
また、基材の水接触角は、接触角計ドロップマスターDM700(協和界面科学社製)を用い、日本工業規格(JIS R3257)に記載の方法に準拠して測定した。水滴の滴量を2μLとして、基材の表面における水滴の着滴から3秒経過後の基材の接触角を測定した。
基材にインクを付与する直前に、塗布バーを用いて処理液を基材上に塗設した。処理液の塗工量は、1.7g/m2とした。
なお、インクを付与する直前に処理液を塗設するとは、画像記録工程で画像を記録する度毎に処理液を塗設することを意味する。
<処理液乾燥の条件>
・風速:15m/s
・温度及び加熱方法:基材の表面温度(処理液が付与された側の表面の温度)が60℃となるように、基材の背面(処理液が付与されていない側の表面)を接触型平面ヒーターで加熱した。
・送風領域:450mm(乾燥時間:0.7秒)
処理液が付与された基材の処理液付与面に、下記条件で4色のインクをシングルパスで吐出して記録する方法により画像を記録した。具体的には、基材に付与された処理液の上に、下記条件で各色のインクを打滴して多色画像(各色のベタ画像部及び2次色画像を含む)を記録した。
<条件>
・ヘッド:1,200dpi(dots per inch)/20inch幅のピエゾフルラインヘッドが4つ配置されたヘッド
・吐出液滴量:2.4pL
・駆動周波数:30kHz(基材搬送速度:635mm/sec)
<インク乾燥の条件>
・風速:15m/秒
・温度及び加熱方法:基材の表面温度(インクが付与された側の表面の温度)が60℃となるように、基材の背面(インクが付与されていない側の表面)を接触型平面ヒーターで加熱した。
・送風領域:640mm(乾燥時間:1秒間)
上記のようにインクを打滴して記録された画像を、シリコンゴムローラ(硬度:50°、ニップ幅:5mm)を用いて下記条件にて加熱定着した。このようにして、基材上に画像が記録された画像サンプルを得た。
<加熱定着の条件>
・ローラ温度:90℃
・圧力(ニップ圧):0.8MPa
上記で得られた画像サンプルに対して以下の評価を行った。評価結果を下記表5~表7に示す。
画像サンプル中の黒色のベタ画像部の濃度を、分光光度計スペクトロアイ(サカタインクス社製)を用い、ビジュアル(V)濃度にて測定した。
ベタ画像部の濃度は、画像を形成しているインク滴(インクドット)の液滴サイズが小さい場合、基材の白地の影響を受けて濃度が低く現れる。また、処理液によるインク中の分散成分の凝集性が低い場合は、隣接するインクドット同士が干渉を起こし、基材の白地が見えやすくなり、濃度が低く現れる。なお、評価は、ランク3~6が実用上の許容範囲であるとして行った。
<評価基準>
6:画像サンプルにおけるベタ画像部の濃度が2.0を超える。
5:画像サンプルにおけるベタ画像部の濃度が1.9を超え2.0以下である。
4:画像サンプルにおけるベタ画像部の濃度が1.7を超え1.9以下である。
3:画像サンプルにおけるベタ画像部の濃度が1.5を超え1.7以下である。
2:画像サンプルにおけるベタ画像部の濃度が1.3を超え1.5以下である。
1:画像サンプルにおけるベタ画像部の濃度が1.3以下である。
上記の画像記録工程で得た画像サンプル中の2次色画像部を目視で観察し、画像のざらつきを下記基準にしたがって評価した。
2次色画像部は、上記した画像記録工程において、塗設された処理液の上にマゼンタインクM1をベタ状に付与してマゼンタ色のベタ画像を形成し、マゼンタ色のベタ画像上に更にシアンインクC1を網点面積率が50%~80%となるように網点状に付与した後、加熱定着工程で加熱定着処理を施して得られたものである。
なお、「ざらつき(graininess)」とは、インク組成物が基材に着滴した後、液滴同士が合一することで、画像中に微小な濃度ムラが発生し、画素の均一性が低下する現象をいう。
<評価基準>
5:全体にざらつきが見られず均一である。
4:わずかに微小なざらつきが見られるが、全体としてはほぼ均一である。
3:微小なざらつきが見られ、実用上許容されない範囲である。
2:ざらつきが目立ち、実用上許容されない範囲である。
1:強い濃淡のある「ざらつき」が多く発生し、均一とはいえず、実用上許容されない範囲である。
画像記録工程において、塗設された処理液の上にシアンインクC1をベタ状に付与してシアン色のベタ画像を形成し、本画像を目視で観察し、搬送方向に対する筋ムラの発生有無を確認し、かつ、画像サンプル中の筋ムラの発生度合いを下記の評価基準にしたがって評価した。なお、評価は、ランク3~5が実用上の許容範囲であるとして行った。
