WO2022186396A1 - 前処理組成物、印刷セット及び捺染方法 - Google Patents
前処理組成物、印刷セット及び捺染方法 Download PDFInfo
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- WO2022186396A1 WO2022186396A1 PCT/JP2022/009567 JP2022009567W WO2022186396A1 WO 2022186396 A1 WO2022186396 A1 WO 2022186396A1 JP 2022009567 W JP2022009567 W JP 2022009567W WO 2022186396 A1 WO2022186396 A1 WO 2022186396A1
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Classifications
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- 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
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- B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
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- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
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- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
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- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
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- D06P1/5242—Polymers of unsaturated N-containing compounds
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- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/54—Substances with reactive groups together with crosslinking agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/001—Special chemical aspects of printing textile materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/002—Locally enhancing dye affinity of a textile material by chemical means
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2066—Thermic treatments of textile materials
- D06P5/2077—Thermic treatments of textile materials after dyeing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
-
- 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
-
- 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
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
-
- 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
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
Definitions
- the present invention relates to a pretreatment composition for inkjet textile printing, an inkjet textile printing method, a printing set containing the pretreatment composition, and a printed matter printed using the printing set.
- Water-soluble dyes are examples of coloring agents used in inkjet textile printing. Such dyes have vivid hues and a wide reproducible color gamut. On the other hand, water-soluble dyes have low light fastness, and have the disadvantage that the steps of fixing the dye on the fiber, washing with water, etc., and the treatment of the waste liquid generated by the washing with water, etc. are complicated. For this reason, the use of water-insoluble colorants instead of water-soluble dyes has attracted attention.
- polyester fiber meh fabric used for sportswear, etc.
- thin or coarsely knitted fabric the other side that is not printed on the fiber will also be printed.
- "Strike-through" in which the colorant permeates, may occur, and this is one of the major problems of density reduction.
- the pretreatment liquid hereinafter also referred to as a pretreatment composition
- the pretreatment liquid is applied.
- the above-mentioned "bleed-through” may occur, which is a major problem of lowering whiteness and hiding properties. It is one.
- unevenness may be observed on the white base due to fluffing of the fibers in the pretreated portion. This unevenness also greatly deteriorates the quality of the printed matter. Therefore, a pretreatment composition that can solve these problems, a textile printing method, a printing set comprising the pretreatment composition and an ink composition are highly desired.
- An object of the present invention is to provide a pretreatment composition that is less likely to cause the above traces, strike-through, and fluffing, and that provides an image with high whiteness and high hiding power when color inks including white are used;
- a print set (and also a print set with color inks) with a pretreatment composition and an ink composition, an inkjet textile printing method.
- the present inventors have found that the above problems can be solved by a pretreatment composition containing a cationic polymer containing a specific structural unit and a cross-linking agent.
- the present inventors have found that the above problems can be solved by an inkjet textile printing method having predetermined steps using a pretreatment composition containing and a water-based ink composition, and completed the present invention. That is, the present invention relates to the following 1) to 39).
- a pretreatment composition used for forming a wet precoat layer that receives a water-based ink composition that forms an image on a fabric by an inkjet method, the pretreatment satisfying all the requirements of [1] to [4] below.
- Composition [1]
- the water-based ink composition contains water, a pigment, a resin emulsion, a water-soluble organic solvent, and a surfactant.
- It is used to form a wet precoat layer in which the amount of the pretreatment composition applied per unit area is more than 0.035 g/cm 2 and less than 0.070 g/cm 2 .
- the pretreatment composition contains more than 1.4% by mass and less than 10.5% by mass of a cationic polymer and the total mass of the pretreatment composition, based on water and the total mass of the pretreatment composition. It contains 0.1% by mass or more and less than 2.7% by mass of a cross-linking agent.
- the cationic polymer contains at least one selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units, and epihalohydrin structural units.
- the pretreatment composition according to 1) wherein the cross-linking agent contains one or more cationic cross-linking agents selected from the group consisting of blocked isocyanate group-containing compounds, carbodiimide group-containing compounds, and oxazoline group-containing compounds.
- the pretreatment composition according to 2) wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or higher.
- a printing set comprising the pretreatment composition according to any one of 1) to 4), and an aqueous ink composition containing water, a pigment, a resin emulsion, a water-soluble organic solvent, and a surfactant.
- a pretreatment composition comprising water, a cationic polymer, a cross-linking agent; a water-based white ink composition containing water, a white pigment, a urethane resin, and a water-soluble organic solvent,
- the content of the cationic polymer in the pretreatment composition is more than 1.4% by mass and less than 10.5% by mass with respect to the total mass of the pretreatment composition, and the content of the cross-linking agent
- a print set of a pretreatment composition and a water-based white ink composition in an amount of 0.1% by weight or more and less than 2.7% by weight relative to the total weight of the pretreatment composition.
- the cationic polymer is a polymer containing at least one structural unit selected from the group consisting of an allylamine structural unit, a diallylamine structural unit, a diallylammonium structural unit, and an epihalohydrin structural unit.
- the cross-linking agent contains one or more cationic cross-linking agents selected from the group consisting of blocked isocyanate group-containing compounds, carbodiimide group-containing compounds, and oxazoline group-containing compounds. . 12) The printing set according to 11), wherein the dissociation temperature of the blocked isocyanate group-containing compound is 120°C or higher.
- a method for inkjet printing comprising the step of forming 21) A pretreatment step of applying the pretreatment composition contained in the printing set according to any one of 9) to 19) to the fabric to form a wet precoat layer, and drying the fabric after the pretreatment step. 9) to all or part of the wet precoat layer without using a water-based white ink composition contained in the printing set according to any one of 9) to 19) by an inkjet method to form an image. and a water-based ink composition included in the printing set according to any one of 17) to 19) in part or all of the area where the image is formed by ejecting the water-based white ink composition.
- a method for inkjet printing comprising a step of ejecting a substance by an inkjet method to form an image. 22) The inkjet textile printing method according to 20) or 21), wherein the fabric is polyester or a blend containing polyester. 23) The inkjet textile printing method according to 22), which includes a step of drying the image-formed fabric at 130° C. or lower after the step of applying the water-based ink composition. 24) The inkjet printing method according to 20) or 21), wherein the fabric is cotton or a cotton-containing blend. 25) 24). The inkjet printing method according to 24), further comprising, after the pretreatment step, a pressurizing step of applying pressure to the area where the wet precoat layer is formed.
- a pretreatment composition comprising water, a cationic polymer, a cross-linking agent;
- the content of the agent is 0.1% by mass or more and less than 2.7% by mass with respect to the total mass of the pretreatment composition
- the water-based ink composition contains water, a pigment, a resin emulsion, a water-soluble organic
- Monomer B A monomer in which R is a C1-C4 alkyl group in the following formula (1).
- Monomer C A monomer in which R is an aryl group or an aryl C1-C4 alkyl group in the following formula (1).
- the cationic polymer contains at least one structural unit selected from the group consisting of an allylamine structural unit, a diallylamine structural unit, a diallylammonium structural unit, and an epihalohydrin structural unit.
- a pretreatment composition a pretreatment composition, and an ink, which are less likely to cause the above traces, strike-through, and fluffing, and which provide an image having high color development when using color inks including white.
- a printing set with the composition furthermore, a printing set with color ink
- an inkjet textile printing method could be provided.
- the present invention provides an inkjet textile printing method that is less likely to cause the above traces, strike-through, and fluffing, and that provides an image with high color development when using color inks including white.
- the pretreatment composition of this embodiment contains water, a cationic polymer, and a cross-linking agent. Further, the printing set of the present embodiment has the pretreatment composition and a water-based ink composition, and the water-based ink composition contains water and a pigment.
- a pretreatment composition according to one preferred embodiment of the present invention is a pretreatment composition used for forming a wet precoat layer that receives a water-based ink composition that forms an image on a fabric by an inkjet method. , satisfy all of the following requirements [1] to [4].
- the water-based ink composition contains water, a pigment, a resin emulsion, a water-soluble organic solvent, and a surfactant.
- the pretreatment composition contains more than 1.4% by mass and less than 10.5% by mass of a cationic polymer and the total mass of the pretreatment composition, based on water and the total mass of the pretreatment composition. It contains 0.1% by mass or more and less than 2.7% by mass of a cross-linking agent.
- the cationic polymer contains at least one selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units, and epihalohydrin structural units.
- a printing set includes a pretreatment composition containing water, a cationic polymer, and a cross-linking agent, and a water-based white ink containing water, a white pigment, a urethane resin, and a water-soluble organic solvent. and a composition.
- the resin in the ink composition agglomerates, and it is possible to suppress the penetration of the pigment into the fabric fibers, so that the color development can be improved.
- the print set of the present embodiment includes a pretreatment composition containing a cationic polymer and a cross-linking agent, thereby maintaining high color development and improving adhesion.
- the print set of the present embodiment can improve the adhesion even when used in such a textile printing method.
- the pretreatment composition contains water, a cationic polymer that is more than 1.4% by mass and less than 10.5% by mass with respect to the total weight of the pretreatment composition, and the total weight of the pretreatment composition It contains 0.1% by mass or more and less than 2.7% by mass of a cross-linking agent.
- the pretreatment composition contains water.
- water pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, or ultrapure water can be used without any particular limitation.
- the content of water is not particularly limited and may be determined as needed. % by mass), preferably 70 to 99% by mass, more preferably 80 to 98% by mass.
- the pretreatment composition is characterized by containing more than 1.4% by mass and less than 10.0% by mass of the cationic polymer relative to the total mass of the pretreatment composition.
- the cationic polymer contains at least one selected from the group consisting of allylamine structural units, diallylamine structural units, diallylammonium structural units, and epihalohydrin structural units, and is selected from the group consisting of allylamine structural units and epihalohydrin structural units. It is more preferable to include at least one of them. All of the cationic polymers described above are strong electrolytes, and the cationic polymers have good dissolution stability in the pretreatment composition and are excellent in ability to reduce pigment dispersion in the ink.
- allylamine acetate copolymer As the cationic polymer containing allylamine structural units, known ones can be appropriately selected and used.
- allylamine acetate copolymer As the cationic polymer containing allylamine structural units, known ones can be appropriately selected and used.
- allylamine acetate copolymer allylamine acetate ⁇ diallylamine acetate copolymer, allylamine hydrochloride ⁇ dimethylallylamine hydrochloride copolymer, allylamine ⁇ dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, poly Methyldiallylamine Acetate, Polydiallyldimethylammonium Chloride, Diallylamine Acetate/Sulfur Dioxide Copolymer, Diallylmethylethylammonium Ethyl Sulfate/Sulfur Dioxide Cop
- cationic polymers containing allylamine structural units can be used, and specific examples include PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA-HCL-10L, PAA-H-HCL, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA-D11-HCL, PAA-D41-HCL, PAA-D19-HCL, PAS-21CL, PAS-M-1L, PAS-M-1, PAS-22SA, PAS-M-1A, PAS-H-1L, PAS-H-5L, PAS-H-10L, PAS-92, PAS-92A, PAS-J-81L, PAS-J-81 (product names, manufactured by Nittobo Medical Co., Ltd.), Himo Neo-600, Himolock Q -101, Q-311, Q-
- cationic polymer containing the diallylamine structural unit known ones can be appropriately selected and used. Specific examples include PAS-21CL, PAS-21, PAS-M-1L, and PAS-M. -1, PAS-M-1A, PAS-92, PAS-92A (manufactured by Nittobo Medical); and Unisense KCA100L and KCA101L (manufactured by Senka).
- the cationic polymer containing the diallylammonium structural unit known ones can be appropriately selected and used, and specific examples thereof include, for example, hydrochlorides or ethyl sulfates of diallyldimethylammonium or diallylmethylethylammonium. etc. can be mentioned.
- the cationic polymer containing the diallylammonium structural unit exhibits particularly excellent cohesiveness, and is preferable because it is possible to obtain a printed matter having excellent color developability with less color bleeding and uneven coloration on the substrate. .
- cationic polymer containing the diallylammonium structural unit a commercially available product can be used, and specific examples thereof include PAS-H-1L, PAS-H-5L, PAS-H-10L, PAS-24. , PAS-J-81L, PAS-J-81, PAS-J-41 (manufactured by Nittobo Medical Co., Ltd.); be able to. Furthermore, PAS-880 (manufactured by Nittobo Medical Co., Ltd.) can be mentioned as a commercial product of a cationic polymer compound containing both a diallylamine structural unit and a diallylammonium structural unit.
- the cationic polymer containing an epihalohydrin structural unit known ones can be appropriately selected and used. Specific examples include epihalohydrin-modified polyamine compounds, epihalohydrin-modified polyamide compounds, epihalohydrin-modified polyamide polyamine compounds, and epihalohydrin. - amine copolymers and the like. Epichlorohydrin or methylepichlorohydrin is preferably selected as the epihalohydrin in terms of availability. A printed matter using a cationic polymer containing the epihalohydrin structural unit is excellent in water resistance, and is also preferably selected from this point of view. As the cationic polymer containing epihalohydrin structural units, commercially available products can be used.
- the above cationic polymer may be synthesized by a known synthesis method, or may be a commercially available product.
- the content of the cationic polymer is more than 1.4% by mass and less than 10.5% by mass, preferably 1.7 to 8.0% by mass, relative to the total mass of the pretreatment composition, More preferably 2.0 to 7.0% by mass, particularly preferably 2.5 to 6.0% by mass.
- the addition amount is less than 10.5% by mass, there is a tendency to be excellent in storage stability and reduction of traces.
- the viscosity of a 10 mass % aqueous solution of the cationic polymer at 25° C. is preferably 1.0 to 5.0 mPa ⁇ s, more preferably 1.0 to 2.5 mPa ⁇ s, still more preferably 1.0 to 2.5 mPa ⁇ s. 0 mPa ⁇ s, most preferably 1.0 to 1.5 mPa ⁇ s.
- the weight-average molecular weight of the cationic polymer is usually 300 to 40,000 in consideration of the miscibility with other components contained in the pretreatment composition, the water resistance of the pretreated fabric, and the fastness to washing and adhesion. , preferably 500 to 18,000, preferably 750 to 15,000, more preferably 1,000 to 10,000.
- the weight-average molecular weight is 300 or more, effective cohesiveness is obtained, and strike-through and whiteness tend to be improved. If the weight average molecular weight is 40000 or less, it can be used as an aqueous solution and tends to be excellent in storage stability.
- the weight average molecular weight of the cationic polymer can be measured by standard polystyrene conversion using gel permeation chromatography (GPC).
- the pretreatment composition is characterized by containing 0.1% by mass or more and less than 2.7% by mass of a cross-linking agent with respect to the total mass of the pretreatment composition.
- the cross-linking agent preferably contains, for example, one or more cationic cross-linking agents selected from the group consisting of blocked isocyanate group-containing compounds, carbodiimide group-containing compounds, and oxazoline group-containing compounds. More preferably, at least a block-type isocyanate group-containing compound and a carbodiimide group-containing compound are included.
- the term "blocked isocyanate group-containing compound” refers to a compound in which the isocyanate group in the polyisocyanate compound is blocked with a blocking agent.
- the above-mentioned blocked isocyanate group-containing compound represents a compound in which the isocyanate group in the polyisocyanate compound is blocked with a blocking agent.
- a polyisocyanate compound is a compound having two or more isocyanate groups in one molecule.
- the polyisocyanate compound include aliphatic isocyanates, alicyclic isocyanates, araliphatic isocyanates, aromatic isocyanates, etc., and these modified form of.
- Modified polyisocyanate compounds include polymers such as isocyanurate; biuret; adducts of trimethylolpropane and pentaerythritol with polyhydric alcohols.
- aliphatic isocyanate for example, a diisocyanate having a linear or branched aliphatic hydrocarbon group between two isocyanate groups is preferable.
- the number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 9 or less, still more preferably 8 or less.
- tetramethylene diisocyanate pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl hexamethylene diisocyanate and the like.
- alicyclic isocyanate examples include hydrogenated xylylene diisocyanate (H6XDI), 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,5- or 2,6-norbornane diisocyanate and the like.
- H6XDI hydrogenated xylylene diisocyanate
- H12MDI 4,4′-dicyclohexylmethane diisocyanate
- IPDI isophorone diisocyanate
- 2,5- or 2,6-norbornane diisocyanate and the like examples include m- or p-xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI).
- aromatic isocyanate examples include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate. (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 1,5-naphthylene diisocyanate, 2, and 6-dimethylbenzene-1,4-diisocyanate.
- MDI 1,3- or 1,4-phenylene diisocyanate
- TDI 2,4- or 2,6-tolylene diisocyanate
- MDI 4,4'- or 2,4'-diphenylmethane diisocyanate.
- MDI m- or p-isocyanatophenyls
- the blocking agent examples include amines such as 3,5-dimethylpyrazole (DMP), 1,2,4-triazole and diisopropylamine; phenols such as phenol and cresol; oximes such as methylethylketoxime; lactams such as caprolactam; and compounds having active hydrogen such as active methylene compounds such as diethyl malonate and ethyl acetoacetate.
- DMP 3,5-dimethylpyrazole
- methylethylketoxime are preferred, and 3,5-dimethylpyrazole (DMP) is more preferred.
- the dissociation temperature of the blocked isocyanate group-containing compound is preferably 120°C or higher, more preferably 125°C or higher, from the viewpoint of storage stability, scratch resistance, and adhesion.
- the temperature is 120° C. or higher, the storage stability of the pretreatment composition tends to be improved.
- the temperature is preferably 200° C. or lower, more preferably 180° C. or lower.
- it is necessary to perform the drying process after printing at a drying temperature of 130 ° C. or less in order to prevent dye migration (hereinafter simply referred to as dye transfer). , preferably 130° C. or less.
- the carbodiimide group-containing compound is preferably a polycarbodiimide compound containing two or more carbodiimide groups in one molecule, from the viewpoints of storage stability, scratch resistance, solvent resistance, and adhesion of the pretreatment composition.
- a carbodiimide group-containing compound for example, a compound obtained by blocking the terminal isocyanate group of a condensation reaction product obtained by a decarboxylation condensation reaction in the presence of a carbodiimidation catalyst of diisocyanates with a hydrophilic group is preferable.
- Diisocyanates used in the decarboxylation condensation reaction include, for example, hexamethylene diisocyanate (HDI), decamethylene diisocyanate, aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate; 4,4′-dicyclohexylmethane diisocyanate ( H12MDI), isophorone diisocyanate (IPDI), 2,5- or 2,6-norbornane diisocyanate, hydrogenated xylylene diisocyanate (H6XDI), hydrogenated tolylene diisocyanate, 2,4-bis-(8-isocyanatooctyl)-1 ,3-dioctylcyclobutane (OCDI) and other alicyclic diisocyanates; m- or p-xylylene diisocyanate (XDI), araliphatic diisocyanates such as tetramethylxylylene diis
- the compound obtained by blocking the terminal isocyanate group of the condensation reaction product with a hydrophilic group is a compound having a functional group capable of reacting with the isocyanate group, such as polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, and the like. is mentioned. Among them, polyethylene glycol monomethyl ether is preferable from the viewpoint of compatibility with the pretreatment composition of the carbodiimide group-containing compound and storage stability of the pretreatment composition. By adjusting the number of moles of ethylene oxide added to the polyethylene glycol monomethyl ether, the form of the obtained carbodiimide group-containing polymer can be incorporated into the aqueous composition as an emulsion or aqueous solution.
- the carbodiimide group-containing compound is preferably formulated as an aqueous solution or emulsion in the pretreatment composition. From the viewpoint of the storage stability of the treatment composition, it is preferable to add it to the pretreatment composition as an aqueous solution.
- Examples of commercially available carbodiimide group-containing compounds include Carbodilite E-02, Carbodilite E-03A, Carbodilite E-05, Carbodilite V-02, Carbodilite V-02-L2, Carbodilite V-04 (Nisshinbo Chemical Co., Ltd. manufactured by a company, trade name), and the like. Among these, Carbodilite E-02 and Carbodilite V-04 are preferred from the viewpoint of storage stability of the pretreatment composition.
- the oxazoline group-containing compound is preferably formulated as an aqueous solution or emulsion in the pretreatment composition.
- Polyoxazoline compounds having two or more oxazoline groups in are preferred.
- Epocross WS series such as “Epocross WS-300", “Epocross WS-500”, and “Epocross WS-700” (manufactured by Nippon Shokubai Co., Ltd., water-soluble type); Epocross K-2010E, Epocross K-2020E, etc., "Epochros K series” (manufactured by Nippon Shokubai Co., Ltd., trade name, emulsion type).
- Epocross WS-300, Epocross WS-500, and Epocross WS-700 are preferred from the viewpoint of storage stability of the pretreatment composition.
- the content of the crosslinking agent is 0.1% by mass or more and less than 2.7% by mass, preferably 0.2 to 2.0% by mass, more preferably 0.4 to 1.5% by mass, more preferably 0.6 to 1.0% by mass. If it is 0.1% by mass or more, effective adhesion tends to be obtained. In addition, if it is 2.7% by mass or less, it tends to be excellent in storage stability and reduction of traces.
- the pretreatment composition contains a resin emulsion, a water-soluble organic solvent, a surface tension adjuster, an anti-mold agent, an antiseptic, a pH adjuster, a chelating reagent, an anti-rust agent, a water-soluble ultraviolet absorber, It may further contain preparation agents such as antioxidants and thickeners.
- resin emulsion-- examples include (meth)acrylic resins, (meth)acrylic resin copolymers, styrene-maleic anhydride copolymer resins, epoxy resins, urethane resins, polyether resins, polyamide resins, and unsaturated polyester resins.
- the resin emulsion may contain two or more resins. Moreover, two or more kinds of resins may form a core/shell structure. One type of resin emulsion may be used alone, or two or more types may be used in combination.
- resin emulsions it is preferable to use a resin that forms a transparent coating film, and from the viewpoint of storage stability, scratch resistance, and adhesion of the pretreatment composition, acrylic resin emulsions and urethane resin emulsions are preferable.