筋ムラは、互いに隣接するインクドットが干渉を起こすことで、基材の白地が見えやすくなって現れる。
<評価基準>
5:画像サンプルにおける筋ムラの発生が認められない。
4:画像サンプルにごく細いスジが1本視認される。
3:画像サンプルにごく細いスジが数本視認される。
2:画像サンプルに容易に視認される2本以下のスジの発生が確認される。
1:画像サンプルに容易に視認される3本以上のスジの発生が確認される。
上記の実施例及び比較例の各々に対応する処理液25gを、30mlのポリエチレン製のボトルに収容した。処理液が収容された各ボトルを、40℃に設定したサーモセル中に入れて2週間保存した。保存後の処理液を用いて、画像記録工程において、塗設された処理液の上にシアンインクC1をベタ状に付与してシアン色のベタ画像を形成し、本画像を目視で観察し、搬送方向に対する筋ムラの発生有無を確認し、筋ムラの発生度合いを下記の評価基準にしたがって評価した。
筋ムラは、互いに隣接するインクドットが干渉を起こすことで、基材の白地が見えやすくなって現れる。なお、評価は、ランク3~5が実用上の許容範囲であるとして行った。
<評価基準>
5:記録物における筋ムラの発生が認められない。
4:記録物にごく細いスジが1本視認される。
3:記録物にごく細いスジが数本視認される。
2:記録物に容易に視認される2本以下のスジの発生が確認される。
1:記録物に容易に視認される3本以上のスジの発生が確認される。
上記の実施例及び比較例の各々に対応する処理液25gを、30mlのポリエチレン製のボトルに収容した。処理液が収容された各ボトルを、40℃に設定したサーモセル中に入れて2週間保存した。保存前後における各処理液の粘度をそれぞれ測定し、下記式にしたがってΔ粘度(mPa・s)を算出した。
Δ粘度=(40℃で2週間保存した後の処理液の粘度)-(保存前の処理液の粘度)
なお、粘度は、VISCOMETER TV-22(TOKI SANGYO CO.LTD製)を用い、各処理液を25℃に調温した状態で測定した。
上記のようにして得たΔ粘度に基づいて、以下の評価基準にしたがって各処理液の40℃での経時安定性を評価した。処理液は、Δ粘度の値が小さいほど経時安定性に優れ、Δ粘度の値が大きいほど経時安定性に劣るといえる。なお、評価は、ランク3~5が実用上の許容範囲であるとして行った。
<評価基準>
5:Δ粘度が0.1mPa・s以下である。
4:Δ粘度が0.1mPa・sを超え0.4mPa・s以下である。
3:Δ粘度が0.4mPa・sを超え1.0mPa・s以下である。
2:Δ粘度が1.0mPa・sを超え2.0mPa・s以下である。
1:Δ粘度が2.0mPa・sを超える。
以下、表5~表7を参照して、実施例について詳述する。
(1)実施例1~5に示されるように、スルホ基等を含む第1の単量体に由来の構成単位の含有比率が水不溶性樹脂の全質量に対して25質量%以下に調整されることで、ベタ画像部における濃度低下及び筋ムラの発生がより効果的に抑えられる。
(2)また、実施例7及び実施例11~12と実施例8~10とを対比すると明らかなように、芳香環構造又は脂環構造を含む第2の単量体に由来の構成単位の含有比率が水不溶性樹脂の全質量に対して40質量%以下である実施例7~10では、第2の単量体に由来の構成単位の含有比率が40質量%を超える実施例10、11に比べ、ベタ画像部における濃度低下及び筋ムラの発生がより効果的に抑えられている。また、芳香環構造又は脂環構造を含む第2の単量体に由来の構成単位の含有比率は、水不溶性樹脂の全質量に対して10質量%以上に調整されることで、第2の単量体に由来の構成単位の含有比率が10質量%を下回る実施例7と実施例8~10との対比から分かるように、経時した際に生じる筋ムラの発生がより効果的に抑えられている。
(3)酸素原子含量が0.1質量%以下である水不溶性樹脂の粒子を含む処理液を用いた例えば実施例3では、分子中の酸素原子含量が0.1質量%を超える水不溶性樹脂の粒子を含む処理液を用いた実施例13~15に比べ、ベタ画像部での濃度低下の抑制効果が大きく現れた。
(4)水不溶性樹脂における第1の単量体に由来の構成単位の種類が異なる実施例3と実施例16とを対比すると明らかなように、一般式1中のL4は、-C(=O)-O-を有する構造に比べ、-C(=O)-NH-を有する構造が、処理液中での経時保存性の点で優れていた。これは-C(=O)-O-の構造が加水分解を受けやすいためと推定している。