- the above (meth)acrylic resin and (meth)acrylic resin copolymer emulsions are commercially available, and most of them are emulsions with a solid content concentration of 30 to 60% by mass.
- emulsions with a solid content concentration of 30 to 60% by mass.
- Movinyl 966A, 6963, 6960 (acrylic resin emulsion, all trade names), 6969D, RA-033A4 (styrene / acrylic resin emulsion, all trade names) and BASF John Krill 7100, PDX-7370, PDX-7341 (styrene/acrylic resin emulsion, all trade names), DIC Corporation Boncoat EC-905EF, 5400EF, CG-8400 (acrylic/styrene emulsion), and the like.
- urethane resin emulsions are commercially available, and most of them are emulsions with a solid content concentration of 30 to 60% by mass.
- examples of commercially available urethane resin emulsions include Permalin UA-150, 200, 310, 368, 3945, Ukote UX-320, 340 (manufactured by Sanyo Kasei Co., Ltd.); Hydran WLS-201, 210, HW-312B.
- polycarbonate-based urethane resins include, for example, Permalin UA-310, 3945; Ukote UX-320; Hydran WLS-210, 213, 250;
- polyether-based urethane resins include Permaline UA-150, 200; Ukote UX-340; Hydran WLS-201, 202, 230;
- the acidic group may be alkali chlorided.
- a urethane resin having an acidic group is added to water and stirred to prepare an aqueous solution, and an alkaline compound is added thereto to adjust the pH to 6.0 to 12.0, whereby the acidic group is alkali chlorided. can do.
- alkaline compounds include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; water of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. oxide; and the like. Alkaline compounds may be used alone or in combination of two or more.
- water-soluble organic solvent examples include glycol-based solvents, polyhydric alcohols, and polyhydric alcohol alkyl ethers.
- glycol solvents include glycerin, polyglycerin (#310, #750, #800), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, undeca glycerin, dodecaglycerin, tridecaglycerin, tetradecaglycerin and the like.
- polyhydric alcohols examples include C2-C6 polyhydric alcohols having 2 to 3 alcoholic hydroxyl groups, di- or tri-C2-C3 alkylene glycols, and poly C2-C3 alkylene glycols having 4 or more repeating units and a molecular weight of about 20,000 or less ( Liquid polyalkylene glycol) and the like are preferred.
- polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, thiodiglycol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4- pentanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol and the like.
- polyhydric alcohol alkyl ethers examples include alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, trialkylene glycol monoalkyl ethers, and the like. Specifically, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoisobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol.
- water-soluble organic solvents include, for example, urea, ethylene urea, sugars and the like.
- water-soluble organic solvent may be used alone, or two or more types may be used in combination.
- water-soluble organic solvent at least one selected from glycerin, diethylene glycol, triethylene glycol, propylene glycol, 1,2-hexanediol, 1,6-hexanediol, 1,5-pentanediol and diethylene glycol monobutyl ether. preferably included.
- the content of the water-soluble organic solvent is usually 0.5 to 20% by mass, preferably 1 to 15% by mass, more preferably 2 to 10% by mass, relative to the total mass of the pretreatment composition.
- the type of the surface tension modifier is not particularly limited, for example, surfactants selected from acetylene glycol and polyalkylene glycol are preferred. Containing a surfactant suppresses an increase in the viscosity of the pretreatment composition, aggregation of components, and the like, and improves storage stability. Among the above, the pretreatment composition containing at least polyalkylene glycol as a surfactant tends to further improve the whiteness of the substrate and the strike-through.
- acetylene glycol surfactant examples include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,4,7,9-tetramethyl-5-decyne-4,7 -diol, 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol or alkylene oxide adducts thereof are preferred, and the alkylene More preferred are surfactants selected from oxide adducts.
- the alkylene oxide examples include C2-C4 linear, branched and cyclic alkylene oxides. Among these, linear or branched alkylene oxides are preferred.
- Surfactants selected from the above alkylene oxide adducts include, for example, the Surfynol series (420, 440, 465, 61, etc.) manufactured by Nissin Chemical Industry Co., Ltd., and the Olphine series (E1004, E1010, EXP-4001, etc.). ).
- Polyalkylene glycol surfactants include, for example, interfaces selected from polyoxyalkylene alkyl ethers (eg, polyoxyethylene alkyl ethers), fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polyoxy C2-C4 alkylene glycols. Activators are preferred. Among these, polyoxy C2-C4 alkylene glycol is preferred.
- Polyoxyalkylene alkyl ethers include polyoxyalkylene branched decyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene lauryl ether, and the like.
- Examples of commercially available products include Noigen XL-40, 50, 60, 70, 80, 100, 140, 160, Noigen TDS-30, 50, 70, 80, 90 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 100, 120 and the like.
- Examples of fatty acid ethylene oxide adducts include stearic acid ethylene oxide adducts, polyethylene glycol lauric acid esters, and the like.
- Examples of commercially available products thereof include Emanone 1112, 3199V, 3299V, 3299VR, 3201M-V manufactured by Kao Corporation.
- Examples of commercial products of higher alkylamine ethylene oxide adducts include Amit 102, 105, 105A, 302 and 320 manufactured by Kao Corporation.
- Examples of commercially available polyoxy C2-C4 alkylene glycols include Emulgen PP-290 (160/30 polyethylene glycol/polypropylene glycol copolymer) manufactured by Kao Corporation; Newpol PE- manufactured by Sanyo Chemical Industries, Ltd.
- PE-108 polyoxyethylene polyoxypropylene block polymer
- polyoxy C2-C4 alkylene glycol polyoxy C2-C3 alkylene glycol is preferable, and polyoxyethylene polyoxypropylene glycol is more preferable.
- the number of oxy-C2 alkylene groups in the total number of oxy-C2-C4 alkylene groups in the polyoxy-C2-C4 alkylene glycol is usually less than 50%, preferably 15-45%, more preferably 20-40%. For example, when the total number of bonds of the oxyC2 alkylene group, the oxyC3 alkylene group and the oxyC4 alkylene group is 10, the number of bonds of the oxyalkylene group is less than 5.
- the numbers of bonds of the oxy C2-C4 alkylene groups are all average values.
- the weight average molecular weight of the hydrophobic group is usually 2250 to 4000, preferably 2750 to 3600.
- Examples of a compound that satisfies both the content of the oxy-C2 alkylene group and the weight-average molecular weight of the hydrophobic group include Epan U-103.
- the content of the surfactant is usually 0.05 to 5%, preferably 0.05 to 3%, more preferably 0.05 to 1%, still more preferably 0, relative to the total mass of the pretreatment composition. .1 to 0.5%. Such a content tends to improve the washing fastness and abrasion resistance of printed fibers. Moreover, the storage stability of the pretreatment composition tends to be excellent.
- Antifungal agents-- Specific examples of the antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof, and the like. are mentioned.
- preservative-- examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloarylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole type, isothiazoline type, dithiol type, pyridine oxide type, nitropropane type, organic tin type, phenol type, quaternary ammonium salt type, triazine type, thiazine type, anilide type, adamantane type, dithiocarbamate type, brominated indanone type , benzyl bromoacetate-based compounds, inorganic salt-based compounds, and the like.
- organic halogen compounds include sodium pentachlorophenol.
- pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide.
- isothiazolin compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. are mentioned.
- antiseptics and antifungal agents include sodium acetate anhydride, sodium sorbate, sodium benzoate, trade names Proxel RTM GXL (S) and Proxel RTM XL-2 (S) manufactured by Lonza. are mentioned.
- pH adjuster-- Any substance can be used as the pH adjuster as long as it can control the pH of the ink in the range of, for example, 3.0 to 9.0 without adversely affecting the pretreatment composition to be prepared.
- pH adjusters include hydroxides of alkali metals, hydroxides of alkaline earth metals, aliphatic amine compounds and alcohol amine compounds.
- Alkali metal hydroxides include, for example, lithium hydroxide, sodium hydroxide and potassium hydroxide.
- Alkaline earth metal hydroxides include, for example, beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. Among these, alkaline earth metal hydroxides are preferred, and lithium hydroxide and sodium hydroxide are more preferred.
- aliphatic amine compounds include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine and triethylamine, preferably ammonia or triethylamine.
- Alcoholamine compounds include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine, diethylethanolamine and N-methyldiethanolamine, but are preferred. is a tertiary amine, more preferably triethanolamine.
- alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate
- alkali metal salts of organic acids such as sodium silicate and potassium acetate
- phosphate and the like.
- chelating reagent-- Specific examples of the chelating reagent include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.
- rust preventive include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
- Water-soluble UV absorber-- examples include sulfonated benzophenone-based compounds, benzotriazole-based compounds, salicylic acid-based compounds, cinnamic acid-based compounds, and triazine-based compounds.
- antioxidant for example, various organic and metal complex antioxidants (also referred to as "anti-fading agent”) can be used.
- organic antioxidants include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. be done.
- the sizing agent examples include starches such as corn and wheat; cellulose compounds such as carboxymethylcellulose and hydroxymethylcellulose; polysaccharides such as sodium alginate, gum arabic, locust bean gum, tranto gum, guar gum, and tamarind seed; gelatin and casein; natural water-soluble polymers such as tannin and lignin; and synthetic water-soluble polymer compounds containing polyvinyl alcohol, polyethylene oxide, acrylic acid, maleic anhydride, and the like.
- the content of the paste is usually about 0 to 20% with respect to the total weight of the pretreatment composition.
- the surface tension of the pretreatment composition at 25° C. is preferably 35 to 60 mN/m, more preferably 36 to 58 mN/m, more preferably 37 from the viewpoint of expressing sufficient wettability to various fabrics. to 56 mN/m, particularly preferably 38 to 54 mN/m.
- the surface tension of the pretreatment composition at 25°C is preferably equal to or higher than the surface tension of the water-based ink composition, which will be described later, from the viewpoint of preventing bleeding of printed matter.
- the surface tension of the pretreatment composition can be measured by the platinum plate method in a 25°C environment using, for example, a surface tensiometer (CBVPZ manufactured by Kyowa Interface Science Co., Ltd.).
- the viscosity of the pretreatment composition at 25° C. is preferably 0.5 to 4.0 mPa ⁇ s, more preferably 0.7 to 3.5 mPa ⁇ s, and particularly preferably 0.8 to 3.0 mPa ⁇ s. be.
- the pretreatment composition can be applied evenly regardless of the application method of the pretreatment composition or the type of fabric, resulting in uneven dot shape or uneven image. can suppress erosion.
- excellent printed matter can be obtained from the viewpoint of wettability to fabrics and suppression of unevenness during drying.
- the viscosity of the pretreatment composition can be measured using, for example, an E-type viscometer (TVE25L type viscometer manufactured by Toki Sangyo Co., Ltd.).
- the pH of the pretreatment composition at 25° C. is preferably 3.0 to 10.0, more preferably 3.5 to 8.0, particularly preferably 4.0 to 6.0. If the pretreatment composition falls within the above pH range, embrittlement of the fabric can be prevented, and a printed material with excellent color developability can be obtained with little color bleeding and uneven color.
- the pH of the pretreatment composition can be measured by a known method, for example, using a desktop pH meter F-72 manufactured by Horiba Ltd., using a standard ToupH electrode or a sleeve ToupH electrode.
- Preparation method of pretreatment composition for example, water, a cationic polymer, a cross-linking agent, and, if necessary, further addition of a preparation agent such as those listed above, followed by stirring and mixing, A method of filtering is mentioned as necessary.
- the method for preparing the pretreatment composition of the present invention is not limited to the above.
- the water-based ink composition of this embodiment contains water and a pigment.
- the water-based ink composition of one preferred embodiment of the present invention preferably contains water, a pigment, a resin emulsion, a water-soluble organic solvent, a surfactant, and further contains a polymer dispersant.
- the water-based ink composition may be abbreviated as ink composition or ink.
- a water-based ink composition according to another preferred embodiment of the present invention is a water-based white ink composition containing water, a white pigment, a urethane resin, a water-soluble organic solvent, and a base. is preferred.
- a water-based white ink composition may be abbreviated as white ink composition or white ink.
- the water-based white ink composition will be described later in detail.
- a water-based ink composition of another preferred embodiment of the present invention contains water, a pigment, a polymer dispersant, and further comprises a urethane resin, a styrene-butadiene resin, a (meth)acrylic resin, and a (meth)acrylic resin. It preferably contains at least one selected from the group consisting of copolymers, and may further contain a water-soluble organic solvent and a surfactant. It is preferably used in combination with a composition.
- water As the water contained in the water-based ink composition, for example, those exemplified for the pretreatment composition can be used.
- the content of water is not particularly limited and may be determined as needed. 20 to 80 mass% is preferably contained with respect to. Although not limited, for example, it is preferably 40 to 80% by mass, more preferably 45 to 75% by mass, still more preferably 50 to 70% by mass.
- the above pigment is not particularly limited, and known pigments can be used. As pigments, inorganic pigments, organic pigments, extender pigments and the like are known.
- the inorganic pigments include carbon black, metal oxides, hydroxides, sulfides, ferrocyanides, and metal chlorides.
- carbon black is preferred as the black pigment.
- metal oxides include zinc oxide, titanium oxide, and zirconia oxide, with titanium oxide being preferred.
- Types of titanium oxide include rutile type and anatase type. Titanium oxide may be used as powder as it is, or may be surface-treated with silicon dioxide, aluminum oxide, zirconia oxide, zinc oxide, or an organic material having a hydroxyl group. Among these, surface-treated titanium oxide is preferred.
- titanium oxide examples include DUAWHITE TCR-52, TITONE R-32, TITONE R-7E, TITONE R-21, TITONE R-62N, and TITONE R-42 (manufactured by Sakai Chemical Industry Co., Ltd.); TIPAQUE CR-50, TIPAQUE CR-50-2, TIPAQUE CR-58, TIPAQUE CR-60, TIPAQUE CR-80, TIPAQUE CR-90 (manufactured by Ishihara Sangyo Co., Ltd.); TITANIX JA-600A, TITANIX JR-605 (manufactured by Tayca Corporation); ST-455, ST-455WB, ST-457SA, ST-457EC (manufactured by Titan Kogyo Co., Ltd.); Since the water-based white ink composition described later contains a white pigment, the water-based ink composition used in combination with the water-based white ink composition preferably contains a pigment other than the white pigment.
- organic pigments examples include azo pigments having at least one azo group in the molecule, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments. pigments.
- organic pigments include C.I. I.
- Violet pigments such as Pigment Violet 19, 23, 29, 37, 38, 50;
- C.I. I. Orange to brown pigments such as C.I. Pigment Orange 13, 16, 36, 34, 43, 68, 69, 71, 73;
- Green pigments such as Pigment Green 7, 36, 54;
- C.I. I. a black pigment such as Pigment Black 1;
- extender pigments examples include silica, calcium carbonate, talc, clay, barium sulfate, and white carbon. Although these extender pigments may be used alone, they are usually used in combination with inorganic or organic pigments.
- a single pigment is usually used as the above pigment.
- two or more types of pigments may be used in combination as necessary. Examples of combined use include organic pigments and extender pigments; organic pigments and inorganic pigments; and the like.
- extender pigments may also be used in combination to improve fluidity.
- two or more pigments selected from inorganic pigments and organic pigments can be used in combination to adjust the hue of the dyed article.
- the hue adjustment referred to here is performed for the purpose of obtaining a dyed product with a shading; widening the color gamut of dyeing; and the like.
- several kinds of organic pigments can be used together to adjust the desired hue.
- the content of the pigment is preferably 1.5 to 15.0% by mass, more preferably 2.0 to 14.0% by mass, relative to the total mass (100% by mass) of the ink composition, More preferably, it is 2.5 to 13.0% by mass.
- resin emulsion examples include styrene-butadiene resin, (meth)acrylic resin, (meth)acrylic resin copolymer, styrene-maleic anhydride copolymer resin, epoxy resin, urethane resin, Polyether resin, polyamide resin, unsaturated polyester resin, phenol resin, silicone resin, fluorine resin, polyvinyl resin (vinyl chloride, vinyl acetate, polyvinyl alcohol, etc.), vinyl acetate-(meth)acrylic copolymer resin, vinyl acetate- Examples include emulsions formed from ethylene copolymer resins, alkyd resins, polyester resins, amino resins (melanin resins, urea resins, urea resins, melanin-formaldehyde resins, etc.).
- the resin emulsion may contain two or more resins. Moreover, two or more kinds of resins may form a core/shell structure. One type of resin emulsion may be used alone, or two or more types may be used in combination. Among resin emulsions, styrene-butadiene resin emulsions, (meth)acrylic resin emulsions, (meth)acrylic resin copolymer emulsions, and urethane resin emulsions are preferable from the viewpoint of ink performance.
- the above styrene-butadiene resin emulsion is often sold in the form of latex (emulsion), for example, and can be easily purchased.
- Specific examples include Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, Nipol 2507H, Nipol LX303A (manufactured by Zeon Corporation), grades 0695, 0696, 0561, 0589, 0602, 2108, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, 0850Z latex (manufactured by JSR Corporation), etc., and most of them are liquids obtained by emulsifying resins with a solid content of 30 to 60%.
- any of the latexes described above can be used, but among them, it is preferable to use a carboxy-modified styrene-butadiene resin.
- resins include, for example, Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, 0695, 0696, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, 0850Z, 0695, 0533, 0568 , 0597C and 0850Z are preferable, and JSR0568 (manufactured by JSR Corporation) is more preferable.
- a single styrene-butadiene resin may be used, or two or three types may be used in combination.
- the content of the styrene-butadiene resin emulsion is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, more preferably 3 to 17% by mass, relative to the total mass of the ink composition. is even more preferable.
- the above (meth)acrylic resin emulsion and (meth)acrylic resin copolymer emulsion are commercially available, and most of them are emulsions with a solid content concentration of 30 to 60% by mass.
- emulsions with a solid content concentration of 30 to 60% by mass.
- Movinyl 966A, 6963, 6960 (acrylic resin emulsion, all trade names), 6969D, RA-033A4 (styrene / acrylic resin emulsion, all trade names), and BASF John Krill 7100, PDX-7370, PDX-7341 (styrene/acrylic resin emulsion, all trade names), DIC Corporation Boncoat EC-905EF, 5400EF, CG-8400 (acrylic/styrene emulsion), and the like.
- the content of the (meth)acrylic resin emulsion and (meth)acrylic resin copolymer emulsion is generally 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 2 to 20% by mass, based on the total mass of the ink composition. is 3 to 17% by mass.
- the urethane resin emulsion is not particularly limited, and known urethane resin emulsions can be used. Examples thereof include emulsions of polyurethane resins such as polyether-based urethane resins, polycarbonate-based urethane resins and polyester-based urethane resins, and emulsions of polyether-based urethane resins and polycarbonate-based urethane resins are preferred.
- the above urethane resin emulsions are commercially available, and most of them are emulsions with a solid concentration of 30 to 60% by mass.
- urethane resin emulsions examples include Permalin UA-150, 200, 310, 368, 3945, Ukote UX-320, 340 (manufactured by Sanyo Kasei Co., Ltd.); Hydran WLS-201, 202, 210, 213.
- polycarbonate-based urethane resins include, for example, Permalin UA-310, 3945; Ukote UX-320; Hydran WLS-210, 213, 250;
- polyether-based urethane resins include Permaline UA-150, 200; Ukote UX-340; Hydran WLS-201, 202, 230;
- a single urethane resin may be used, or two or three types may be used in combination.
- the acidic group may be alkali chlorided.
- a urethane resin having an acidic group is added to water and stirred to prepare an aqueous solution, and an alkaline compound is added thereto to adjust the pH to 6.0 to 12.0, whereby the acidic group is alkali chlorided. can do.
- alkaline compounds include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; water of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. oxide; and the like. Alkaline compounds may be used alone or in combination of two or more.
- the glass transition temperature of the urethane resin is preferably -90°C to 0°C, more preferably -85°C to -20°C, and even more preferably -85°C to -30°C. Those having a glass transition temperature exceeding 0° C. are not preferable because the texture of the printed matter becomes hard. If the glass transition temperature is less than ⁇ 90° C., the coating film of the printed matter tends to be tacky due to strong adhesion, and the washing fastness is also inferior.
- the glass transition temperature can be measured, for example, by a differential scanning calorimeter (DSC).
- the above urethane resin is preferably a urethane resin with a freezing point of -8°C or lower.
- a freezing point of ⁇ 8° C. or less means that the material freezes or solidifies at ⁇ 8° C. or less, that is, it does not undergo so-called denaturation such as gelation and returns to an emulsion state when the temperature is returned to room temperature.
- a urethane resin having a freezing point of ⁇ 8° C. or lower is used, a white ink composition having excellent low-temperature storage stability can be obtained. More preferably, the freezing point is -11°C or lower.
- the freezing point can be measured, for example, by placing 30 cc of the urethane resin emulsion in a 50 cc plastic bottle, allowing it to stand still for 20 hours in a constant temperature bath at a predetermined temperature, and then checking for freezing.
- the content of the urethane resin emulsion is usually 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 3 to 17% by mass, relative to the total mass of the ink composition.
- the water-based ink composition contains a water-soluble organic solvent.
- the water-soluble organic solvent include C1-C4 monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol; ethylene glycol, 1,2- or C2-, such as 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,3-pentanediol, 1,5-pentanediol, 1,2-hexanediol and 1,6-hexanediol C6 diol; glycerin, hexane-1,2,6-triol, C3-C6 triol such as trimethylolpropane; N,N-dimethylformamide, N,N-dimethylacetamide and other carboxylic acid amides; 2-pyrroli
- C1-C4 alkyl ethers of alcohols cyclic esters such as ⁇ -butyrolactone and ethylene carbonate ter or carbonate; dimethylsulfoxide; acetic acid; Among these are C2-C6 diols (in 1,2-propylene glycol); C3-C6 triols (in glycerine); polyglyceryl ethers (in diglycerine); and C1-C4 alkyl ethers of polyhydric alcohols. (among butyl carbitol); is preferred. These water-soluble organic solvents may be used alone or in combination. Among these, it is preferable to contain polyglyceryl ether (preferably glycerin and/or diglycerin).
- polyglyceryl ether preferably glycerin and/or diglycerin.
- the content of the water-soluble organic solvent is preferably 10 to 50% by mass, more preferably 14 to 45% by mass, and still more preferably 16 to 50% by mass, relative to the total mass (100% by mass) of the ink composition. 35% by mass.
- content of the water-soluble organic solvent is within the above range, it tends to be excellent in terms of reduction of ejection failure.
- surfactant examples of the surfactant contained in the water-based ink composition include known surfactants such as anionic, cationic, nonionic, amphoteric, silicone, and fluorine-based surfactants.
- anionic surfactants include alkyl sulfonates, alkyl carboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurate salts, and alkyl sulfates.
- Cationic surfactants include 2-vinylpyridine derivatives, poly-4-vinylpyridine derivatives and the like.
- Nonionic surfactants include ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Esters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol Acetylene glycol (alcohol) system such as Nissin Kagaku Co., Ltd., trade name Surfyn
- Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, and the like. is mentioned.
- silicone-based surfactants include polyether-modified siloxane and polyether-modified polydimethylsiloxane.
- fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups having side chains.
- polyoxyalkylene ether polymer compounds having Specific examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (manufactured by DuPont); PF-151N. , PF-154N (manufactured by Omnova Co., Ltd.) and the like.
- the water-based ink composition preferably contains a polymer dispersant.
- a method for stabilizing a pigment dispersion in an aqueous medium a method of stabilizing a pigment dispersion by entropy, ionic repulsion, steric repulsion, etc., using a dispersant such as a resin is generally used.
- the dispersant has a hydrophilic portion and a hydrophobic portion, and it is believed that the hydrophobic portion adsorbs to the surface of the pigment and the hydrophilic portion disperses in the aqueous medium.
- the polymer dispersant described above can be used as a dispersant having such properties.
- the polymeric dispersant is a polymer containing at least two constituent monomers selected from the group consisting of monomer A, monomer B, and monomer C represented by formula (1) below. Preferably, at least one each of monomer A, monomer B, and monomer C is selected.
- Monomer A A monomer in which R is a hydrogen atom in the following formula (1).
- Monomer B A monomer in which R is a C1-C4 alkyl group in the following formula (1).
- Monomer C A monomer in which R is an aryl group or an aryl C1-C4 alkyl group in the following formula (1).
- R is an aryl group
- R is a benzyl group.
- polymeric dispersant may be any of random copolymers, alternating copolymers, block copolymers, and graft copolymers of these monomers.
- the mass average molecular weight of the polymer dispersant is usually 10,000 to 60,000, preferably 10,000 to 40,000, and more preferably 10,000 to 30,000. When the weight average molecular weight is within these ranges, the stability of the pigment dispersion is improved.
- the acid value of the polymer dispersant is usually 50-300, preferably 90-200, and more preferably 100-150 in units of mgKOH/g. If the acid value is too small, the solubility of the polymer dispersant in water or an aqueous medium will be reduced, and if it is too large, the color developability may be reduced.
- polymer dispersants examples include Hylos X VS-1202 (a random polymer consisting of methyl methacrylate, butyl methacrylate, and methacrylic acid, having an acid value of 140 mgKOH/g and a mass average molecular weight of 11,000) manufactured by Seiko PMC.
- the polymer dispersant may be used after neutralizing its acid value, if necessary.
- the degree of neutralization is 100% when neutralized with the theoretical equivalent of the acid value of the polymer dispersant.
- the degree of neutralization of the polymeric dispersant in the ink composition is generally about 50 to 200%, preferably about 80 to 150%, more preferably about 100 to 120%.
- neutralizing agents used for neutralizing the polymer dispersant include alkali metal hydroxides, alkaline earth metal hydroxides, inorganic bases such as ammonia, aliphatic amine compounds, alkanolamine compounds, and the like. Organic bases and the like can be mentioned.
- alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
- alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide.
- alkali metal hydroxides and ammonia are preferred, among which lithium hydroxide, sodium hydroxide and ammonia are preferred.
- alkanolamine compound examples include mono-, di-, or tri-C1 such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine, and N-methyldiethanolamine.
- -C3 alkanolamine compounds examples include tertiary amines are preferred, and triethanolamine is particularly preferred.
- aliphatic amine compounds include mono-, di-, and tri-C1-C3 amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine, and trimethylamine. Among these, triethylamine is preferred.
- neutralizing agents may be used singly or in combination of two or more.
- Monomer A is a monomer in which R is a hydrogen atom in the above formula (1), that is, methacrylic acid.
- Monomer B is a monomer in which R is a C1-C4 alkyl group in the above formula (1).
- Monomer B includes methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and the like.
- Monomer C is a monomer in which R is an aryl group or an aryl C1-C4 alkyl group in the above formula (1).
- the above aryl is preferably a C6-C10 aryl group, and more preferably a phenyl group or a naphthyl group.
- aryl C1-C4 alkyl groups include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and other alkyl moieties that are linear or branched, preferably linear phenyl C1-C4 alkyl groups; naphthylmethyl, naphthylethyl, A naphthyl C1-C4 alkyl group in which the alkyl moiety is linear or branched, preferably linear, such as naphthylpropyl and naphthylbutyl; and the like. Among these, a phenyl C1-C4 alkyl group is preferred.
- monomer C include phenyl methacrylate, benzyl methacrylate, and phenethyl methacrylate.
- the content of the polymeric dispersant is usually 0.1 to 15.0% by mass, preferably 0.1 to 9.0% by mass, relative to the total mass (100% by mass) of the ink composition. , more preferably 0.2 to 6.0% by mass.
- the water-based ink composition preferably further contains at least one selected from the group consisting of urethane resins, styrene-butadiene resins, (meth)acrylic resins, and (meth)acrylic resin copolymers.
- the water-based ink composition containing water, a pigment, and a polymer dispersant is further selected from the group consisting of urethane resins, styrene-butadiene resins, (meth)acrylic resins, and (meth)acrylic resin copolymers. It is preferable to include at least one of them.
- the above resins may be used singly or in combination of two or more.
- urethane resins and styrene-butadiene resins are preferable from the viewpoint of ink performance.
- urethane resin used in the water-based ink composition examples include those listed for the white ink composition.
- a single urethane resin may be used, or two or three types may be used in combination.
- the acidic group may be alkali chlorided.
- a urethane resin having an acidic group is added to water and stirred to prepare an aqueous solution, and an alkaline compound is added thereto to adjust the pH to 6.0 to 12.0, whereby the acidic group is alkali chlorided. can do.
- alkaline compounds include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; water of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. oxide; and the like. Alkaline compounds may be used alone or in combination of two or more.
- the content of the urethane resin is usually 1-30% by mass, preferably 2-20% by mass, more preferably 3-17% by mass, relative to the total mass of the ink composition.
- the styrene-butadiene resin is often sold in the form of latex (emulsion), for example, and can be easily purchased.
- specific examples include Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, Nipol 2507H, Nipol LX303A (manufactured by Zeon Corporation), grades 0695, 0696, 0561, 0589, 0602, 2108, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, 0850Z latex (manufactured by JSR Corporation), etc., and most of them are liquids obtained by emulsifying resins with a solid content of 30 to 60%.
- any of the latexes described above can be used, but among them, it is preferable to use a carboxy-modified styrene-butadiene resin.
- resins include Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, 0695, 0696, 0533, 0545, 0548, 0568, 0569, 0573, 0597C, 0850Z, 0695, 0533, 0568, 0597C and 0850Z are preferred, and JSR0568 (manufactured by JSR Corporation) is more preferred.
- a single styrene-butadiene resin may be used, or two or three types may be used in combination.
- the content of the styrene-butadiene resin is usually 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 3 to 17% by mass, relative to the total mass of the ink composition.
- (meth)acrylic resins and (meth)acrylic resin copolymers are commercially available, and most of them are emulsions with a solid content concentration of 30 to 60% by mass.
- emulsions with a solid content concentration of 30 to 60% by mass.
- Movinyl 966A, 6963, 6960 (acrylic resin emulsion, all trade names), 6969D, RA-033A4 (styrene / acrylic resin emulsion, all trade names), and BASF John Krill 7100, PDX-7370, PDX-7341 (styrene/acrylic resin emulsion, all trade names), DIC Corporation Boncoat EC-905EF, 5400EF, CG-8400 (acrylic/styrene emulsion), and the like.
- the content of the (meth)acrylic resin and (meth)acrylic resin copolymer is usually 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 3% by mass, based on the total mass of the ink composition. ⁇ 17% by mass.
- the ink composition may further contain additives.
- additives examples include preservatives, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity modifiers, pigment solubilizers, anti-fading agents, and antioxidants.
- antiseptics in the above additives include organic sulfur, organic nitrogen sulfur, organic halogen, haloarylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, and 8-oxyquinoline.
- organic halogen compounds include sodium pentachlorophenol
- specific examples of pyridine oxide compounds include 2-pyridinethiol-1-oxide sodium
- specific examples of isothiazoline compounds include sodium pentachlorophenol
- chelating reagent-- Specific examples of the chelating reagent in the additive include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.
- anti-rust-- examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
- Water-soluble polymer compounds examples include polyvinyl alcohol, cellulose derivatives, polyamines and polyimine.
- Viscosity modifier-- Viscosity modifiers in the additives include the water-soluble organic solvents and water-soluble polymer compounds described in the section on the water-based ink composition.
- water-soluble polymer compounds include polyvinyl alcohol and cellulose derivatives. , polyamines, polyimines, and the like.
- pigment dissolving agent-- examples include urea, ⁇ -caprolactam, ethylene carbonate and the like.
- the anti-fading agent in the above additives is used for the purpose of improving the storability of images.
- various organic and metal complex antifading agents can be used.
- Organic compounds include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles.
- metal complexes include nickel complexes and zinc complexes.
- antioxidants for example, various organic and metal complex anti-fading agents can be used.
- organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocyclics, and the like.
- the surface tension of the water-based ink composition at 25° C. is preferably 20 to 48 mN/m, more preferably 25 to 46 mN/m, from the viewpoint of expressing sufficient wettability to various fabrics. , more preferably 30 to 44 mN/m, particularly preferably 32 to 42 mN/m.
- the surface tension at 25° C. of the water-based ink composition which is preferably combined with the water-based white ink composition described below, is preferably 20 to 48 mN from the viewpoint that sufficient wettability can be exhibited for various fabrics. /m, more preferably 25 to 44 mN/m, more preferably 30 to 42 mN/m, particularly preferably 32 to 40 mN/m.
- the surface tension of the water-based ink composition can be measured by the platinum plate method in a 25°C environment using, for example, a surface tensiometer (CBVPZ manufactured by Kyowa Interface Science Co., Ltd.).
- the viscosity of the water-based ink composition at 25° C. is preferably 2 to 20 mPa ⁇ s, more preferably 3 to 18 mPa ⁇ s. Water-based ink compositions satisfying the above viscosity range tend to have good ejection responsiveness in high-speed printing.
- the pH of the water-based ink composition is preferably pH 5.0 to 11.0, more preferably pH 7.0 to 10.0, for the purpose of improving storage stability.
- Method for preparing water-based ink composition The method for preparing the water-based ink composition is not particularly limited. is further added.
- a pigment, a dispersant e.g., the above-mentioned polymer dispersant, resin, etc.
- water or an aqueous solvent e.g., water or an aqueous solvent
- a sand mill (bead mill) e.g., the above-mentioned polymer dispersant, resin, etc.
- water or an aqueous solvent e.g., water or an aqueous solvent
- a sand mill e.g., the above-mentioned polymer dispersant, resin, etc.
- water or an aqueous solvent e.g., water or an aqueous solvent
- a sand mill e.g., the above-mentioned polymer dispersant, resin, etc.
- water or an aqueous solvent e.g., water or an aqueous solvent
- a sand mill e.g., the above-mentioned polymer dispersant,
- the dispersant may be in a state of being adsorbed on a part of the pigment surface, or may be in a state of covering the entire pigment surface (referred to as a microencapsulated pigment or the like). The latter is preferred.
- a polymer dispersant is preferable as a dispersant for pigments.
- any known microencapsulation method can be used.
- the methods are roughly classified into two, namely physical/mechanical methods and chemical methods.
- a surface precipitation method, a kneading method, an interfacial polymerization method (also referred to as a surface polymerization method), and the like have been proposed.
- the surface precipitation method includes an acid precipitation method, a phase inversion emulsification method, and the like. Any method may be used for microencapsulation, and there is no particular limitation. Among them, the surface precipitation method is preferable, and the phase inversion emulsification method is particularly preferable.
- phase inversion emulsification method for example, a solution of a hydrophobic organic solvent in which a dispersant is dissolved is mixed with a liquid containing a neutralizer and water to form an emulsified (emulsion or microemulsion) liquid, and a pigment is further added.
- the solvent is removed to obtain an aqueous pigment dispersion.
- the average particle size of the pigment in the pigment dispersion prepared as described above is usually 200 nm or less, preferably 50 to 150 nm, more preferably 60 to 120 nm. By setting the average particle size within this range, the dispersion stability and ejection stability are excellent, and the dyeing density is increased.
- the average particle size can be measured using a laser light scattering method.
- the water-based ink composition may be subjected to precision filtration using a membrane filter or the like.
- a membrane filter or the like In particular, when the ink is used as an ink for inkjet textile printing, it is preferable to perform microfiltration for the purpose of preventing nozzle clogging and the like.
- the pore size of the filter used for microfiltration is usually 0.1-1 ⁇ m, preferably 0.1-0.8 ⁇ m.
- the content of the polymer dispersant can be represented by a numerical value called the fractional ratio, and the fractional ratio can be obtained by the following formula. .
- Part ratio parts of dispersant / parts of pigment
- the originality ratio is usually 0.1 to 1.0, preferably 0.1 to 0.6, more preferably 0.2 to 0.4. When the ratio is within this range, a highly stable pigment dispersion and a good dyeing can be obtained.
- the water-based white ink composition contains water, a white pigment, a urethane resin, and a water-soluble organic solvent.
- the water-based white ink composition may be abbreviated as white ink composition or white ink.
- water As the water contained in the white ink composition, for example, those exemplified for the pretreatment composition can be used.
- the content of water is not particularly limited and may be determined as appropriate as needed. 20 to 80% by mass is preferably contained. Also, although not limited, it is preferably 40 to 80% by mass, more preferably 45 to 75% by mass, still more preferably 50 to 70% by mass.
- a metal oxide is preferably used as the white pigment.
- metal oxides include zinc oxide, titanium oxide, and zirconia oxide, with titanium oxide being preferred.
- Types of titanium oxide include rutile type and anatase type. Titanium oxide may be used as powder as it is, or may be surface-treated with silicon dioxide, aluminum oxide, zirconia oxide, zinc oxide, or an organic material having a hydroxyl group. Among these, surface-treated titanium oxide is preferred.
- titanium oxide examples include DUAWHITE TCR-52, TITONE R-32, TITONE R-7E, TITONE R-21, TITONE R-62N, and TITONE R-42 (manufactured by Sakai Chemical Industry Co., Ltd.); TIPAQUE CR-50, TIPAQUE CR-50-2, TIPAQUE CR-58, TIPAQUE CR-60, TIPAQUE CR-80, TIPAQUE CR-90 (manufactured by Ishihara Sangyo Co., Ltd.); TITANIX JA-600A, TITANIX JR-605 (manufactured by Tayca Corporation); ST-455, ST-455WB, ST-457SA, ST-457EC (manufactured by Titan Kogyo Co., Ltd.);
- the content of the white pigment is preferably 3.0 to 16.0% by mass, more preferably 4.0 to 15.0% by mass, relative to the total mass (100% by mass) of the white ink composition. Yes, more preferably 5.0 to 14.0% by mass.
- the urethane resin is not particularly limited, and known urethane resins can be used. Specific examples of the urethane resin include polyurethane resins such as polyether-based urethane resins, polycarbonate-based urethane resins, and polyester-based urethane resins, and polyether-based urethane resins and polycarbonate-based urethane resins are preferable.
- urethane resins are commercially available, and most of them are emulsions with a solid content concentration of 30 to 60% by mass.
- Commercially available urethane resins include, for example, Permalin UA-150, 200, 310, 368, 3945, Ukote UX-320, 340 (manufactured by Sanyo Kasei Co., Ltd.); Hydran WLS-201, 202, 210, 213; 221, 230, 250, HW-312B latex (manufactured by DIC Corporation); Superflex 150, 170, 470 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.);
- polycarbonate-based urethane resins include, for example, Permalin UA-310, 3945; Ukote UX-320; Hydran WLS-210, 213, 250;
- Examples of polyether-based urethane resins include Permaline UA-150, 200; Ukote UX-340
- the glass transition temperature of the urethane resin is preferably -90°C to 0°C, more preferably -85°C to -20°C, and even more preferably -85°C to -30°C. Those having a glass transition temperature exceeding 0° C. are not preferable because the texture of the printed matter becomes hard. If the glass transition temperature is less than ⁇ 90° C., the coating film of the printed matter tends to be tacky due to strong adhesion, and the washing fastness is also inferior.
- the glass transition temperature can be measured, for example, by a differential scanning calorimeter (DSC).
- the above urethane resin is preferably a urethane resin with a freezing point of -8°C or lower.
- a freezing point of ⁇ 8° C. or less means that the material freezes or solidifies at ⁇ 8° C. or less, that is, it does not undergo so-called denaturation such as gelation and returns to an emulsion state when the temperature is returned to room temperature.
- a urethane resin having a freezing point of ⁇ 8° C. or lower is used, a white ink composition having excellent low-temperature storage stability can be obtained. More preferably, the freezing point is -11°C or lower.
- the freezing point can be measured, for example, by placing 30 cc of the urethane resin emulsion in a 50 cc plastic bottle, allowing it to stand still for 20 hours in a constant temperature bath at a predetermined temperature, and then checking for freezing.
- the content of the urethane resin is usually 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 3 to 17% by mass, relative to the total mass of the white ink composition.
- the white ink composition contains a water-soluble organic solvent.
- Water-soluble organic solvents include, for example, C1-C4 monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol; C2-C6 such as ,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,3-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol Diols; C3-C6 triols such as glycerin, hexane-1,2,6-triol and trimethylolpropane; Carboxylic acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide; 2-pyrrolidone, N-methyl -hexane
- Alkylene glycol or thioglycol tetraethylene glycol, polyethylene glycol (preferably having a molecular weight of 400, 800, 1540, etc., with a molecular weight of 2000 or less), polypropylene glycol, etc., having a repeating unit of 4 or more and a molecular weight of about 20000 or less
- Poly C2-C3 alkylene glycol preferably liquid
- polyglyceryl ethers such as diglycerin, triglycerin and polyglycerin
- polyoxy C2-C3 alkylene polyglyceryl ethers such as polyoxyethylene polyglyceryl ether and polyoxypropylene polyglyceryl ether
- ethylene glycol Polyhydric alcohols such as monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl
- C2-C6 diols in 1,2-propylene glycol
- C3-C6 triols in glycerine
- polyglyceryl ethers in diglycerine
- C1-C4 alkyl ethers of polyhydric alcohols is preferred.
- These water-soluble organic solvents may be used alone or in combination.
- it is preferable to contain polyglyceryl ether preferably glycerin and/or diglycerin).
- the content of the water-soluble organic solvent is preferably 10 to 50% by mass, more preferably 14 to 45% by mass, still more preferably 16% by mass, relative to the total mass (100% by mass) of the white ink composition. ⁇ 35% by mass.
- content of the water-soluble organic solvent is within the above range, it tends to be excellent in terms of reduction of ejection failure.
- the white ink composition preferably further contains a base.
- the base is not particularly limited, but for example, alkali hydroxide bases such as alkali metal hydroxides and alkaline earth metal hydroxides, inorganic bases such as ammonia, and organic bases such as aliphatic amine compounds and alkanolamine compounds. A base etc. are mentioned.
- alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like.
- hydroxides of alkaline earth metals include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide.
- alkali metal hydroxides and ammonia are preferred, among which lithium hydroxide, potassium hydroxide, sodium hydroxide and ammonia are preferred, with sodium hydroxide being most preferred.
- Examples of the aliphatic amine compounds include mono-, di-, or tri-C1-C3 amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine, and trimethylamine. Among these, triethylamine is preferred.
- alkanolamine compound examples include mono-, di-, or tri-C1 such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine, and N-methyldiethanolamine.
- -C3 alkanolamine compounds examples include tertiary amines are preferred, and diethanolamine and triethanolamine are more preferred.
- one type may be used, or two or more types may be used in combination.
- the mixing ratio of each base may be set arbitrarily according to the purpose.
- the white ink composition may further contain additives.
- additives examples include preservatives, surfactants, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity modifiers, pigment solubilizers, anti-fading agents, antioxidants, and the like. is mentioned.
- preservative-- examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloallyl sulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole type, isothiazoline type, dithiol type, pyridine oxide type, nitropropane type, organic tin type, phenol type, quaternary ammonium salt type, triazine type, thiazine type, anilide type, adamantane type, dithiocarbamate type, brominated indanone type , benzyl bromoacetate-based compounds, inorganic salt-based compounds, and the like.
- organic halogen compounds include sodium pentachlorophenol
- specific examples of pyridine oxide compounds include 2-pyridinethiol-1-oxide sodium
- specific examples of isothiazoline compounds is, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like.
- antiseptic and antifungal agents include sodium acetate anhydride, sodium sorbate, sodium benzoate, trade names Proxel RTM GXL (S) and Proxel RTM XL-2 (S) manufactured by Arch Chemicals.
- surfactant examples include known surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and silicone surfactants.
- anionic surfactants include alkyl sulfonates, alkyl carboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurate salts, and alkyl sulfates.