(5)実施例18~20のように、水不溶性樹脂のガラス転移温度(Tg)が100℃を下回る場合、筋ムラの抑制効果が低下し、処理液の経時安定性の低下をも招く傾向がみられた。そのため、水不溶性樹脂のTgは100℃以上であることが望ましい。
また、水不溶性樹脂がモノマー成分としてMAを含み、かつ、Tgが100℃以上である場合、実施例21~22に示されるように、ベタ画像部における濃度低下の抑制効果が著しく、所望とする濃度のベタ画像部が得られた。
(6)実施例3、31、32のように、水不溶性樹脂の添加量が3質量%~10質量%の範囲では、いずれもベタ画像部における濃度低下が抑制されており、筋ムラの発生及び画像のざらつきを抑えた画像が得られた。
例えば、比較例1のように水溶性樹脂を用いた場合、樹脂が基材に浸透して基材の表面に偏在しにくいため、ベタ画像部の濃度低下及び筋ムラの発生を抑制することはできなかった。また、比較例1のインクセットは、処理液の経時での安定性は比較的良好なものの、初期の粘度が上昇する傾向がみられた。
また、比較例2、3では、水不溶性樹脂が芳香環構造及び脂環構造を有しないため、経時した際の筋ムラの発生が顕著にみられ、処理液の経時安定性に劣っていた。
比較例4では、水不溶性樹脂がスルホ基又はスルホ基の塩を有しないため、ベタ画像部における濃度低下が抑えられず、筋ムラ及び画像のざらつきが顕著にみられた。また、処理液の経時安定性にも著しい悪化が認められた。
下記表8に示す組成となるように各成分を混合し、18種のインク組成物(マゼンタインク、シアンインク、イエローインク、ブラックインク、オレンジインク、グリーンインク、及びバイオレットインクの各々について3種)を調製した。そして、18種のインク組成物のいずれか1つと、既述の処理液A-3、A-9、A-14、A-16及びA-22のいずれか1つと、を任意に選択して組み合わせることでインクセットを用意した。
なお、ベタ画像の濃度及び筋ムラの評価については、各色のベタ画像を形成し、上記の実施例1等と同様にして評価した。
また、画像のざらつきの評価については、下記の表8に示す18種のインク組成物から任意の2種を選択し、以下のようにして評価した。すなわち、
上記の画像記録工程にて表8から選択した2種のインク組成物を用いて画像サンプルを得、得られた画像サンプル中の2次色画像部を目視で観察し、上記の「-2.画像のざらつき-」と同様にして評価した。なお、2次色画像部は、塗設された処理液の上に2種のインク組成物うちの一方をベタ状に付与してベタ画像を形成し、さらにベタ画像上に他方を網点面積率が50%~80%となるように網点状に付与し、加熱定着処理を施して得られたものである。
・Pro-Jet Cyan APD3000:ピグメント・ブルー15:3を含有する顔料分散液(顔料濃度:12.0質量%、不揮発分濃度:21.8質量%)、FUJIFILM Imaging Colorants社製
・Pro-Jet Magenta APD3000:ピグメント・レッド122を含有する顔料分散液(顔料濃度:15.0質量%、不揮発分濃度:21.6質量%)、FUJIFILM Imaging Colorants社製
・Pro-Jet Yellow APD3000:ピグメントイエロー74を含有する顔料分散液(顔料濃度:13.6質量%、不揮発分濃度:24.6質量%)、FUJIFILM Imaging Colorants社製
・Pro-Jet Black APD3000;ピグメント・ブラック7を含有する顔料分散液(顔料濃度:10.0質量%、不揮発分濃度:18.9質量%)、FUJIFILM Imaging Colorants社製
・FUJI SP ORANGE 651:ピグメント・オレンジ43を含有する顔料分散液(顔料濃度:15.0質量%、不揮発分濃度:19.0質量%)、冨士色素(株)製
・FUJI SP GREEN 7409:ピグメント・グリーン7を含有する顔料分散液(顔料濃度:15.0質量%、不揮発分濃度:17.5質量%)、冨士色素(株)製
・FUJI SP VIOLET 9609:ピグメント・バイオレット23を含有する顔料分散液(顔料濃度:16.0質量%、不揮発分濃度:18.5質量%)、冨士色素(株)製
・ラテックスA:上記の樹脂粒子(B-01)と水とを混合して固形分23.20質量%に調整した樹脂粒子の水分散物
・PE-108:ニューポール(登録商標) PE-108、ポリオキシエチレン・ポリオキシプロピレン・ブロックポリマー(三洋化成工業(株)製)
・GP250:サンニックス GP-250、ポリオキシプロピレングリセリルエーテル(三洋化成工業(株)製)
・PEG-200:ポリエチレングリコール(三洋化成工業(株)製)