- Cationic surfactants include 2-vinylpyridine derivatives, poly-4-vinylpyridine derivatives and the like.
- Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, and the like. are mentioned.
- Nonionic surfactants include ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Esters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol Acetylene glycol (alcohol) system such as Nissin Kagaku Co., Ltd., trade name Surfyn
- silicone surfactant examples include polyether-modified siloxane and polyether-modified polydimethylsiloxane. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane); BYK-345 and BYK-348 (polyether-modified polydimethylsiloxane), all of which are manufactured by BYK-Chemie.
- fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups having side chains.
- polyoxyalkylene ether polymer compounds having Specific examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (manufactured by DuPont); PF-151N , PF-154N (manufactured by Omnova Co., Ltd.) and the like.
- chelating reagent-- Specific examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.
- rust preventive examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate and dicyclohexylammonium nitrite.
- water-soluble polymer compounds examples include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.
- Viscosity modifier examples include water-soluble organic solvents and water-soluble polymer compounds such as polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.
- pigment dissolving agent-- examples include urea, ⁇ -caprolactam, and ethylene carbonate.
- the anti-fading agent is used for the purpose of improving the storability of images.
- various organic and metal complex antifading agents can be used.
- Organic compounds include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles.
- Metal complexes include nickel complexes, zinc complexes, and the like.
- antioxidant for example, various organic and metal complex anti-fading agents can be used.
- organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocyclics, and the like.
- Method for preparing water-based white ink composition for example, a method of preparing an aqueous dispersion containing the above components and, if necessary, further adding the above additives can be mentioned.
- a method for preparing the aqueous dispersion there is a method of dispersing with a pigment, a dispersant, water or an aqueous solvent using a sand mill (bead mill), roll mill, ball mill, paint shaker, ultrasonic disperser, microfluidizer, or the like.
- a sand mill (bead mill) is preferred.
- small beads (approximately 0.01 to 1 mm in diameter) are used, and the dispersion efficiency is increased by increasing the filling rate of the beads. is preferred.
- the particle size of the pigment can be reduced, and a dispersion having good dispersibility can be obtained.
- After preparation of the dispersion it is also preferable to remove components having large particle sizes by filtration and/or centrifugation. If foaming occurs violently during the preparation of the dispersion, a very small amount of antifoaming agent such as silicone or acetylene glycol may be added for the purpose of suppressing the foaming. However, since some antifoaming agents hinder the dispersion and microparticulation of pigments, it is preferable to appropriately select and use those that do not have such adverse effects.
- the dispersant may be in a state of being adsorbed on a part of the pigment surface, or may be in a state of covering the entire pigment surface (referred to as a microencapsulated pigment or the like). The latter is preferred.
- any known microencapsulation method can be used.
- the methods are roughly classified into two, namely physical/mechanical methods and chemical methods.
- a surface precipitation method, a kneading method, an interfacial polymerization method (also referred to as a surface polymerization method), and the like have been proposed.
- the surface precipitation method includes an acid precipitation method, a phase inversion emulsification method, and the like. Any method may be used for microencapsulation, and there is no particular limitation. Among them, the surface precipitation method is preferable, and the phase inversion emulsification method is particularly preferable.
- phase inversion emulsification method for example, a solution of a hydrophobic organic solvent in which a dispersant is dissolved is mixed with a liquid containing a neutralizer and water to form an emulsified (emulsion or microemulsion) liquid, and a pigment is further added.
- the solvent is removed to obtain an aqueous pigment dispersion.
- the average particle size of the pigment in the pigment dispersion prepared as described above is usually 200 nm or less, preferably 50 to 150 nm, more preferably 60 to 120 nm. By setting the average particle size within this range, the dispersion stability and ejection stability are excellent, and the dyeing density is increased.
- the average particle size can be measured using a laser light scattering method.
- the white ink composition may be subjected to precision filtration using a membrane filter or the like.
- a membrane filter or the like In particular, when the ink is used as an ink for inkjet textile printing, it is preferable to perform microfiltration for the purpose of preventing nozzle clogging and the like.
- the pore size of the filter used for microfiltration is usually 0.1-1 ⁇ m, preferably 0.1-0.8 ⁇ m.
- the white ink composition according to the present embodiment it is possible to effectively prevent the particles in the ink composition from aggregating during storage and increasing the average particle diameter. Sedimentation can also be effectively suppressed. That is, according to the white ink composition according to the present embodiment, it is possible to stably maintain the dispersed state of the particles in the ink composition.
- the white ink composition according to the present embodiment has good initial fillability into an inkjet printer head and good continuous printing stability. In addition, it is possible to obtain an image with no unevenness and high whiteness and hiding power.
- the viscosity at 25° C. of the white ink composition according to the present embodiment is preferably about 2 to 20 mPa ⁇ s when measured with an E-type viscometer in terms of high-speed ejection response. Further, the surface tension at 25° C. of the white ink composition according to this embodiment is preferably about 20 to 45 mN/m when measured by the plate method. In practice, the physical properties are adjusted to appropriate values in consideration of the ejection volume, response speed, ink droplet flight characteristics, etc. of the ink jet printer to be used.
- the fabric used in this embodiment is not particularly limited, but examples thereof include natural fibers such as silk, cotton, wool, cellulose, nylon, polyester, and rayon, or synthetic fibers.
- the fabric may be a blend comprising two or more types of fibers.
- the pretreatment composition is preferably combined with one or more water-based ink compositions and used in the form of a printing set (also referred to as an "ink set").
- the constituent elements of the water-based ink composition constituting the print set are as described above.
- a printing set includes a pretreatment composition containing water, a cationic polymer, and a cross-linking agent, and a water-based white ink composition containing water, a white pigment, a urethane resin, and a water-soluble organic solvent. , have The components of the water-based white ink composition that constitutes the print set are as described above.
- the resin in the ink composition agglomerates, and it is possible to suppress the penetration of the pigment into the fabric fibers, so that the color development can be improved.
- the print set of the present embodiment includes a pretreatment composition containing a cationic polymer and a cross-linking agent, thereby maintaining high color development and improving adhesion.
- the ink composition when adhered to the fabric without drying after applying the pretreatment composition in order to speed up printing, the above-mentioned decrease in adhesion becomes more pronounced. With the print set of the embodiment, the adhesion can be improved even if such high speed is achieved.
- the print set of the present embodiment can improve the adhesion even when used in such a textile printing method.
- the inkjet textile printing method of the present embodiment includes a pretreatment step of applying a pretreatment composition to a fabric to form a wet precoat layer, and applying a water-based ink composition to at least a part of the region where the wet precoat layer is formed. and applying an object.
- An inkjet textile printing method (hereinafter also simply referred to as textile printing method) of a preferred embodiment of the present invention includes a pretreatment step of applying the above pretreatment composition to a fabric to form a wet precoat layer, and a pretreatment step.
- Water, a pigment, a resin emulsion (resin fine particles), a water-soluble organic solvent, and a surfactant are applied to at least a portion of the region where the wet precoat layer is formed, without drying the fabric later. and a recording step of forming an image area by adhering the containing water-based ink composition.
- the printing method using the pretreatment composition includes a wet-on-dry method in which the ink composition is applied after coating and drying the pretreatment composition, and a method in which the ink composition is attached without coating and drying the pretreatment composition.
- a wet-on-wet method There is a wet-on-wet method.
- the wet-on-dry method is advantageous in that an image with high adhesion can be obtained, although the printing time is long due to drying.
- the inkjet textile printing method of the embodiment of the present application uses a pretreatment composition containing a cationic polymer and a cross-linking agent to improve the adhesion of the printed textile obtained by the wet-on-wet method and to generate unevenness. This is intended to reduce.
- the inkjet printing method of the embodiment of the present application it is possible to suppress strike-through when using polyester fibers, thin fibers of fabric, fibers with coarse stitches, etc., high density and adhesion It is particularly useful because it gives a high print quality.
- two or more ink compositions are sequentially applied to the same recording area, even the ink composition applied later can be effectively agglomerated. Specifically, a white ink composition is adhered to dark-colored fibers including black to form a base, and then colored inks are adhered to perform printing. In such a case, the inkjet textile printing method of the embodiment of the present application is particularly useful.
- the pretreatment step refers to the step of applying the pretreatment composition to the fabric.
- the means for applying the pretreatment composition is not particularly limited, but roller coating, spray coating, and inkjet coating can be used, for example. Among these, it is preferable to apply the pretreatment composition to the fabric in a non-contact manner, and it is more preferable to apply the composition by a spray coating method or an inkjet method. By applying the pretreatment composition in a non-contact manner, the application amount of the pretreatment composition can be more easily controlled, which tends to further improve the image quality obtained.
- the amount of pretreatment composition applied per unit area of fabric is greater than 0.035 g/cm 2 and less than 0.070 g/cm 2 to form a wet precoat layer.
- the coating amount is preferably 0.039 to 0.063 g/cm 2 , more preferably 0.040 to 0.060 g/cm 2 .
- the amount of the pretreatment composition applied per unit area of the fabric is 0.035 g/cm 2 in another embodiment (especially the embodiment using the water-based white ink composition). It is preferably greater than and less than 0.070 g/cm 2 and is used to form a wet precoat layer.
- the coating amount is more preferably 0.039 to 0.063 g/cm 2 , still more preferably 0.040 to 0.060 g/cm 2 .
- the application amount of the pretreatment composition exceeds 0.035 g / cm 2
- Ink droplets ejected from which easily permeate (penetrate) the opposite side of the fabric that is not printed on the fabric, can suppress ink strike-through and set the base with white ink.
- the inkjet textile printing method of the present embodiment preferably has a pressurizing step of applying pressure to the region where the wet precoat layer is formed after the pretreatment step.
- the method used in the above-described pressurization step of applying pressure is not particularly limited, but examples include a method using a commercially available roller or spatula, a method using a flat press, a roller type press, and the like. .
- the recording step applies the at least one water-based ink composition from a head to at least a part of the area where the wet precoat layer is formed without drying the fabric after the pretreatment step.
- This is a step of ejecting and depositing a water-based ink composition to form an image area.
- the recording step includes: In this step, the water-based white ink composition is ejected from a head to adhere the water-based white ink composition to form an image area.
- the recording step using a printing set that further includes a water-based ink composition includes applying the water-based white color to at least a part of the area where the wet precoat layer is formed without drying the fabric after the pretreatment step.
- the ink composition is ejected from the head to form a white image region
- the water-based ink composition is ejected from the head to part or all of the image-formed region by ejecting the water-based white ink composition. to form a color image area.
- the recording process After the pretreatment process, it is preferable to perform the recording process in a state in which 20% by mass or more of the volatile components remain in the pretreatment composition applied to the fabric. That is, in the printing method of the present embodiment, heating, air blowing, and standing for drying the pretreatment composition can be omitted. Therefore, in the case of in-line processing from the pretreatment process to the recording process, there is no need to provide a drying process in between, which makes it possible to simplify the apparatus and improve production efficiency. In the case of a normal ink composition, the adhesion of the cohesive resin in the water-based ink composition tends to decrease as the pretreatment composition remains.
- the residual rate of the volatile component of the pretreatment composition is the amount of the volatile component remaining on the fabric when performing the recording process, out of the applied amount (mass) of the volatile component contained in the pretreatment composition applied to the fabric. (mass) rate.
- the amount of volatile components in the pretreatment composition can be measured by the method described in Examples. Volatile components are components that do not remain on the fabric after drying the pretreatment composition, such as water and water-soluble organic solvents.
- the printing method of the present embodiment preferably further includes a drying step of heating the fabric after the recording step.
- a drying step of heating the fabric after the recording step By heating, the resin emulsion that can be contained in the pretreatment composition or the water-based ink composition is fused to the surface of the fabric, and the cross-linking reaction between the cross-linking agent and the resin emulsion is promoted, and at the same time water is evaporated.
- the obtained image tends to be more excellent in abrasion resistance and adhesion.
- the water-based ink composition-attached surface on the fabric may be pressure-treated even if the water-based ink composition-attached surface on the fabric is not pressure-treated.
- a non-contact heating method that does not apply pressure to the surface on which the composition is adhered is preferred. Examples of non-contact heating methods include oven drying (methods without pressing such as conveyor ovens and batch ovens). By having such a drying process, the production efficiency is further improved.
- dye transfer can be achieved by drying the white ink-adhered surface with a non-contact heating method. It is possible to suppress the decrease in whiteness due to
- the contact-type heating method which also pressurizes the surface of the fabric on which the water-based ink composition is adhered, is not particularly limited, but an example thereof includes a heat press.
- the heat source for heating is not particularly limited, infrared rays (lamps) can be used, for example.
- the temperature during drying should fuse the resin emulsion that may be contained in the ink composition, promote the cross-linking reaction between the cross-linking agent and the resin emulsion, and evaporate water.
- the temperature is preferably 130° C. or less, more preferably 120 to 130° C., from the viewpoint of preventing dye migration.
- the drying temperature is within the above range, it tends to be possible to suppress a decrease in whiteness due to migration of the dye, and to improve abrasion resistance and adhesion.
- the temperature is preferably 150°C or higher, more preferably 150 to 190°C, and particularly preferably 150 to 180°C.
- the drying temperature is within the above range, the abrasion resistance and adhesion tend to be improved. Further, by setting the temperature to 190° C. or less, it is possible to prevent thermal deterioration of the components contained in the fiber and the pretreatment composition.
- the drying time is preferably 3-20 minutes, more preferably 5-16 minutes.
- the time is preferably 3 to 10 minutes, more preferably 4 to 8 minutes, and particularly 5 to 7 minutes. preferable.
- the fabric may be washed with water and dried.
- a soaping treatment that is, a treatment for washing off unfixed pigments with a hot soap solution or the like may be performed.
- the pretreatment composition of the present invention has a high degree of whiteness and high concealability when a white ink is used as a base, and also has excellent adhesion to fabrics and leaves little trace of pretreatment, so that high-quality white textile printing can be achieved. make it possible. In addition, it is excellent in storage stability. Since the whiteness and opacity of the base can be increased, the color development of the image printed on the base with color ink can be increased, and a printed matter having a high-quality color image can be obtained. In addition, the printed matter obtained using the pretreatment composition of the present invention is excellent in various fastnesses such as lightfastness, water resistance and fastness to washing.
- the printing set of the present invention has high whiteness and high opacity when a white ink is used as a base, has excellent adhesion to the fabric, and leaves few traces of pretreatment, making it possible to print high-quality white textiles. do.
- the whiteness and opacity of the undercoat can be increased, the color developability of the image printed on the undercoat with color ink can be increased, and a printed matter having a high-quality color image can be obtained. .
- the textile printing method of the present invention provides a high degree of whiteness and hiding power when a white ink is used as a base, has excellent adhesion to the fabric, and leaves few traces of pretreatment, enabling high-quality white textile printing. do.
- the whiteness and opacity of the undercoat can be increased, the color developability of the image printed on the undercoat with color ink can be increased, and a printed matter having a high-quality color image can be obtained. .
- Preparation Example 1 Preparation of Dispersion 1 Hylos XVS-1202 (9 parts) manufactured by Seiko PMC was dissolved in 2-butanone (30 parts). To this solution was added a solution obtained by dissolving 0.9 parts of sodium hydroxide in ion-exchanged water (76 parts), and the mixture was stirred for 1 hour to obtain an emulsion. C.I. I. Pigment Black 7 (30 parts) was added, and dispersion treatment was performed with a sand grinder at 1500 rpm for 15 hours. After ion-exchanged water (150 parts) was added dropwise to the obtained liquid, the dispersing beads were separated by filtration.
- Dispersion 1 Part of the 2-butanone and water in the obtained mother liquor was distilled off under reduced pressure using an evaporator to concentrate, thereby obtaining a dispersion having a solid content of 11.9%. This is referred to as "dispersion 1".
- the solid content in the aqueous solution was obtained by the dry weight method using MS-70 manufactured by A&D Co., Ltd.
- the average particle size of the pigment contained in Dispersion 1 was 88 nm, and the viscosity of Dispersion 1 at 25° C. was 4.6 mPa ⁇ s.
- Preparation Examples 2 and 3 Preparation of water-based white ink composition and water-based ink composition. Inks 1 and 2 were obtained by thoroughly stirring and mixing the components shown in Table 1 below. The resulting ink was filtered through a mixed cellulose ester filter with a pore size of 5 ⁇ m, and then degassed using a vacuum pump to obtain test inks 1 and 2.
- Ink 1 Water-based white ink composition prepared in Preparation Example 2
- Ink 2 Water-based ink composition prepared in Preparation Example 3
- Dispersion 1 Dispersion 1 obtained in Preparation Example 1)
- Hydran WLS-201 urethane resin emulsion, solid content 35%, freezing point -11°C, glass transition temperature -79°C, manufactured by DIC Corporation
- JSR0568 styrene-butadiene resin latex, solid content 50%, manufactured by JSR Corporation
- Olfine EXP-4001 surfactant, manufactured by Nissin Chemical Industry Co., Ltd.
- Surfynol 420 Surfactant, manufactured by Nissin Chemical Industry Co., Ltd.
- Surfynol DF-110D Surfactant, manufactured by Nissin Chemical Industry Co.
- Examples 1-5, Comparative Examples 1-7 Preparation of pretreatment composition. Each component shown in Table 2 below was mixed to obtain a total amount of 100 parts of a pretreatment composition. The obtained liquid was filtered through a membrane filter having an average pore size of 3 ⁇ m to obtain pretreatment compositions 1 to 8 for evaluation test.
- DK6850 Epihalohydrin-modified polyamine resin (manufactured by Seiko PMC, weight average molecular weight: 1703, cationic polymer containing epihalohydrin structural units, active ingredient 70%)
- DK6854 Epihalohydrin-modified polyamine resin (manufactured by Seiko PMC, weight average molecular weight: 5853, cationic polymer containing epihalohydrin structural units, active ingredient 50%)
- PAA-HCL-03 allylamine hydrochloride polymer (manufactured by Nittobo Medical, weight average molecular weight: 6611, cationic polymer containing allylamine structural units, active ingredient 40%)
- Meikanate FM-1 blocked isocyanate-based cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature 120
- Meikanate ST blocked isocyanate cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature 120 ° C. or higher, active ingredient 30%)
- Mass % of cationic polymer content (%) of cationic polymer relative to total mass of pretreatment composition
- Pretreatment process Each of the pretreatment compositions 1 to 8 obtained above was applied to a polyester fabric (dry T-shirt, black 00300-ACT (manufactured by glimmer)) in an amount shown in Table 2 above, and each was applied to a size of A4 and wetted. A precoat layer was formed. At that time, pretreatment compositions 1 to 8 were applied using a commercially available sprayer (manufactured by Mitsugiron Co., Ltd., Fine Spray). Immediately after applying the pretreatment composition, the following recording process was carried out.
- a commercially available sprayer manufactured by Mitsugiron Co., Ltd., Fine Spray
- the water-based white ink composition (ink 1) prepared as described above was filled in an industrial inkjet evaluation device (extended coating device EV2500: manufactured by Ricoh Co., Ltd.). Then, under the conditions of ink droplet weight of 29 pl/dot, head temperature of 25° C., resolution of 600 ⁇ 1200 dpi, and 6 times of overprinting, the water-based ink composition (ink 1) was applied to the wet precoat layer obtained as described above. A white solid pattern image was formed by adhering to a part of the area of . In the examples and comparative examples, after the ink composition was deposited, drying was performed by heating and drying at 130° C. for 3 minutes using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO).
- DDC-6A drawer-type electric dryer
- recorded matter was also created by subjecting the fabric to a pretreatment process and not attaching ink, but performing heat drying in the same manner as when attaching ink.
- the pretreatment compositions of Examples which contain a cationic polymer containing a specific structural unit and a cross-linking agent, are superior to the pretreatment compositions of Comparative Examples 1 to 4.
- the whiteness, hiding power, and adhesion were good, there was no trace of pretreatment, and the storage stability was excellent.
- Comparative Example 1 which does not contain a cross-linking agent, the whiteness, hiding property, and adhesion are lowered, and in Comparative Example 2, in which the amount of the cationic polymer added is small, the whiteness and adhesion are lowered, and the cationic polymer is reduced.
- Comparative Example 3 in which the addition amount was large, the trace was worse.
- storage stability deteriorated in Comparative Example 4 in which the amount of the cross-linking agent added was large.
- Examples 6-18, Comparative Examples 8-13 Preparation of pretreatment compositions. Each component shown in Table 3 below was mixed to obtain a total amount of 100 parts of a pretreatment composition. The obtained liquid was filtered through a membrane filter having an average pore size of 3 ⁇ m to obtain pretreatment compositions 9 to 24 for evaluation test.
- DK6850 Epihalohydrin-modified polyamine resin (manufactured by Seiko PMC, weight average molecular weight: 1703, cationic polymer containing epihalohydrin structural units, active ingredient 70%)
- DK6854 Epihalohydrin-modified polyamine resin (manufactured by Seiko PMC, weight average molecular weight: 5853, cationic polymer containing epihalohydrin structural units, active ingredient 50%)
- DK6885 Epihalohydrin-modified polyamine resin (manufactured by Seiko PMC, weight average molecular weight: 2038, cationic polymer containing epihalohydrin structural units, active ingredient 70%)
- PAA-HCL-01 allylamine hydrochloride polymer (manufactured by Nittobo Medical, weight average molecular weight: 1955, cationic polymer containing allylamine structural
- Pretreatment process The pretreatment compositions 9 to 24 obtained above were applied to a polyester fabric (dry T-shirt, black 00300-ACT (manufactured by glimmer)) at the coating amount shown in Table 3 above, respectively, to A4 size, and wet. A precoat layer was formed. At that time, pretreatment compositions 9 to 24 were applied using a commercially available sprayer (manufactured by Mitsugiron Co., Ltd., Fine Spray). Immediately after applying the pretreatment composition, the following recording process was carried out.
- a commercially available sprayer manufactured by Mitsugiron Co., Ltd., Fine Spray
- the water-based ink composition (ink 1) prepared as described above was filled in an industrial inkjet evaluation device (extended coating device EV2500: manufactured by Ricoh Co., Ltd.). Then, under the conditions of ink droplet weight of 29 pl/dot, head temperature of 25° C., resolution of 600 ⁇ 1200 dpi, and 6 times of overprinting, the water-based ink composition (ink 1) was applied to the wet precoat layer obtained as described above. A white solid pattern image was formed by adhering to a part of the area of . After the ink composition was adhered, it was dried by heating at 130° C. for 3 minutes using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO).
- DDC-6A drawer-type electric dryer
- the pretreatment compositions of Examples which contain a cationic polymer containing a specific structural unit and a cross-linking agent, are superior to the pretreatment compositions of Comparative Examples 8-10.
- the whiteness, hiding power, and adhesion were good, there was no trace of pretreatment, and the storage stability was excellent.
- Comparative Example 8 in which the amount of the cationic polymer added was small, resulted in a decrease in whiteness and adhesion, while Comparative Example 9, in which the amount of the cationic polymer added was large, resulted in a worsening of marks.
- Comparative Example 10 in which the amount of the cross-linking agent added was large, the storage stability deteriorated. It was found that Comparative Example 11, in which the pretreatment composition was applied in a large amount, produced a bad trace, while Comparative Examples 12 and 13, in which the pretreatment composition was applied in a small amount, exhibited a decrease in whiteness, hiding power, and adhesion.
- Examples 19-22, Comparative Examples 14-17 Preparation of pretreatment compositions. Each component shown in Table 4 below was mixed to obtain a total amount of 100 parts of a pretreatment composition. The obtained liquid was filtered through a membrane filter having an average pore size of 3 ⁇ m to obtain pretreatment compositions 1, 2, 4 to 8 for evaluation test.
- DK6850 Epihalohydrin-modified polyamine resin (manufactured by Seiko PMC, weight average molecular weight: 1703, cationic polymer containing epihalohydrin structural units, active ingredient 70%)
- PAA-HCL-03 allylamine hydrochloride polymer (manufactured by Nittobo Medical, weight average molecular weight: 6611, cationic polymer containing allylamine structural units, active ingredient 40%)
- Meikanate FM-1 blocked isocyanate-based cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature 120 ° C.
- Meikanate ST blocked isocyanate-based cross-linking agent (manufactured by Meisei Chemical Industry Co., Ltd., cationic, dissociation temperature 120 ° C. or higher, active ingredient 30%)
- the pretreatment compositions 1, 2, 4 to 8 are applied in the amounts shown in Table 4 to a polyester fabric (dry T-shirt, black 00300-ACT (manufactured by glimmer)) in A4 size and wet precoat. formed a layer. At that time, the pretreatment compositions 1, 2, 4 to 8 were applied using a commercially available sprayer (manufactured by Mitsugiron Co., Ltd., Fine Spray). Immediately after applying the pretreatment composition, the following recording process was carried out.
- the water-based white ink composition (ink 1) and the water-based ink composition (ink 2) prepared as described above were filled in an industrial inkjet evaluation device (extended type coating device EV2500: manufactured by Ricoh Co., Ltd.). Thereafter, under the conditions of an ink droplet weight of 29 pl/dot, a head temperature of 25° C., a resolution of 600 ⁇ 1200 dpi, and 6 times of overprinting, the water-based white ink composition (ink 1) obtained as described above was wetted. It was deposited over a portion of the area of the precoat layer to form a solid white pattern image.
- an industrial inkjet evaluation device extended type coating device EV2500: manufactured by Ricoh Co., Ltd.
- the water-based ink composition (ink 2) was applied under the conditions of an ink droplet weight of 27 pl/dot, a head temperature of 25° C., a resolution of 600 ⁇ 1200 dpi, and 6 times of overprinting. was applied to half of the applied area to form a black solid pattern image.
- the resulting printed material was dried by heating at 130° C. for 3 minutes using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO). The pretreatment process and recording process were performed at room temperature of 25°C.
- recorded matter was also produced by subjecting the fabric to a pretreatment process and not attaching ink, but performing heat drying in the same manner as when attaching ink.
- Examples 23-30, Comparative Examples 18-29 Preparation of pretreatment compositions. Each component shown in Table 5 below was mixed to obtain a total amount of 100 parts of a pretreatment composition. The obtained liquid was filtered through a membrane filter having an average pore size of 3 ⁇ m to obtain pretreatment compositions 1, 2, 4 to 8 for evaluation test.
- Pretreatment process Pretreatment compositions 1, 2, 4 to 8 were applied in the amounts shown in Table 5, cotton fabric 1 (heavyweight T-shirt, black 00085-CVT (manufactured by PrintStar)), cotton fabric 2 (sheeting, (10000L) 300 .
- Black (B) Shinjuku Okadaya
- Cotton fabric 3 (Daily fine call, (KOF-14) BK.
- Black (B) (Shinjuku Okadaya)
- 35% cotton / 65% polyester blend T/C broad, (AD40000) 300.
- Example 30 after applying the pretreatment composition, the wet precoat layer was subjected to a step of laying down the fluff of the fabric using a roller (wallpaper construction tool roller manufactured by Yayoi Kagaku Co., Ltd.), and immediately thereafter, the following recording step was performed. rice field.
- the water-based white ink composition (ink 1) and the water-based ink composition (ink 2) prepared as described above were filled in an industrial inkjet evaluation device (extended type coating device EV2500: manufactured by Ricoh Co., Ltd.). Thereafter, under the conditions of an ink droplet weight of 29 pl/dot, a head temperature of 25° C., a resolution of 600 ⁇ 1200 dpi, and 6 times of overprinting, the water-based white ink composition (ink 1) obtained as described above was wetted. It was deposited over a portion of the area of the precoat layer to form a solid white pattern image.
- an industrial inkjet evaluation device extended type coating device EV2500: manufactured by Ricoh Co., Ltd.
- the water-based ink composition (ink 2) was applied under the conditions of an ink droplet weight of 27 pl/dot, a head temperature of 25° C., a resolution of 600 ⁇ 1200 dpi, and 6 times of overprinting. was applied to half of the applied area to form a black solid pattern image.
- the resulting printed matter was dried at 150°C using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO). It was dried by heat drying at °C for 10 minutes.
- the resulting printed material was dried at 130° C. for 3 minutes using a drawer-type electric dryer (DDC-6A, manufactured by ADELCO). was dried by heating.
- the pretreatment process and recording process were performed at room temperature of 25°C.
- recorded matter was also created by subjecting the fabric to a pretreatment process and not attaching ink, but performing heat drying in the same manner as when attaching ink.
- the pretreatment compositions of the examples had good whiteness, hiding properties, and adhesion to various fabrics compared to the textile printing methods of the comparative examples.
- the result was that the ink composition (color ink) had little solid unevenness and no trace of pretreatment.
- Comparative Example 18 which does not contain a cross-linking agent, the whiteness, hiding properties, and adhesion are lowered. It was found that in Comparative Example 20 in which the addition amount was large, traces were worse. In addition, it was found that storage stability deteriorated in Comparative Example 21 in which the amount of the cross-linking agent added was large.
- Comparative Example 22 in which the pretreatment composition was applied in an amount of 0.070 g/cm 2 or more, traces of the pretreatment were poor, and in Comparative Example 23, in which the pretreatment composition was applied in an amount of 0.035 g/cm 2 or less. , 24, it was found that the whiteness, the hiding property, and the adhesion property were lowered. In addition, in Comparative Examples 25 to 29 in which drying was performed after the pretreatment, it was found that a poor decrease in whiteness causes a decrease in whiteness and hiding property, and the solid color unevenness is conspicuous.
- the pretreatment composition of the present invention has good whiteness, hiding properties, and adhesion, and can give excellent prints without traces of pretreatment, and the pretreatment composition has good storage stability. Therefore, it is extremely useful as a pretreatment composition for a wide variety of fabrics.
- the printing set of the present invention it is possible to obtain excellent printed matter with good whiteness, hiding properties, and adhesion on various fabrics, and without traces of pretreatment. Because of its good storage stability, it is extremely useful as a printing set for a wide variety of fabrics.
- the inkjet textile printing method of the present invention can obtain excellent printed matter with good whiteness, hiding properties, and adhesion on various fabrics, and without traces of pretreatment. Since the storage stability of is good, the range of application of fabrics can be expanded, and it is extremely useful as an inkjet printing method for a wide variety of fabrics.
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Abstract
Description
インクジェット捺染方法は、スクリーン印刷やグラビア印刷等のアナログ印刷方法よりも、少量多品種の印刷物に適しており、インクジェット捺染方法による布帛の適用範囲の拡大が望まれている。このような適用範囲の拡大に伴い、ガーメント印刷やホームテキスタイル印刷において、様々な布帛(例えば、綿、ポリエステル、ナイロン、又は2種以上の繊維を含む混紡等)や様々な生地の種類(例えば、ニット、シーチング、ブロード、オックスフォード、シャンブレー、メッシュなど)に対して、濃度、堅牢性(例えば、摩擦堅牢度、洗濯堅牢度、耐光性等)の更なる向上が求められている。
また、この裏抜けを防止する目的で、繊維に前処理を行うことも提案されている。しかし、裏抜けの防止を重視するあまり高濃度の前処理液(以下、前処理組成物ともいう)や、多量の前処理液を繊維に塗布すると(付着させると)、前処理液が付与された部分の繊維に、その前処理液を付与した「痕跡」が残ってしまう問題も生じ、これも問題の1つとなっている。「痕跡」とは、例えば黒色等の濃色の繊維においては、白っぽく見える状態として観察される。一方、例えば水色等の淡色の繊維においては、水に濡れたように色が濃く見える状態として観察される。そのような痕跡が残ると、捺染物の見た目が著しく悪化する。このため、捺染物の商品としての価値の低下、又は消失にもつながるため、裏抜けの防止と共に、「痕跡」が残らない前処理液が強く望まれている。
また、濃色の繊維に白色インクで下地を設置するときも、繊維(生地)の種類によっては、上記の「裏抜け」が生じることがあり、これが白色度及び隠蔽性の低下の大きな問題の1つとなっている。
裏抜け以外にも、前処理された部分の繊維が毛羽立ってしまうことにより、白色の下地にムラが観察されることがある。このムラによっても捺染物としての品質が大きく低下する。
このため、これらの問題を解決できる前処理組成物と、捺染方法、前処理組成物及びインク組成物を有する印刷セット、が強く望まれている。
即ち、本発明は以下の1)~39)に関する。
インクジェット方式により布帛に画像を形成する水系インク組成物を受容する湿潤したプレコート層を形成するために用いられる前処理組成物であって、下記[1]~[4]の要件を全て満たす前処理組成物。
[1]上記水系インク組成物が、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有する。
[2]単位面積当たりの上記前処理組成物塗布量が0.035g/cm2を超え、かつ、0.070g/cm2未満である、湿潤したプレコート層を形成するために用いられる。
[3]上記前処理組成物が、水、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満のカチオン性ポリマー、上記前処理組成物全質量に対して0.1質量%以上、かつ、2.7質量%未満の架橋剤を含有する。
[4]カチオン性ポリマーが、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかを含む。
2)
前記架橋剤が、ブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物、オキサゾリン基含有化合物からなる群から選択される1種以上のカチオン性の架橋剤を含む、1)に記載の前処理組成物。
3)
前記ブロック型イソシアネート基含有化合物の解離温度が120℃以上である、2)に記載の前処理組成物。
4)
25℃における表面張力が35~60mN/mである、1)~3)のいずれか一項に記載の前処理組成物。
5)
1)~4)のいずれか一項に記載の前処理組成物と、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有する水系インク組成物と、を含む印刷セット。
6)
1)~4)のいずれか一項に記載の前処理組成物を布帛に塗布し、湿潤したプレコート層を形成する前処理工程と、前記湿潤したプレコート層を形成した領域の少なくとも一部に対し、インクジェット方式により、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有する水系インク組成物を付着させて、画像領域を形成する記録工程と、を有するインクジェット捺染方法。
7)
上記前処理工程後、上記布帛に塗布した前処理組成物の残存量が、上記前処理工程における塗布量の総量に対し、20質量%以上の状態で、上記記録工程を有する、6)に記載のインクジェット捺染方法。
8)
1)~4)のいずれか一項に記載の前処理組成物を塗布した布帛に、前記水系インク組成物が印刷されてなる印刷物。
水、カチオン性ポリマー、架橋剤、を含む前処理組成物と、
水、白色顔料、ウレタン樹脂、水溶性有機溶剤、を含む水系の白色インク組成物と、を有する印刷セットであって、
上記前処理組成物中の上記カチオン性ポリマーの含有量が、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満であり、上記架橋剤の含有量が、前処理組成物全質量に対して、0.1質量%以上、かつ、2.7質量%未満である、前処理組成物と水系の白色インク組成物の印刷セット。
10)
上記カチオン性ポリマーが、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかの構造単位を含むポリマーである、9)に記載の印刷セット。