・MFTG:トリプロピレングリコールモノメチルエーテル(日本乳化剤(株)製)
・PVP K15:ポリビニルピロリドン(東京化成工業(株)製)
・オルフィン E1010:アセチレングリコール系界面活性剤(日信化学工業(株)製)
・オルフィン E1020:アセチレングリコール系界面活性剤(日信化学工業(株)製)
・セロゾール(登録商標) 524D:エステルワックス(中京油脂(株)製)
・スノーテックス(登録商標) XS:コロイダルシリカ(日産化学工業(株)製)
・BYK-024:シリコーン系消泡剤(ビックケミー・ジャパン社製)
・Capstone FS-63:フッ素系界面活性剤(デュポン社製)
Claims (12)
- 着色剤及び水を含むインク組成物、並びに、
スルホ基及びスルホ基の塩から選ばれる少なくとも一つの基を含む第1の単量体に由来の構成単位、及び、芳香環構造及び脂環構造から選ばれる少なくとも一つの構造を含む第2の単量体に由来の構成単位を有する水不溶性樹脂の粒子と、前記インク組成物中の着色剤を凝集させる化合物と、水と、を含む処理液、
を有するインクセット。 - 前記第2の単量体に由来の構成単位は、下記一般式A~一般式Eのいずれかで表される構成単位の群より選ばれる少なくとも一つの構成単位である請求項1に記載のインクセット。
式中、R11は、メチル基又は水素原子を表し、R12は、水素原子又は炭素数1~10の直鎖状若しくは分岐鎖状のアルキル基を表す。nは、0~5の整数を表し、nが2以上である場合は複数のR12は互いに同一でも異なっていてもよい。L11は、単結合、炭素数1~18の直鎖状、分岐鎖状若しくは環状のアルキレン基、炭素数6~18のアリーレン基、-O-、-NH-、-S-、及び-C(=O)-からなる群より選ばれる1つ又は2つ以上を連結した2価の連結基を表す。 - 前記第2の単量体に由来の構成単位の合計の、前記水不溶性樹脂中における含有比率が、前記水不溶性樹脂の全質量に対して、10質量%~40質量%である請求項1又は請求項2に記載のインクセット。
- 前記第2の単量体に由来の構成単位に対する、前記第1の単量体に由来の構成単位の質量比率が、0.15~0.90である請求項1~請求項3のいずれか1項に記載のインクセット。
- 前記第1の単量体に由来の構成単位の前記水不溶性樹脂中における含有比率が、前記水不溶性樹脂の全質量に対して、5質量%~25質量%である請求項1~請求項5のいずれか1項に記載のインクセット。
- 前記第2の単量体の少なくとも一つは、単量体の分子量に対する単量体中の酸素原子の質量の比率が、0.1以下である請求項1~請求項6のいずれか1項に記載のインクセット。
- 前記第2の単量体の少なくとも一つが、スチレンである請求項1~請求項7のいずれか1項に記載のインクセット。
- 前記水不溶性樹脂のガラス転移温度が、100℃以上である請求項1~請求項8のいずれか1項に記載のインクセット。
- 前記着色剤を凝集させる化合物に対する、前記水不溶性樹脂の粒子の含有比率が、質量基準で0.19~0.5である請求項1~請求項9のいずれか1項に記載のインクセット。
- 表面に水滴を付与して3秒経過したときの接触角が70°以上である基材の少なくとも一方の面に、請求項1~請求項10のいずれか1項に記載のインクセットの処理液を付与する前処理工程と、
前記処理液が付与された前記一方の面に、請求項1~請求項10のいずれか1項に記載のインクセットのインク組成物をインクジェット法により吐出して画像を記録する画像記録工程と、
を有する画像記録方法。 - 前記基材は、塗工層を有する紙基材である請求項11に記載の画像記録方法。
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EP3434742B1 (en) | 2023-10-25 |
US20190010349A1 (en) | 2019-01-10 |
JPWO2017163738A1 (ja) | 2018-09-27 |
EP3434742A1 (en) | 2019-01-30 |
EP3434742A4 (en) | 2019-04-10 |
JP6678731B2 (ja) | 2020-04-08 |
CN109071986B (zh) | 2021-09-14 |
US10639905B2 (en) | 2020-05-05 |
CN109071986A (zh) | 2018-12-21 |
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