11)
前記架橋剤が、ブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物、オキサゾリン基含有化合物からなる群から選択される1種以上のカチオン性の架橋剤を含む、9)又は10)に記載の印刷セット。
12)
上記ブロック型イソシアネート基含有化合物の解離温度が120℃以上である、11)に記載の印刷セット。
13)
上記前処理組成物の25℃における表面張力が、35~60mN/mである、9)~12)のいずれか一項に記載の印刷セット。
14)
上記ウレタン樹脂が、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂からなる群から選択される少なくともいずれかを含む、9)~13)のいずれか一項に記載の印刷セット。
15)
上記ウレタン樹脂のガラス転移温度が、0℃以下である、9)~14)のいずれか一項に記載の印刷セット。
16)
上記水系の白色インク組成物が、更に塩基を含む、9)~15)のいずれか一項に記載の印刷セット。
17)
水、顔料、高分子分散剤を含む水系インク組成物をさらに有する、9)~16)のいずれか一項に記載の印刷セット。
18)
上記高分子分散剤が、下記式(1)で表されるモノマーA、モノマーB、及びモノマーCよりなる群から選択される少なくとも2種類の構成モノマーを含むポリマーである、17)に記載の印刷セット。
モノマーA:下記式(1)中、Rが水素原子であるモノマー。
モノマーB:下記式(1)中、RがC1-C4アルキル基であるモノマー。
モノマーC:下記式(1)中、Rがアリール基又はアリールC1-C4アルキル基であるモノマー。
上記水系インク組成物が、更にウレタン樹脂、スチレン-ブタジエン樹脂、アクリル樹脂からなる群から選択される少なくともいずれかを含む、17)又は18)に記載の印刷セット。
20)
布帛に、9)~19)のいずれか一項に記載の印刷セットに含まれる前処理組成物を塗布し、湿潤したプレコート層を形成する前処理工程と、該前処理工程後に上記布帛を乾燥することなく、上記湿潤したプレコート層の一部又は全部の領域に、9)~19)のいずれか一項に記載の印刷セットに含まれる水系の白インク組成物をインクジェット方式により吐出して画像を形成する工程と、を有する、インクジェット捺染方法。
21)
布帛に、9)~19)のいずれか一項に記載の印刷セットに含まれる前処理組成物を塗布し、湿潤したプレコート層を形成する前処理工程と、該前処理工程後に上記布帛を乾燥することなく、上記湿潤したプレコート層の一部又は全部の領域に、9)~19)のいずれか一項に記載の印刷セットに含まれる水系の白色インク組成物をインクジェット方式により吐出して画像を形成する工程と、上記水系の白色インク組成物を吐出して画像を形成した領域の一部又は全部に、17)~19)のいずれか一項に記載の印刷セットに含まれる水系インク組成物をインクジェット方式により吐出して画像を形成する工程と、を有する、インクジェット捺染方法。
22)
上記布帛が、ポリエステル、又は、ポリエステルを含む混紡である、20)又は21)に記載のインクジェット捺染方法。
23)
上記水系インク組成物を付与する工程後、画像を形成した布帛を130℃以下で乾燥する工程を含む、22)に記載のインクジェット捺染方法。
24)
上記布帛が、綿、又は、綿を含む混紡である、20)又は21)に記載のインクジェット捺染方法。
25)
上記前処理工程後、上記湿潤したプレコート層を形成した領域に圧力を加える加圧工程を有する、24)に記載のインクジェット捺染方法。
水、カチオン性ポリマー、架橋剤、を含む前処理組成物と、
少なくとも1種の水系インク組成物と、を用い、布帛に対して画像を形成するインクジェット捺染方法であって、
上記布帛に上記前処理組成物を塗布し、湿潤したプレコート層を形成する前処理工程と、該前処理工程後に上記布帛を乾燥することなく、上記湿潤したプレコート層の領域に、上記少なくとも1種の水系インク組成物を付与する工程と、を有し、上記布帛における前処理組成物の単位面積当たりの塗布量が0.035g/cm2を超え、かつ、0.070g/cm2未満であり、かつ、上記前処理組成物中の上記カチオン性ポリマーの含有量が、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満であり、上記架橋剤の含有量が、前処理組成物全質量に対して、0.1質量%以上、かつ、2.7質量%未満であり、上記水系インク組成物が水、顔料、樹脂エマルション、水溶性有機溶剤及び界面活性剤を含有する、インクジェット捺染方法。
27)
上記樹脂エマルションが、ウレタン樹脂、スチレン-ブタジエン樹脂、アクリル樹脂からなる群から選択される少なくともいずれかを含む、26)に記載のインクジェット捺染方法。
28)
上記水系インク組成物が、さらに、高分子分散剤を含む、26)又は27)に記載のインクジェット捺染方法。
29)
前記高分子分散剤が、下記式(1)で表されるモノマーA、モノマーB、及びモノマーCよりなる群から選択される少なくとも2種類の構成モノマーを含むポリマーである、28)に記載のインクジェット捺染方法。
モノマーA:下記式(1)中、Rが水素原子であるモノマー。
モノマーB:下記式(1)中、RがC1-C4アルキル基であるモノマー。
モノマーC:下記式(1)中、Rがアリール基又はアリールC1-C4アルキル基であるモノマー。
上記顔料が、白色顔料である、26)~29)のいずれか一項に記載のインクジェット捺染方法。
31)
上記ウレタン樹脂が、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂からなる群から選択される少なくともいずれかを含む、27)~30)のいずれか一項に記載のインクジェット捺染方法。
32)
前記カチオン性ポリマーが、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかの構造単位を含むポリマーである、26)~31)のいずれか一項に記載のインクジェット捺染方法。
33)
上記架橋剤が、ブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物、オキサゾリン基含有化合物からなる群から選択される1種以上のカチオン性の架橋剤を含む、26)~32)のいずれか一項に記載のインクジェット捺染方法。
34)
上記ブロック型イソシアネート基含有化合物の解離温度が120℃以上である、33)に記載のインクジェット捺染方法。
35)
上記前処理組成物の25℃における表面張力が、35~60mN/mである、26)~34)のいずれか一項に記載のインクジェット捺染方法。
36)
上記布帛が、ポリエステル、又は、ポリエステルを含む混紡である、26)~35)のいずれか一項に記載のインクジェット捺染方法。
37)
上記水系インク組成物を付与する工程後、画像を形成した布帛を130℃以下で乾燥する工程を含む、36)に記載のインクジェット捺染方法。
38)
上記布帛が、綿、又は、綿を含む混紡である、26)~35)のいずれか一項に記載のインクジェット捺染方法。
39)
上記前処理工程後、上記湿潤したプレコート層を形成した領域に圧力を加える加圧工程を有する、26)~38)のいずれか一項に記載のインクジェット捺染方法。
また、本発明により、上記の痕跡、裏抜け、及び毛羽立ちを生じにくく、白色を含むカラーインクを使用したときに、高い発色性を有する画像が得られる、インクジェット捺染方法を提供できた。
また、本実施形態の印刷セットは、上記前処理組成物と、水系インク組成物と、を有し、該水系インク組成物は、水、顔料を含む。
[1]上記水系インク組成物が、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有する。
[2]単位面積当たりの上記前処理組成物塗布量が0.035g/cm2を超え、かつ、0.070g/cm2未満である、湿潤したプレコート層を形成するために用いられる。
[3]上記前処理組成物が、水、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満のカチオン性ポリマー、上記前処理組成物全質量に対して0.1質量%以上、かつ、2.7質量%未満の架橋剤を含有する。
[4]カチオン性ポリマーが、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかを含む。
上記前処理組成物は、水、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満のカチオン性ポリマー、上記前処理組成物全質量に対して0.1質量%以上、かつ、2.7質量%未満の架橋剤を含有する。
上記前処理組成物は水を含有する。水としては、特に制限されることなく、イオン交換水、限外濾過水、逆浸透水、蒸留水等の純水、又は超純水を用いることができる。水の含有量は、特に制限されることなく必要に応じて適宜決定すればよいが、前処理組成物中の重量固形分を好適な範囲に調整するため、前処理組成物の総質量(100質量%)に対して70~99質量%含まれていることが好ましく、80~98質量%含まれていることがより好ましい。
上記前処理組成物は、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.0質量%未満のカチオン性ポリマーを含有することを特徴とする。該カチオン性ポリマーは、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、及びエピハロヒドリン構造単位からなる群から選択される少なくともいずれかを含み、アリルアミン構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかを含んでいることがより好ましい。上記のカチオン性ポリマーはいずれも強電解質であり、前処理組成物中における前記カチオン性ポリマーの溶解安定性が良好であるとともに、インキ中の顔料の分散低下能力に優れている。
上記カチオン性ポリマーの重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)法を用いて、標準ポリスチレン換算によって測定することが可能である。
上記前処理組成物は、上記前処理組成物全質量に対して0.1質量%以上、かつ、2.7質量%未満の架橋剤を含有することを特徴とする。該架橋剤は、例えば、ブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物、オキサゾリン基含有化合物からなる群から選択される1種以上のカチオン性の架橋剤を含むことが好ましい。少なくともブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物を含んでいることがより好ましい。
また、本発明において、「ブロック型イソシアネート基含有化合物」とは、ポリイソシアネート化合物中のイソシアネート基をブロック剤でブロックされている化合物を表す。
上記カルボジイミド基含有化合物の市販品としては、例えば、カルボジライトE-02、カルボジライトE-03A、カルボジライトE-05、カルボジライトV-02、カルボジライトV-02-L2、カルボジライトV-04(以上、日清紡ケミカル株式会社製、商品名)等が挙げられる。これらの中では、前処理組成物の保存安定性の観点から、カルボジライトE-02、カルボジライトV-04が好ましい。
上記前処理組成物は、上記各成分以外に、樹脂エマルション、水溶性有機溶剤、表面張力調整剤、防黴剤、防腐剤、pH調整剤、キレート試薬、防錆剤、水溶性紫外線吸収剤、酸化防止剤、糊剤等の調製剤をさらに含有していてもよい。
上記樹脂エマルションとしては、例えば、(メタ)アクリル樹脂、(メタ)アクリル樹脂共重合体、スチレン-無水マレイン酸共重合体樹脂、エポキシ樹脂、ウレタン樹脂、ポリエーテル樹脂、ポリアミド樹脂、不飽和ポリエステル樹脂、フェノール樹脂、シリコーン樹脂、フッ素樹脂、ポリビニル樹脂(塩化ビニル、酢酸ビニル、ポリビニルアルコール等)、酢酸ビニル-(メタ)アクリル共重合体樹脂、酢酸ビニル-エチレン共重合体樹脂、アルキド樹脂、ポリエステル樹脂、アミノ樹脂(メラニン樹脂、ユリア樹脂、尿素樹脂、メラニンホルムアルデヒド樹脂等)等から形成されたエマルションを挙げることができる。樹脂エマルションは、2種類以上の樹脂を含んでいてもよい。また、2種類以上の樹脂がコア/シェル構造を形成していてもよい。樹脂エマルションは、1種類を単独で使用してもよく、2種類以上を併用してもよい。樹脂エマルションの中でも、透明の塗膜を形成する樹脂を用いることが好ましく、前処理組成物の保存安定性、耐擦過性及び密着性の観点から、アクリル樹脂エマルション、ウレタン樹脂エマルションが好ましい。
上記水溶性有機溶剤としては、例えば、グリコール系溶剤、多価アルコール類、多価アルコールアルキルエーテル類等を挙げることができる。グリコール系溶剤としては、グリセリン、ポリグリセリン(#310、#750、#800)、ジグリセリン、トリグリセリン、テトラグリセリン、ペンタグリセリン、ヘキサグリセリン、ヘプタグリセリン、オクタグリセリン、ノナグリセリン、デカグリセリン、ウンデカグリセリン、ドデカグリセリン、トリデカグリセリン、テトラデカグリセリン等が挙げられる。多価アルコール類としては、アルコール性水酸基を2~3個有するC2-C6多価アルコール、ジ又はトリC2-C3アルキレングリコール、繰り返し単位が4以上で分子量20000程度以下のポリC2-C3アルキレングリコール(好ましくは液状のポリアルキレングリコール)等が挙げられる。多価アルコール類の具体例としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、チオジグリコール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、3-メチル-1,3-ブタンジオール、1,2-ペンタンジオール、1,5-ペンタンジオール、2-メチル-2,4-ペンタンジオール、3-メチル-1,5-ペンタンジオール、1,2-ヘキサンジオール、1,6-ヘキサンジオール、トリメチロールプロパン、1,3-ペンタンジオール、1,5-ペンタンジオール等が挙げられる。多価アルコールアルキルエーテル類としては、アルキレングリコールモノアルキルエーテル、ジアルキレングリコールモノアルキルエーテル、トリアルキレングリコールモノアルキルエーテル等が挙げられる。具体的には、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノイソブチルエーテル、テトラエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル等が挙げられる。また、トリエチレングリコールモノブチルエーテル等が挙げられる。
また、水に溶解して湿潤剤としての役割をする化合物等も、便宜上、水溶性有機溶剤に含めるものとする。そのような化合物としては、例えば、尿素、エチレン尿素、糖類等が挙げられる。水溶性有機溶剤は、1種類を単独で使用してもよく、2種類以上を併用してもよい。
上記表面張力調整剤の種類は特に限定されないが、例えば、アセチレングリコール、及びポリアルキレングリコールから選択される界面活性剤が好ましい。界面活性剤を含有することにより、前処理組成物の粘度の増加、成分の凝集等が抑制され、保存安定性が良好となる。
前記のうち、界面活性剤として少なくともポリアルキレングリコールを含有する前処理組成物は、さらに下地の白色度、及び裏抜けが良好になる傾向がある。
脂肪酸エチレンオキシド付加物としては、ステアリン酸エチレンオキシド付加物、ポリエチレングリコールラウリン酸エステル等が挙げられる。その市販品の例としては、例えば、花王株式会社製のエマノーン1112、3199V、3299V、3299VR、3201M-V等が挙げられる。
高級アルキルアミンエチレンオキシド付加物の市販品の例としては、例えば、花王株式会社製のアミート102、105、105A、302、320等が挙げられる。
ポリオキシC2-C4アルキレングリコールの市販品の例としては、例えば、花王株式会社製のエマルゲンPP-290(ポリエチレングリコール/ポリプロピレングリコールが160/30のコポリマー);三洋化成工業株式会社製のニューポールPE-61、PE-62、PE-64、PE-68、PE-71、PE-74、PE-75、PE-78、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);第一工業製薬株式会社製のエパン410、420、450、485、680、710、720、740、750、785、U-103、U-105、U-108(ポリプロピレングリコールの重量平均分子量が約950~4000、ポリオキシエチレンの含有量が5~95%程度のポリオキシエチレンポリオキシプロピレングリコール)等が挙げられる。ポリオキシC2-C4アルキレングリコールとしてはポリオキシC2-C3アルキレングリコールが好ましく、ポリオキシエチレンポリオキシプロピレングリコールがより好ましい。また、ポリオキシC2-C4アルキレングリコール中のオキシC2-C4アルキレン基の総数における、オキシC2アルキレン基の数が通常50%より小さく、好ましくは15~45%、より好ましくは20~40%である。一例を挙げると、オキシC2アルキレン基、オキシC3アルキレン基、及びオキシC4アルキレン基の結合数の合計が10のとき、オキシアルキレン基の結合数は5より小さいことを意味する。なお、オキシC2-C4アルキレン基の結合数は、いずれも平均値である。また、ポリオキシアルキレングリコールのうち、ポリオキシC3-C4アルキレン基を疎水基とし、ポリオキシC2アルキレン基を親水基としたとき、疎水基の重量平均分子量が通常2250~4000、好ましくは2750~3600である。オキシC2アルキレン基の含有率、及び、疎水基の重量平均分子量の両方を満たすものとしては、例えば、エパンU-103が挙げられる。カチオン性ポリマーを含有する前処理組成物が、このような界面活性剤を含有することにより、保存安定性を良好にすることができる。
上記防黴剤の具体例としては、例えば、デヒドロ酢酸ナトリウム、安息香酸ナトリウム、ナトリウムピリジンチオン-1-オキシド、p-ヒドロキシ安息香酸エチルエステル、1,2-ベンズイソチアゾリン-3-オン及びその塩等が挙げられる。
上記防腐剤としては、例えば、有機硫黄系、有機窒素硫黄系、有機ハロゲン系、ハロアリルスルホン系、ヨードプロパギル系、N-ハロアルキルチオ系、ニトリル系、ピリジン系、8-オキシキノリン系、ベンゾチアゾール系、イソチアゾリン系、ジチオール系、ピリジンオキシド系、ニトロプロパン系、有機スズ系、フェノール系、第4アンモニウム塩系、トリアジン系、チアジン系、アニリド系、アダマンタン系、ジチオカーバメイト系、ブロム化インダノン系、ベンジルブロムアセテート系、無機塩系等の化合物が挙げられる。有機ハロゲン系化合物の具体例としては、ペンタクロロフェノールナトリウム等が挙げられる。ピリジンオキシド系化合物の具体例としては、2-ピリジンチオール-1-オキサイドナトリウム等が挙げられる。イソチアゾリン系化合物の具体例としては、1,2-ベンズイソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オンマグネシウムクロライド、5-クロロ-2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド、2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド等が挙げられる。その他の防腐剤(防腐防黴剤)の具体例としては、無水酢酸ソーダ、ソルビン酸ソーダ、安息香酸ナトリウム、Lonza社製の商品名プロクセルRTMGXL(S)、プロクセルRTMXL-2(S)等が挙げられる。
上記pH調整剤としては、調製される前処理組成物に悪影響を及ぼさずに、インクのpHを例えば3.0~9.0の範囲に制御できるものであれば任意の物質を使用することができる。pH調整剤としてはアルカリ金属の水酸化物、アルカリ土類金属の水酸化物、脂肪族アミン化合物及びアルコールアミン化合物等が挙げられる。アルカリ金属の水酸化物としては、例えば水酸化リチウム、水酸化ナトリウム及び水酸化カリウムが挙げられる。アルカリ土類金属の水酸化物として、例えば水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム及び水酸化ストロンチウム等が挙げられる。これらの中ではアルカリ土類金属の水酸化物が好ましく、水酸化リチウム及び水酸化ナトリウムがより好ましい。脂肪族アミン化合物としては、例えばアンモニア、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン及びトリエチルアミンが挙げられるが、好ましくはアンモニア又はトリエチルアミンである。アルコールアミン化合物としては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン、メチルエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン及びN-メチルジエタノールアミンが挙げられるが、好ましくは3級アミン類であり、さらに好ましくは、トリエタノールアミンである。
他の具体例としては、例えば、炭酸リチウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩;ケイ酸ナトリウム、酢酸カリウム等の有機酸のアルカリ金属塩;リン酸二ナトリウム等のリン酸塩;等が挙げられる。
上記キレート試薬の具体例としては、例えば、エチレンジアミン四酢酸二ナトリウム、ニトリロ三酢酸ナトリウム、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸ナトリウム、ウラシル二酢酸ナトリウム等が挙げられる。
上記防錆剤の具体例としては、例えば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオグリコール酸アンモニウム、ジイソプロピルアンモニウムナイトライト、四硝酸ペンタエリスリトール、ジシクロヘキシルアンモニウムナイトライト等が挙げられる。
上記水溶性紫外線吸収剤としては、例えば、スルホン化したベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸系化合物、桂皮酸系化合物、トリアジン系化合物等が挙げられる。
上記酸化防止剤としては、例えば、各種の有機系及び金属錯体系の酸化防止剤(「褪色防止剤」とも呼ぶ。)を使用することができる。前記有機系の酸化防止剤の具体例としては、ハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、複素環類等が挙げられる。
上記糊剤としては、例えば、トウモロコシ及び小麦などのデンプン;カルボキシメチルセルロース及びヒドロキシメチルセルロース等のセルロース化合物;アルギン酸ナトリウム、アラビヤゴム、ローカストビーンガム、トラントガム、グアーガム、及びタマリンド種子等の多糖類、ゼラチン及びカゼイン等のタンパク質;タンニン及びリグニン等の天然水溶性高分子;及びポリビニルアルコール、ポリエチレンオキサイド、アクリル酸、及び無水マレイン酸等を含有する、合成の水溶性高分子化合物等が挙げられる。糊剤の含有量は、前処理組成物の総質量に対して、通常0~20%程度である。
上記前処理組成物の25℃における表面張力は、様々な布帛に対して十分な濡れ性が発現できる観点から、好ましくは35~60mN/m、より好ましくは36~58mN/m、より好ましくは37~56mN/m、特に好ましくは38~54mN/mである。
上記前処理組成物の25℃における粘度は、好ましくは0.5~4.0mPa・s、より好ましくは0.7~3.5mPa・s、特に好ましくは0.8~3.0mPa・sである。上記粘度範囲を満たす前処理組成物であれば、前処理組成物の塗布方法や布帛の種類によらず、前処理組成物をムラなく塗布することができ、ドット形状のムラや画像の不均質化を抑制できる。更に、布帛への濡れ性や乾燥時のムラ抑制の観点からも優れた印刷物が得られる。
上記前処理組成物の25℃におけるpHは、好ましくは3.0~10.0、より好ましくは3.5~8.0、特に好ましくは4.0~6.0である。上記pH範囲に収まる前処理組成物であれば、布帛の脆化を防ぐことができ、また混色滲みや色ムラが少なく、かつ発色性に優れた印刷物が得られる。
本実施形態に係る前処理組成物の調製方法としては、例えば、水、カチオン性ポリマー、架橋剤、及び、必要に応じて上記で挙げたような調製剤をさらに加え、撹拌・混合した後、必要に応じて濾過する方法が挙げられる。ただし本発明の前処理組成物の調整方法は上記に限定されるものではない。
本実施形態の水系インク組成物は、水、顔料を含む。
そして、本発明の一好適実施形態の水系インク組成物は、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有し、更に高分子分散剤を含有することが好ましい。なお、本明細書中において、水系インク組成物をインク組成物あるいはインクと略記する場合がある。
また、本発明の他の一好適実施形態の水系インク組成物は、水系の白色インク組成物であって、水、白色顔料、ウレタン樹脂、水溶性有機溶剤、を含有し、更に塩基を含むことが好ましい。なお、本明細書中において、水系の白色インク組成物を白色インク組成物あるいは白色インクと略記する場合がある。該水系の白色インク組成物には、詳しく後述する。
また、本発明の他の一好適実施形態の水系インク組成物は、水、顔料、高分子分散剤を含有し、更にウレタン樹脂、スチレン-ブタジエン樹脂、(メタ)アクリル樹脂、(メタ)アクリル樹脂共重合体からなる群から選択される少なくともいずれかを含むことが好ましく、また更に、水溶性有機溶剤、界面活性剤を含有してもよく、該水系インク組成物は、上記の水系の白色インク組成物と組み合わせて、使用することが好ましい。
上記水系インク組成物が含む水としては、例えば、上記前処理組成物で例示したものを用いることができる。水の含有量は、特に制限されることなく必要に応じて適宜決定すればよいが、水系インク組成物の粘度を好適な範囲に調整するため、水系インク組成物の総質量(100質量%)に対して20~80質量%含まれているとよい。また、限られるものではないが、例えば、好ましくは40~80質量%であり、より好ましくは45~75質量%であり、さらに好ましくは50~70質量%である。
上記の顔料としては、特に限定されるものではなく、公知の顔料が使用できる。顔料としては、無機顔料、有機顔料、体質顔料等が知られている。
カーボンブラックには複数の種類があり、例えば、熱分解法により得られるサーマルブラック、アセチレンブラック;不完全燃焼法により得られるオイルファーネスブラック、ガスファーネスブラック、ランプブラック、ガスブラック、及びチャンネルブラック;等が挙げられる。
カーボンブラックの具体例としては、例えば、Raven760ULTRA、Raven780ULTRA、Raven790ULTRA、Raven1060ULTRA、Raven1080ULTRA、Raven1170、Raven1190ULTRA II、Raven1200、Raven1250、Raven1255、Raven1500、Raven2000、Raven2500ULTRA、Raven3500、Raven5000ULTRA II、Raven5250、Raven5750、Raven7000(以上、コロンビア・カーボン社製);Monarch700、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Regal1330R、Regal1400R、Regal1660R、Mogul L(以上、キャボット社製);Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW200、Color Black S150、Color Black S160、Color Black S170、Printex 35、Printex U、Printex V、Printex 140U、Printex 140V、SpecIal Black 4、SpecIal Black 4A、SpecIal Black 5、Special Black 6(以上、デグサ社製);MA7、MA8、MA100、MA600、MCF-88、No.25、No.33、No.40、No.47、No.52、No.900、No.2300(以上、三菱化学社製);等が挙げられる。
酸化チタンの具体例としては、例えば、DUAWHITE TCR-52、TITONE R-32、TITONE R-7E、TITONE R-21、TITONE R-62N、TITONE R-42(以上、堺化学工業株式会社製);TIPAQUE CR-50、TIPAQUE CR-50-2、TIPAQUE CR-58、TIPAQUE CR-60、TIPAQUE CR-80、TIPAQUE CR-90(以上、石原産業株式会社製);TITANIX JA-600A、TITANIX JR-605(以上、テイカ株式会社製);ST-455、ST-455WB、ST-457SA、ST-457EC(以上、チタン工業株式会社製);等が挙げられる。
なお、後述する水系の白色インク組成物は、白色顔料を含むため、該水系の白色インク組成物と組み合わせて使用する水系インク組成物は、白色顔料以外の顔料を含むことが好ましい。
有機顔料の具体例としては、例えば、C.I.Pigment Yellow 1、2、3、12、13、14、16、17、24、55、73、74、75、83、93、94、95、97、98、108、114、128、129、138、139、150、151、154、155、180、185、193、199、202等のイエロー色の顔料;C.I.Pigment Red 5、7、12、48、48:1、57、88、112、122、123、146、149、166、168、177、178、179、184、185、202、206、207、254、255、257、260、264、272等のレッド色の顔料;C.I.Pigment Blue 1、2、3、15、15:1、15:2、15:3、15:4、15:6、16、22、25、60、66、80等のブルー色の顔料;C.I.Pigment Violet 19、23、29、37、38、50等のバイオレット色の顔料;C.I.Pigment Orange 13、16、36、34、43、68、69、71、73等のオレンジ~ブラウン色の顔料;C.I.Pigment Green 7、36、54等のグリーン色の顔料;C.I.Pigment Black 1等のブラック色の顔料;等が挙げられる。
上記水系インク組成物が含む樹脂エマルションとしては、例えば、スチレン-ブタジエン樹脂、(メタ)アクリル樹脂、(メタ)アクリル樹脂共重合体、スチレン-無水マレイン酸共重合体樹脂、エポキシ樹脂、ウレタン樹脂、ポリエーテル樹脂、ポリアミド樹脂、不飽和ポリエステル樹脂、フェノール樹脂、シリコーン樹脂、フッ素樹脂、ポリビニル樹脂(塩化ビニル、酢酸ビニル、ポリビニルアルコール等)、酢酸ビニル-(メタ)アクリル共重合体樹脂、酢酸ビニル-エチレン共重合体樹脂、アルキド樹脂、ポリエステル樹脂、アミノ樹脂(メラニン樹脂、ユリア樹脂、尿素樹脂、メラニンホルムアルデヒド樹脂等)等から形成されたエマルションを挙げることができる。樹脂エマルションは、2種類以上の樹脂を含んでいてもよい。また、2種類以上の樹脂がコア/シェル構造を形成していてもよい。樹脂エマルションは、1種類を単独で使用してもよく、2種類以上を併用してもよい。樹脂エマルションの中でも、インク性能の観点から、スチレン-ブタジエン樹脂エマルション、(メタ)アクリル樹脂エマルション、(メタ)アクリル樹脂共重合体エマルション、ウレタン樹脂エマルションが好ましい。
例えば、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂、ポリエステル系ウレタン樹脂等のポリウレタン樹脂のエマルションが挙げられ、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂のエマルションであることが好ましい。
上記ウレタン樹脂エマルションは、市販品として入手することができ、その多くは固形分濃度30~60質量%の乳化液である。ウレタン樹脂エマルションの市販品としては、例えば、パーマリンUA-150、200、310、368、3945、ユーコートUX-320、340(以上、三洋化成株式会社製);ハイドランWLS-201、202、210、213、221、230、250、HW-312Bのラテックス(以上、DIC株式会社製);スーパーフレックス150、170、470(以上、第一工業製薬株式会社製);等が挙げられる。これらのうち、ポリカーボネート系ウレタン樹脂としては、例えば、パーマリンUA-310、3945;ユーコートUX-320;ハイドランWLS-210、213、250;等が挙げられる。また、ポリエーテル系ウレタン樹脂としては、例えば、パーマリンUA-150、200;ユーコートUX-340;ハイドランWLS-201、202、230;等が挙げられる。ウレタン樹脂は単一のものを使用してもよいし、2~3種類を併用してもよい。
上記水系インク組成物は、一実施形態において、水溶性有機溶剤を含む。該水溶性有機溶剤としては、例えば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、第二ブタノール、第三ブタノール等のC1-C4モノオール;エチレングリコール、1,2-又は1,3-プロピレングリコール、1,2-又は1,4-ブチレングリコール、1,3-ペンタンジオール、1,5-ペンタンジオール、1,2-ヘキサンジオール、1,6-ヘキサンジオール等のC2-C6ジオール;グリセリン、ヘキサン-1,2,6-トリオール、トリメチロールプロパン等のC3-C6トリオール;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のカルボン酸アミド;2-ピロリドン、N-メチル-2-ピロリドン、1,3-ジメチルイミダゾリジン-2-オン、1,3-ジメチルヘキサヒドロピリミド-2-オン等の複素環式尿素類;アセトン、メチルエチルケトン、2-メチル-2-ヒドロキシペンタン-4-オン等のケトン又はケトアルコール;1,2-ジメトキシエタン、テトラヒドロフラン、ジオキサン等の直鎖又は環状エーテル;ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、チオジグリコール等のジ若しくはトリC2-C3アルキレングリコール又はチオグリコール;テトラエチレングリコール、ポリエチレングリコール(好ましくは分子量400、800、1540等の分子量が2000以下のもの)、ポリプロピレングリコール等の、繰り返し単位が4以上で、分子量が約20000以下程度のポリC2-C3アルキレングリコール(好ましくは液状のもの);ジグリセリン、トリグリセリン、ポリグリセリン等のポリグリセリルエーテル;ポリオキシエチレンポリグリセリルエーテル、ポリオキシプロピレンポリグリセリルエーテル等のポリオキシC2-C3アルキレンポリグリセリルエーテル;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル(ブチルカルビトール)、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル等の多価アルコールのC1-C4アルキルエーテル;γ-ブチロラクトン、エチレンカーボネート等の環状エステル又はカーボネート;ジメチルスルホキシド;酢酸;等が挙げられる。
これらの中では、C2-C6ジオール(中では1,2-プロピレングリコール);C3-C6トリオール(中ではグリセリン);ポリグリセリルエーテル(中ではジグリセリン);及び、多価アルコールのC1-C4アルキルエーテル(中ではブチルカルビトール);が好ましい。
これらの水溶性有機溶剤は1種類を使用してもよく、また複数を併用してもよい。これらの中では、ポリグリセリルエーテル(好ましくはグリセリン及び/又はジグリセリン)を含有するのが好ましい。
上記水系インク組成物が含む界面活性剤としては、アニオン系、カチオン系、ノニオン系、両性、シリコーン系、フッ素系等の公知の界面活性剤が挙げられる。アニオン界面活性剤としては、アルキルスルホン酸塩、アルキルカルボン酸塩、α-オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、N-アシルアミノ酸及びその塩、N-アシルメチルタウリン塩、アルキル硫酸塩ポリオキシアルキルエーテル硫酸塩、アルキル硫酸塩ポリオキシエチレンアルキルエーテル燐酸塩、ロジン酸石鹸、ヒマシ油硫酸エステル塩、ラウリルアルコール硫酸エステル塩、アルキルフェノール型燐酸エステル、アルキル型燐酸エステル、アルキルアリールスルホン酸塩、ジエチルスルホ琥珀酸塩、ジエチルヘキルシルスルホ琥珀酸塩、ジオクチルスルホ琥珀酸塩等が挙げられる。その市販品の具体例としては、例えば、いずれも第一工業製薬社製のハイテノールLA-10、LA-12、LA-16、ネオハイテノールECL-30S、ECL-45などが挙げられる。カチオン界面活性剤としては、2-ビニルピリジン誘導体、ポリ4-ビニルピリジン誘導体等が挙げられる。ノニオン界面活性剤としては、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル等のエーテル系;ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等のエステル系;2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、3,5-ジメチル-1-ヘキシン-3-オール等のアセチレングリコール(アルコール)系;日信化学社製、商品名サーフィノール104、105、82、465、オルフィンSTG等;ポリグリコールエーテル系(例えばSIGMA-ALDRICH社製のTergitol 15-S-7等);等が挙げられる。両性界面活性剤としては、ラウリルジメチルアミノ酢酸ベタイン、2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、ポリオクチルポリアミノエチルグリシン、イミダゾリン誘導体等が挙げられる。シリコーン系界面活性剤としては、例えば、ポリエーテル変性シロキサン、ポリエーテル変性ポリジメチルシロキサン等が挙げられる。市販品の具体例としては、例えば、いずれもビックケミー社製の、BYK-347(ポリエーテル変性シロキサン);BYK-345、BYK-348(ポリエーテル変性ポリジメチルシロキサン)等が挙げられる。フッ素系界面活性剤としては、例えば、パーフルオロアルキルスルホン酸化合物、パーフルオロアルキルカルボン酸系化合物、パーフルオロアルキルリン酸エステル化合物、パーフルオロアルキルエチレンオキサイド付加物、及びパーフルオロアルキルエーテル基を側鎖に有するポリオキシアルキレンエーテルポリマー化合物等が挙げられる。市販品の具体例としては、例えば、Zonyl TBS、FSP、FSA、FSN-100、FSN、FSO-100、FSO、FS-300、Capstone FS-30、FS-31(DuPont社製);PF-151N、PF-154N(オムノバ社製)等が挙げられる。
上記水系インク組成物は、一実施形態において、高分子分散剤を含むことが好ましい。
水性媒体中で顔料分散物を安定化させる方法としては、一般に樹脂等の分散剤を用いてエントロピー的、イオン反発力、立体反発力等によって顔料分散物を安定化する方法が用いられる。ここで、分散剤は親水性部分と疎水性部分とを有し、疎水性部分が顔料表面に吸着し、親水性部分で水性媒体に分散する性質を有すると考えられる。さらに、顔料表面への吸着状態によっては、顔料を水性媒体に溶解させることも可能である。上記の高分子分散剤は、このような性質を有する分散剤として使用できる。
高分子分散剤は、下記式(1)で表されるモノマーA、モノマーB、及びモノマーCよりなる群から選択される少なくとも2種類の構成モノマーを含むポリマーである。好ましくは、モノマーA、モノマーB、及びモノマーCから少なくとも1種類ずつが選択される。
モノマーA:下記式(1)中、Rが水素原子であるモノマー。
モノマーB:下記式(1)中、RがC1-C4アルキル基であるモノマー。
モノマーC:下記式(1)中、Rがアリール基又はアリールC1-C4アルキル基であるモノマー。好ましくは、Rがアリール基、より好ましくは、Rがベンジル基であるモノマー。
また、アルカリ土類金属の水酸化物として、例えば、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム等が挙げられる。
無機塩基の中ではアルカリ金属の水酸化物及びアンモニアが好ましく、中でも水酸化リチウム、水酸化ナトリウム、及びアンモニアが好ましい。
モノマーAは、上記式(1)中、Rが水素原子であるモノマー、すなわちメタクリル酸である。
モノマーBは、上記式(1)中、RがC1-C4アルキル基であるモノマーである。モノマーBとしては、メチルメタクリレート、エチルメタクリレート、n-プロピルメタクリレート、イソプロピルメタクリレート、n-ブチルメタクリレート、イソブチルメタクリレート等が挙げられる。
モノマーCは、上記式(1)中、Rがアリール基又はアリールC1-C4アルキル基であるモノマーである。
上記アリールとしては、C6-C10アリール基が好ましく、中でもフェニル基又はナフチル基が好ましい。
上記アリールC1-C4アルキル基としては、フェニルメチル、フェニルエチル、フェニルプロピル、フェニルブチル等のアルキル部分が直鎖又は分岐鎖、好ましくは直鎖のフェニルC1-C4アルキル基;ナフチルメチル、ナフチルエチル、ナフチルプロピル、ナフチルブチル等のアルキル部分が直鎖又は分岐鎖、好ましくは直鎖のナフチルC1-C4アルキル基;等が挙げられる。これらの中ではフェニルC1-C4アルキル基が好ましい。モノマーCの具体例としては、例えば、フェニルメタクリレート、ベンジルメタクリレート、フェネチルメタクリレートが挙げられる。
上記水系インク組成物は、一実施形態において、更にウレタン樹脂、スチレン-ブタジエン樹脂、(メタ)アクリル樹脂、(メタ)アクリル樹脂共重合体からなる群から選択される少なくともいずれかを含むことが好ましい。
特には、水、顔料、高分子分散剤を含有する水系インク組成物は、更にウレタン樹脂、スチレン-ブタジエン樹脂、(メタ)アクリル樹脂、(メタ)アクリル樹脂共重合体からなる群から選択される少なくともいずれかを含むことが好ましい。
上記インク組成物は、さらに添加剤を含んでいても良い。
上記添加剤における防腐剤としては、例えば、有機硫黄系、有機窒素硫黄系、有機ハロゲン系、ハロアリルスルホン系、ヨードプロパギル系、N-ハロアルキルチオ系、ニトリル系、ピリジン系、8-オキシキノリン系、ベンゾチアゾール系、イソチアゾリン系、ジチオール系、ピリジンオキシド系、ニトロプロパン系、有機スズ系、フェノール系、第4アンモニウム塩系、トリアジン系、チアジン系、アニリド系、アダマンタン系、ジチオカーバメイト系、ブロム化インダノン系、ベンジルブロムアセテート系、無機塩系等の化合物が挙げられる。有機ハロゲン系化合物の具体例としては、例えばペンタクロロフェノールナトリウムが挙げられ、ピリジンオキシド系化合物の具体例としては、例えば2-ピリジンチオール-1-オキサイドナトリウムが挙げられ、イソチアゾリン系化合物の具体例としては、例えば、1,2-ベンズイソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オンマグネシウムクロライド、5-クロロ-2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド、2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド等が挙げられる。その他の防腐防黴剤の具体例として、無水酢酸ソーダ、ソルビン酸ソーダ又は安息香酸ナトリウム、アーチケミカル社製、商品名プロクセルRTMGXL(S)やプロクセルRTMXL-2(S)等が挙げられる。
上記添加剤におけるキレート試薬の具体例としては、例えば、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸ナトリウム、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸ナトリウム、ウラシル二酢酸ナトリウム等があげられる。
上記添加剤における防錆剤としては、例えば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオグルコール酸アンモニウム、ジイソプロピルアンモニウムナイトライト、四硝酸ペンタエリスリトール又はジシクロヘキシルアンモニウムナイトライト等があげられる。
上記添加剤における水溶性紫外線吸収剤としては、例えば、スルホン化したベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸系化合物、桂皮酸系化合物、トリアジン系化合物が挙げられる。
上記添加剤における水溶性高分子化合物としては、例えば、ポリビニルアルコール、セルロース誘導体、ポリアミン又はポリイミン等があげられる。
上記添加剤における粘度調整剤としては、上記水系インク組成物の項で述べた、水溶性有機溶剤や水溶性高分子化合物が挙げられ、水溶性高分子化合物としては、例えば、ポリビニルアルコール、セルロース誘導体、ポリアミン、ポリイミン等が挙げられる。
上記添加剤における色素溶解剤としては、例えば、尿素、ε-カプロラクタム、エチレンカーボネート等が挙げられる。
上記添加剤における褪色防止剤は、画像の保存性を向上させる目的で使用される。褪色防止剤としては、例えば、各種の有機系及び金属錯体系の褪色防止剤を使用することができる。有機系としては、ハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、及びヘテロ環類等が挙げられる。金属錯体系としては、ニッケル錯体、亜鉛錯体等が挙げられる。
上記添加剤における酸化防止剤としては、例えば、各種の有機系及び金属錯体系の褪色防止剤を使用することができる。前記有機系の褪色防止剤の例としては、ハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、複素環類等が挙げられる。
一実施形態において、上記水系インク組成物の25℃における表面張力は、様々な布帛に対して十分な濡れ性が発現できる観点から、好ましくは20~48mN/m、より好ましくは25~46mN/m、より好ましくは30~44mN/m、特に好ましくは32~42mN/mである。
また、後述する水系の白色インク組成物と組み合わることが好適な水系インク組成物の25℃における表面張力は、様々な布帛に対して十分な濡れ性が発現できる観点から、好ましくは20~48mN/m、より好ましくは25~44mN/m、より好ましくは30~42mN/m、特に好ましくは32~40mN/mである。
上記水系インク組成物の25℃における粘度は、好ましくは2~20mPa・s、より好ましくは3~18mPa・sである。上記粘度範囲を満たす水系インク組成物であれば、高速印刷において吐出応答性が良好になる傾向にある。
上記水系インク組成物のpHとしては、保存安定性を向上させる目的で、pH5.0~11.0が好ましく、pH7.0~10.0がより好ましい。
上記水系インク組成物の調製方法としては、特に制限はないが、例えば、上記各成分を含有する水性分散液(顔料分散液)を調製し、必要に応じて、水溶性有機溶剤等の添加剤をさらに加える方法が挙げられる。
分原比=分散剤の部数/顔料の部数
上記水系の白色インク組成物は、水、白色顔料、ウレタン樹脂、水溶性有機溶剤、を含有する。なお、本明細書中において、水系の白色インク組成物を白色インク組成物あるいは白色インクと略記する場合がある。
上記白色インク組成物が含む水としては、例えば、上記前処理組成物で例示したものを用いることができる。水の含有量は、特に制限されることなく必要に応じて適宜決定すればよいが、白色インク組成物の粘度を好適な範囲に調整するため、インク組成物の総質量(100質量%)に対して20~80質量%含まれているとよい。また、限られるものではないが、例えば、好ましくは40~80質量%であり、より好ましくは45~75質量%であり、さらに好ましくは50~70質量%である。
白色顔料としては、金属酸化物を使用するのが好ましい。金属酸化物としては、酸化亜鉛、酸化チタン、酸化ジルコニア等が挙げられ、酸化チタンが好ましい。酸化チタンの種類としては、ルチル型、アナターゼ型;等が挙げられる。酸化チタンは粉体としてそのまま使用してもよいし、二酸化ケイ素、酸化アルミ、酸化ジルコニア、酸化亜鉛、又は水酸基を有する有機物等で、表面を処理したものを使用してもよい。これらの中では表面処理した酸化チタンが好ましく挙げられる。
酸化チタンの具体例としては、例えば、DUAWHITE TCR-52、TITONE R-32、TITONE R-7E、TITONE R-21、TITONE R-62N、TITONE R-42(以上、堺化学工業株式会社製);TIPAQUE CR-50、TIPAQUE CR-50-2、TIPAQUE CR-58、TIPAQUE CR-60、TIPAQUE CR-80、TIPAQUE CR-90(以上、石原産業株式会社製);TITANIX JA-600A、TITANIX JR-605(以上、テイカ株式会社製);ST-455、ST-455WB、ST-457SA、ST-457EC(以上、チタン工業株式会社製);等が挙げられる。
上記ウレタン樹脂の具体例としては、例えば、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂、ポリエステル系ウレタン樹脂等のポリウレタン樹脂が挙げられ、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂であることが好ましい。
上記白色インク組成物は、水溶性有機溶剤を含む。水溶性有機溶剤としては、例えば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、第二ブタノール、第三ブタノール等のC1-C4モノオール;エチレングリコール、1,2-又は1,3-プロピレングリコール、1,2-又は1,4-ブチレングリコール、1,3-ペンタンジオール、1,5-ペンタンジオール、1,2-ヘキサンジオール、1,6-ヘキサンジオール等のC2-C6ジオール;グリセリン、ヘキサン-1,2,6-トリオール、トリメチロールプロパン等のC3-C6トリオール;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のカルボン酸アミド;2-ピロリドン、N-メチル-2-ピロリドン、1,3-ジメチルイミダゾリジン-2-オン、1,3-ジメチルヘキサヒドロピリミド-2-オン等の複素環式尿素類;アセトン、メチルエチルケトン、2-メチル-2-ヒドロキシペンタン-4-オン等のケトン又はケトアルコール;1,2-ジメトキシエタン、テトラヒドロフラン、ジオキサン等の直鎖又は環状エーテル;ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、チオジグリコール等のジ若しくはトリC2-C3アルキレングリコール又はチオグリコール;テトラエチレングリコール、ポリエチレングリコール(好ましくは分子量400、800、1540等の分子量が2000以下のもの)、ポリプロピレングリコール等の、繰り返し単位が4以上で、分子量が約20000以下程度のポリC2-C3アルキレングリコール(好ましくは液状のもの);ジグリセリン、トリグリセリン、ポリグリセリン等のポリグリセリルエーテル;ポリオキシエチレンポリグリセリルエーテル、ポリオキシプロピレンポリグリセリルエーテル等のポリオキシC2-C3アルキレンポリグリセリルエーテル;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル(ブチルカルビトール)、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル等の多価アルコールのC1-C4アルキルエーテル;γ-ブチロラクトン、エチレンカーボネート等の環状エステル又はカーボネート;ジメチルスルホキシド;酢酸;等が挙げられる。
これらの中では、C2-C6ジオール(中では1,2-プロピレングリコール);C3-C6トリオール(中ではグリセリン);ポリグリセリルエーテル(中ではジグリセリン);及び、多価アルコールのC1-C4アルキルエーテル(中ではブチルカルビトール);が好ましい。
これらの水溶性有機溶剤は1種類を使用してもよく、また複数を併用してもよい。これらの中では、ポリグリセリルエーテル(好ましくはグリセリン及び/又はジグリセリン)を含有するのが好ましい。
上記白色インク組成物は、更に塩基を含むことが好ましい。塩基としては特に限定はないが、例えば、アルカリ金属の水酸化物、アルカリ土類金属の水酸化物等の水酸化アルカリ塩基、アンモニア等の無機塩基、脂肪族アミン化合物やアルカノールアミン化合物等の有機塩基等が挙げられる。
上記白色インク組成物は、さらに添加剤を含んでいても良い。
上記防腐剤としては、例えば、有機硫黄系、有機窒素硫黄系、有機ハロゲン系、ハロアリルスルホン系、ヨードプロパギル系、N-ハロアルキルチオ系、ニトリル系、ピリジン系、8-オキシキノリン系、ベンゾチアゾール系、イソチアゾリン系、ジチオール系、ピリジンオキシド系、ニトロプロパン系、有機スズ系、フェノール系、第4アンモニウム塩系、トリアジン系、チアジン系、アニリド系、アダマンタン系、ジチオカーバメイト系、ブロム化インダノン系、ベンジルブロムアセテート系、無機塩系等の化合物が挙げられる。有機ハロゲン系化合物の具体例としては、例えばペンタクロロフェノールナトリウムが挙げられ、ピリジンオキシド系化合物の具体例としては、例えば2-ピリジンチオール-1-オキサイドナトリウムが挙げられ、イソチアゾリン系化合物の具体例としては、例えば、1,2-ベンズイソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オンマグネシウムクロライド、5-クロロ-2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド、2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド等が挙げられる。その他の防腐防黴剤の具体例として、無水酢酸ソーダ、ソルビン酸ソーダ又は安息香酸ナトリウム、アーチケミカル社製、商品名プロクセルRTMGXL(S)やプロクセルRTMXL-2(S)等が挙げられる。
上記界面活性剤としては、アニオン系、カチオン系、ノニオン系、シリコーン系等の公知の界面活性剤が挙げられる。
アニオン界面活性剤としては、アルキルスルホン酸塩、アルキルカルボン酸塩、α-オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、N-アシルアミノ酸及びその塩、N-アシルメチルタウリン塩、アルキル硫酸塩ポリオキシアルキルエーテル硫酸塩、アルキル硫酸塩ポリオキシエチレンアルキルエーテル燐酸塩、ロジン酸石鹸、ヒマシ油硫酸エステル塩、ラウリルアルコール硫酸エステル塩、アルキルフェノール型燐酸エステル、アルキル型燐酸エステル、アルキルアリールスルホン酸塩、ジエチルスルホ琥珀酸塩、ジエチルヘキルシルスルホ琥珀酸塩、ジオクチルスルホ琥珀酸塩等が挙げられる。その市販品の具体例としては、例えば、いずれも第一工業製薬社製のハイテノールLA-10、LA-12、LA-16、ネオハイテノールECL-30S、ECL-45などが挙げられる。
カチオン界面活性剤としては、2-ビニルピリジン誘導体、ポリ4-ビニルピリジン誘導体等が挙げられる。
両性界面活性剤としては、ラウリルジメチルアミノ酢酸ベタイン、2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、ポリオクチルポリアミノエチルグリシン、イミダゾリン誘導体等が挙げられる。
ノニオン界面活性剤としては、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル等のエーテル系;ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等のエステル系;2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、3,5-ジメチル-1-ヘキシン-3-オール等のアセチレングリコール(アルコール)系;日信化学社製、商品名サーフィノール104、105、82、465、オルフィンSTG等;ポリグリコールエーテル系(例えばSIGMA-ALDRICH社製のTergitol 15-S-7等);等が挙げられる。
上記キレート試薬の具体例としては、例えば、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸ナトリウム、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸ナトリウム、ウラシル二酢酸ナトリウム等があげられる。
上記防錆剤としては、例えば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオグルコール酸アンモニウム、ジイソプロピルアンモニウムナイトライト、四硝酸ペンタエリスリトール又はジシクロヘキシルアンモニウムナイトライト等があげられる。
上記水溶性紫外線吸収剤としては、例えばスルホン化したベンゾフェノン系化合物、ベンゾトリアゾ-ル系化合物、サリチル酸系化合物、桂皮酸系化合物、トリアジン系化合物が挙げられる。
上記水溶性高分子化合物としては、ポリビニルアルコール、セルロース誘導体、ポリアミン又はポリイミン等があげられる。
上記粘度調整剤としては、水溶性有機溶剤の他に、水溶性高分子化合物が挙げられ、例えば、ポリビニルアルコール、セルロース誘導体、ポリアミン、ポリイミン等が挙げられる。
上記色素溶解剤としては、例えば、尿素、ε-カプロラクタム、エチレンカーボネート等が挙げられる。
上記褪色防止剤は、画像の保存性を向上させる目的で使用される。褪色防止剤としては、各種の有機系及び金属錯体系の褪色防止剤を使用することができる。有機系としては、ハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、及びヘテロ環類等が挙げられる。金属錯体系としては、ニッケル錯体、亜鉛錯体等が挙げられる。
上記酸化防止剤としては、例えば、各種の有機系及び金属錯体系の褪色防止剤を使用することができる。前記有機系の褪色防止剤の例としては、ハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、複素環類等が挙げられる。
本実施形態に係る白色インク組成物の調製方法としては、例えば、上記各成分を含有する水性分散液を調製し、必要に応じて、上記の添加剤をさらに加える方法が挙げられる。
本実施形態で用いる布帛としては、特に限定されないが、例えば、絹、綿、羊毛、セルロース、ナイロン、ポリエステル、レーヨン等の天然繊維又は合成繊維が挙げられる。布帛は、2種以上の繊維を含む混紡であってもよい。
上記前処理組成物は、1種類以上の水系インク組成物と組み合わせ、印刷セット(「インクセット」とも呼ぶ。)の形態として用いることが好ましい。該印刷セットを構成する水系インク組成物の構成要素は上記で説明したとおりである。
本実施形態のインクジェット捺染方法は、前処理組成物を布帛に塗布し、湿潤したプレコート層を形成する前処理工程と、前記湿潤したプレコート層を形成した領域の少なくとも一部に対し、水系インク組成物を付与する工程と、を有する。
また、2種以上のインク組成物を同じ記録領域に順次付着させる場合において、後に付着させるインク組成物までも効果的に凝集させることができる。具体的には、黒色を含む濃色の繊維に対して、白色インク組成物を付着させて下地を設置してから、カラーインクを付着させて捺染を行う場合がある。このような場合において、本願実施形態のインクジェット捺染方法は特に有用となる。
上記前処理工程は、前処理組成物を布帛に塗布させる工程を指す。前処理組成物を塗布させる手段としては、特に限定されないが、例えば、ローラー塗布、スプレー塗布、インクジェット塗布を利用することができる。このなかでも、前処理組成物を前記布帛へ非接触式で塗布することが好ましく、スプレー塗布、インクジェット方式により塗布させることがより好ましい。前処理組成物を非接触式で塗布させることにより、前処理組成物の塗布量がより制御しやすく、これにより得られる画質がより向上する傾向にある。
また、上記布帛単位面積当たりの上記前処理組成物塗布量は、他の一実施形態(特には、上述の水系の白色インク組成物を使用する実施形態)においては、0.035g/cm2を超え、かつ、0.070g/cm2未満であることが好ましく、湿潤したプレコート層を形成するために用いられる。上記塗布量は、より好ましくは0.039~0.063g/cm2であり、より一層好ましくは0.040~0.060g/cm2である。
前処理組成物の塗布量が0.035g/cm2を超えることにより、ポリエステル繊維(スポーツウェア等に使用されるメッシュ生地)や生地の薄い繊維、編み目の粗い繊維等を用いる場合に、インクジェット方式で吐出したインク液滴が、繊維の捺染を行っていない反対側の面に浸透しやすい(貫通しやすい)布帛に対して、インクの裏抜けを抑制することができ、白色インクで下地を設置したときの白色度及び隠蔽性を高くできる傾向にある。また、白色下地の設置を行わずに、カラーインクを印刷したときも同様に、インクの裏抜けを抑制することができ、発色性の高いカラー画像が得られる傾向にある。また、前処理組成物の塗布量が0.070g/cm2未満であることにより、前処理組成物を付与した「痕跡」が残るのを抑制できる傾向にある。
一実施形態においては、記録工程は、前処理工程後に上記布帛を乾燥することなく、上記湿潤したプレコート層を形成した領域の少なくとも一部に対し、上記少なくとも1種の水系インク組成物をヘッドから吐出して、水系インク組成物を付着さ、画像領域を形成する工程である。
本実施形態の印捺方法は、記録工程後、布帛を加熱する乾燥工程をさらに有することが好ましい。加熱することにより、前処理組成物又は水系インク組成物に含まれ得る樹脂エマルションを布帛の表面に融着させ、かつ、上記の架橋剤と樹脂エマルションとの架橋反応を促進させ、同時に水分を蒸発させることができる。また、乾燥工程を行うことにより、得られる画像は耐擦性、密着性により優れる傾向にある。
また、実施例中で使用した「水」は、イオン交換水である。
星光PMC社製ハイロスXVS-1202(9部)を、2-ブタノン(30部)に溶解した。この溶液に、0.9部の水酸化ナトリウムをイオン交換水(76部)に溶解させた液を加え、1時間撹拌することにより乳化液を得た。得られた液にC.I.Pigment Black 7(30部)を加え、サンドグラインダーで1500rpmの条件下、15時間分散処理を行った。得られた液にイオン交換水(150部)を滴下した後、分散用ビーズを濾別した。得られた母液中の2-ブタノン及び水の一部を、エバポレータで減圧留去して濃縮することにより、固形分11.9%の分散液を得た。これを「分散液1」とする。なお、水溶液中の固形分は、株式会社エイ・アンド・デイ社製、MS-70を用いて乾燥重量法により求めた。分散液1に含まれる顔料の平均粒子径は88nm、分散液1の25℃における粘度は4.6mPa・sであった。
下記表1に記載の成分を十分に撹拌して混合し、インク1~2を得た。得られたインクを孔径5μmのミックスセルロースエステルのフィルターでろ過した後、真空ポンプを用いて脱気処理することにより、試験用のインク1~2を得た。
インク1:調製例2で調製した水系の白色インク組成物
インク2:調製例3で調製した水系インク組成物
FUJI SP SAMPLE 138(白顔料分散液、固形分50%、冨士色素株式会社製)
分散液1(調製例1で得た分散液1)
ハイドランWLS-201(ウレタン樹脂エマルション、固形分35%、凍結点-11℃、ガラス転移温度-79℃、DIC株式会社製)
JSR0568(スチレン-ブタジエン樹脂ラテックス、固形分50%、JSR株式会社製)
オルフィンEXP-4001(界面活性剤、日信化学工業株式会社製)
サーフィノール420(界面活性剤、日信化学工業株式会社製)
サーフィノールDF-110D(界面活性剤、日信化学工業株式会社製)
PROXEL GXL(S)(防腐剤、Lonza株式会社製)
TEA:純正化学株式会社製トリエタノールアミン
下記表2に記載の各成分を混合して、それぞれ総量100部の前処理組成物を得た。得られた液を平均孔径3μmのメンブランフィルターで濾過することにより、評価試験用の前処理組成物1~8を得た。
DK6850:エピハロヒドリン変性ポリアミン樹脂(星光PMC社製、重量平均分子量:1703、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分70%)
DK6854:エピハロヒドリン変性ポリアミン樹脂(星光PMC社製、重量平均分子量:5853、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分50%)
PAA-HCL-03:アリルアミン塩酸塩重合体(ニットーボーメディカル社製、重量平均分子量:6611、アリルアミン構造単位を含むカチオン性ポリマー、有効成分40%)
メイカネートFM-1:ブロックイソシアネート系架橋剤(明成化学工業社製、カチオン性、解離温度120℃以上、有効成分30%)
メイカネートST:ブロックイソシアネート系架橋剤(明成化学工業社製、カチオン性、解離温度120℃以上、有効成分30%)
カチオンポリマーの質量%:前処理組成物全質量に対するカチオン性ポリマーの含有質量(%)
塗布量[g/cm2]:布帛単位面積当たりの前処理組成物塗布量
酢酸(500mM)とNa2NO3(200mM)の水溶液を展開溶媒としたゲル浸透クロマトグラフィー法〔東ソー株式会社製GPC装置(HLC-8320GPC EcoSEC)、東ソー株式会社製カラム(TSKgel Super AW4000、TSKgel Super AW3000×2本を連結)、流速:0.6mL/min〕により、標準物質としてポリスチレンを用いて測定した。
〔前処理工程〕
上記で得た前処理組成物1~8を上記表2に記載の塗布量で、ポリエステル布帛(ドライTシャツ、黒色の00300-ACT(glimmer製))に対し、それぞれA4サイズに塗布し、湿潤したプレコート層を形成した。その際、市販の霧吹き((株)ミツギロン社製、ファインスプレー)を用いて前処理組成物1~8を塗布した。前処理組成物塗布後、直ちに下記記録工程を行った。
記録工程前の前処理組成物の残存量は、下記式により算出した。実施例及び比較例はいずれも95%以上であった。
前処理組成物の残存量(%)=(記録工程前の布帛の重量-前処理工程前の布帛の重量)/(前処理工程の塗布の直後の布帛の重量-前処理工程前の布帛の重量)×100%
上記のようにして調製した水系の白色インク組成物(インク1)を産業用インクジェット評価装置(拡張型塗布装置EV2500:リコー株式会社製)に充填した。その後、インク液滴重量29pl/dot、ヘッド温度は25℃、解像度600×1200dpi、6回重ね印刷の条件で、水系インク組成物(インク1)を、前記のようにして得た湿潤したプレコート層の領域の一部に対し付着させて、白色のベタパターン画像を形成した。実施例及び比較例においては、インク組成物付着後、引き出し式電気乾燥機(DDC-6A、ADELCO社製)を用いて130℃で3分の加熱乾燥を行い、乾燥させた。
上記のように得られた印捺物の、水系の白色インク組成物(インク1)により記録した印捺面のL*値を測定した。測色機としては分光測色計(X-Rite Ci62、X-Rite社製)を用いて、光源がD65、視野角が2°の測定条件で、CIE/L*a*b*表色系における、L*値を測定した。各印捺物に対して5回測定を行い、その平均値を測定結果として表2に示す。L*値は大きい程、高い白色度を示すため好ましい。なお、L*値は小数点以下第1位を四捨五入した数値を示している。
上記のように得られた印捺物の、水系の白色インク組成物(インク1)により記録した印捺面の隠蔽性を、パーソナル画質評価装置PIAS II(クオリティ・エンジニアリング・アソシエイツ社製)を用いて、エリア(ベタ領域)分析ツールの粒状度[%](Graininess)を測定した。測定により得られた、Cyan、Magenta、Yellow、Blackの各カラーにおける粒状度[%]の平均値を求めて、下記評価基準により評価した。評価結果を表2に示す。粒状度[%](Graininess)の値が小さい程、隠蔽性が高いことを示す。
(評価基準)
A:粒状度[%]が4.5未満。
B:粒状度[%]が4.5以上、6.0未満。
C:粒状度[%]が6.0以上、8.5未満。
D:粒状度[%]が8.5以上。
上記のように得られた印捺物の、水系の白色インク組成物(インク1)により記録した印捺面の密着性を、洗濯堅牢性試験により判定した。洗濯堅牢性試験は、「AATCC61 2A」に準じて、3回繰り返し行い、下記評価基準により評価した。評価結果を表2に示す。
(評価基準)
A:3回繰り返し試験後も被膜の脱落無し。
B:3回繰り返し試験後において、被膜の脱落があるが、半分以上の脱落せずに残っている。
C:2回繰り返し試験後において、被膜の脱落あり。
D:1回の試験後において、被膜の脱落あり。
前処理工程を行いインク付着は行わなかった記録物を用いて、その記録物の前処理塗布部(インクは付着していない)と非塗布部(布帛自身)とを目視で比較し、前処理塗布部における前処理組成物由来の白い後残りを確認した。評価結果を表2に示す。
(評価基準)
A:跡残り無し。
B:若干後残りがある。
C:跡残りがかなりある。
30mlのガラス管瓶(日電理化硝子社製、SV-30A)に、上記調製した前処理組成物1~9をそれぞれ10g秤量し、キャップ蓋をして密閉することにより、試験用の各サンプルを作製した。得られた各サンプルを60℃の条件で1週間保存し、保存後の外観の変化により下記の基準で評価した。評価結果を表2に示す。
(評価基準)
A:保存後、外観上変化がなく良好
B:保存後、僅かに凝集物が見られるが、沈殿が無い。
C:保存後、凝集が著しく発生しており、高さ2cmの液のうち、厚さ1mm以上の沈殿がある。
下記表3に記載の各成分を混合して、それぞれ総量100部の前処理組成物を得た。得られた液を平均孔径3μmのメンブランフィルターで濾過することにより、評価試験用の前処理組成物9~24を得た。
DK6850:エピハロヒドリン変性ポリアミン樹脂(星光PMC社製、重量平均分子量:1703、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分70%)
DK6854:エピハロヒドリン変性ポリアミン樹脂(星光PMC社製、重量平均分子量:5853、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分50%)
DK6885:エピハロヒドリン変性ポリアミン樹脂(星光PMC社製、重量平均分子量:2038、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分70%)
PAA-HCL-01:アリルアミン塩酸塩重合体(ニットーボーメディカル社製、重量平均分子量:1955、アリルアミン構造単位を含むカチオン性ポリマー、有効成分34%)
PAA-HCL-03:アリルアミン塩酸塩重合体(ニットーボーメディカル社製、重量平均分子量:6611、アリルアミン構造単位を含むカチオン性ポリマー、有効成分40%)
ユニセンスKHE100L:エピハロヒドリン変性ポリアミン樹脂(センカ社製、重量平均分子量:2191、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分60%)
カルボジライトE-02:カルボジイミド系架橋剤(日清紡ケミカル社製、カチオン性、有効成分40%)
エポクロスWS-700:オキサゾリン系架橋剤(日本触媒社製、カチオン性、有効成分25%)
Trixene Aqua BI522:ブロックイソシアネート系架橋剤(Baxenden社製、カチオン性、有効成分40%)
カチオンポリマーの質量%:前処理組成物全質量に対するカチオン性ポリマーの含有質量(%)
塗布量[g/cm2]:布帛単位面積当たりの前処理組成物塗布量
〔前処理工程〕
上記で得た前処理組成物9~24を上記表3に記載の塗布量で、ポリエステル布帛(ドライTシャツ、黒色の00300-ACT(glimmer製))に対し、それぞれA4サイズに塗布し、湿潤したプレコート層を形成した。その際、市販の霧吹き((株)ミツギロン社製、ファインスプレー)を用いて前処理組成物9~24を塗布した。前処理組成物塗布後、直ちに下記記録工程を行った。
上記のようにして調製した水系インク組成物(インク1)を産業用インクジェット評価装置(拡張型塗布装置EV2500:リコー株式会社製)に充填した。その後、インク液滴重量29pl/dot、ヘッド温度は25℃、解像度600×1200dpi、6回重ね印刷の条件で、水系インク組成物(インク1)を、前記のようにして得た湿潤したプレコート層の領域の一部に対し付着させて、白色のベタパターン画像を形成した。インク組成物付着後、引き出し式電気乾燥機(DDC-6A、ADELCO社製)を用いて130℃で3分の加熱乾燥を行い、乾燥させた。
下記表4に記載の各成分を混合して、それぞれ総量100部の前処理組成物を得た。得られた液を平均孔径3μmのメンブランフィルターで濾過することにより、評価試験用の前処理組成物1、2、4~8を得た。
DK6850:エピハロヒドリン変性ポリアミン樹脂(星光PMC社製、重量平均分子量:1703、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分70%)
PAA-HCL-03:アリルアミン塩酸塩重合体(ニットーボーメディカル社製、重量平均分子量:6611、アリルアミン構造単位を含むカチオン性ポリマー、有効成分40%)
メイカネートFM-1:ブロックイソシアネート系架橋剤(明成化学工業社製、カチオン性、解離温度120℃以上、有効成分30%)
メイカネートST:ブロックイソシアネート系架橋剤(明成化学工業社製、カチオン性、解離温度120℃以上、有効成分30%)
〔前処理工程〕
前処理組成物1、2、4~8を表4に記載の塗布量で、ポリエステル布帛(ドライTシャツ、黒色の00300-ACT(glimmer製))に対し、A4サイズに塗布し、湿潤したプレコート層を形成した。その際、市販の霧吹き((株)ミツギロン社製、ファインスプレー)を用いて前処理組成物1、2、4~8を塗布させた。前処理組成物塗布後、直ちに下記記録工程を行った。
記録工程前の前処理組成物の残存量は、下記式により算出した。実施例及び比較例はいずれも95%以上であった。
前処理組成物の残存量(%)=(記録工程前の布帛の重量-前処理工程前の布帛の重量)/(前処理工程の塗布の直後の布帛の重量-前処理工程前の布帛の重量)×100%
上記のようにして調製した水系の白色インク組成物(インク1)、および水系インク組成物(インク2)を産業用インクジェット評価装置(拡張型塗布装置EV2500:リコー株式会社製)に充填した。その後、インク液滴重量29pl/dot、ヘッド温度は25℃、解像度600×1200dpi、6回重ね印刷の条件で、水系の白色インク組成物(インク1)を、前記のようにして得た湿潤したプレコート層の領域の一部に対し付着させて、白色のベタパターン画像を形成した。その後、続けて水系インク組成物(インク2)をインク液滴重量27pl/dot、ヘッド温度は25℃、解像度600×1200dpi、6回重ね印刷の条件で、水系の白色インク組成物(インク1)を付与した領域の半分に付着させ、黒色のベタパターン画像を形成した。水系インク組成物(インク2)付着後、得られた捺染物を、引き出し式電気乾燥機(DDC-6A、ADELCO社製)を用いて130℃で3分の加熱乾燥を行い、乾燥させた。前処理工程及び記録工程は室温25℃で行った。
水系インク組成物のベタムラは、上記のように得られた黒色のベタパターン画像を、目視で観察し、下記評価基準により評価した。評価結果を表4に示す。
(評価基準)
A:水系インク組成物のベタ埋まりが均一である。
B:水系インク組成物のベタ埋まりが不均一であり、濃度ムラが若干認められる。
C:水系インク組成物のベタ埋まりが不均一であり、濃度ムラがかなり認められる。
一方、架橋剤を含まない前処理組成物を使用した比較例14、カチオン性ポリマーの添加量が少ない前処理組成物を使用した比較例15では、白色度と隠蔽性、密着性が低下し、カラーのベタムラが著しく悪くなることが分かった。カチオン性ポリマーの添加量が多い前処理組成物を使用した比較例16では、痕跡が悪くなることが分かった。また、架橋剤の添加量が多い前処理組成物を使用した比較例17では、保存安定性が悪くなることが分かった。
下記表5に記載の各成分を混合して、それぞれ総量100部の前処理組成物を得た。得られた液を平均孔径3μmのメンブランフィルターで濾過することにより、評価試験用の前処理組成物1、2、4~8を得た。
DK6850:エピハロヒドリン変性ポリアミン樹脂(星光PMC社製、重量平均分子量:1703、エピハロヒドリン構造単位を含むカチオン性ポリマー、有効成分70%)
PAA-HCL-03:アリルアミン塩酸塩重合体(ニットーボーメディカル社製、重量平均分子量:6611、アリルアミン構造単位を含むカチオン性ポリマー、有効成分40%)
メイカネートFM-1:ブロックイソシアネート系架橋剤(明成化学工業社製、カチオン性、解離温度120℃以上、有効成分30%)
メイカネートST:ブロックイソシアネート系架橋剤(明成化学工業社製、カチオン性、解離温度120℃以上、有効成分30%)
〔前処理工程〕
前処理組成物1、2、4~8を表5に記載の塗布量で、綿布帛1(ヘビーウェイトTシャツ、黒色の00085-CVT(PrintStar製))、綿布帛2(シーチング、(10000L)300.黒(B)(新宿オカダヤ))、綿布帛3(Daily 細コール、(KOF-14) BK.ブラック(B)(新宿オカダヤ))、綿35%/ポリエステル65%混紡(T/Cブロード、(AD40000)300.黒(B)(新宿オカダヤ))、ポリエステル布帛(ドライTシャツ、黒色の00300-ACT(glimmer製))に対し、A4サイズに塗布し、湿潤したプレコート層を形成した。その際、市販の霧吹き((株)ミツギロン社製、ファインスプレー)を用いて前処理組成物1、2、4~8を塗布させた。
実施例30においては、前処理組成物塗布後、湿潤したプレコート層を、ローラー(ヤヨイ化学社製、壁紙施工道具ローラ)を用いて布帛の毛羽立ちを寝かせる工程を施し、その後直ちに下記記録工程を行った。
また、比較例25~29においては、前処理組成物塗布後、卓上自動平プレス機(アサヒ繊維機械株式会社製:AF-65TEN)を用いて170℃で60秒の加熱乾燥を行い、その後下記記録工程を行った。
さらに、その他の実施例及び比較例においては、前処理組成物塗布後、直ちに下記記録工程を行った。
記録工程前の前処理組成物の残存量は、下記式により算出した。記録工程前の比較例25~29においては、前処理組成物の残存量が20%未満であり、その他の実施例及び比較例はいずれも95%以上であった。
前処理組成物の残存量(%)=(記録工程前の布帛の重量-前処理工程前の布帛の重量)/(前処理工程の塗布の直後の布帛の重量-前処理工程前の布帛の重量)×100%
上記のようにして調製した水系の白色インク組成物(インク1)、および水系インク組成物(インク2)を産業用インクジェット評価装置(拡張型塗布装置EV2500:リコー株式会社製)に充填した。その後、インク液滴重量29pl/dot、ヘッド温度は25℃、解像度600×1200dpi、6回重ね印刷の条件で、水系の白色インク組成物(インク1)を、前記のようにして得た湿潤したプレコート層の領域の一部に対し付着させて、白色のベタパターン画像を形成した。
その後、続けて水系インク組成物(インク2)をインク液滴重量27pl/dot、ヘッド温度は25℃、解像度600×1200dpi、6回重ね印刷の条件で、水系の白色インク組成物(インク1)を付与した領域の半分に付着させ、黒色のベタパターン画像を形成した。
実施例28~30及び比較例27~29においては、水系インク組成物(インク2)付着後、得られた捺染物を、引き出し式電気乾燥機(DDC-6A、ADELCO社製)を用いて150℃で10分の加熱乾燥を行い、乾燥させた。その他の実施例及び比較例においては、水系インク組成物(インク2)付着後、得られた捺染物を、引き出し式電気乾燥機(DDC-6A、ADELCO社製)を用いて130℃で3分の加熱乾燥を行い、乾燥させた。前処理工程及び記録工程は室温25℃で行った。
一方、架橋剤を含まない比較例18では、白色度と隠蔽性、密着性が低下し、カチオン性ポリマーの添加量が少ない比較例19では、白色度と密着性が低下し、カチオン性ポリマーの添加量が多い比較例20では、痕跡が悪くなることが分かった。また、架橋剤の添加量が多い比較例21では、保存安定性が悪くなることが分かった。
前処理組成物の塗布量が0.070g/cm2以上である比較例22では、前処理の痕跡が悪くなり、前処理組成物の塗布量が0.035g/cm2以下である比較例23、24では、白色度や、隠蔽性、密着性の低下が起きることが分かった。また、前処理後に乾燥を行った比較例25~29では、白色度の低下が劣ることが白色度と隠蔽性の低下が起き、カラーのベタムラが目立つことが分かった。
Claims (39)
- インクジェット方式により布帛に画像を形成する水系インク組成物を受容する湿潤したプレコート層を形成するために用いられる前処理組成物であって、下記[1]~[4]の要件を全て満たす前処理組成物。
[1]上記水系インク組成物が、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有する。
[2]単位面積当たりの上記前処理組成物塗布量が0.035g/cm2を超え、かつ、0.070g/cm2未満である、湿潤したプレコート層を形成するために用いられる。
[3]上記前処理組成物が、水、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満のカチオン性ポリマー、上記前処理組成物全質量に対して0.1質量%以上、かつ、2.7質量%未満の架橋剤を含有する。
[4]カチオン性ポリマーが、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかを含む。 - 前記架橋剤が、ブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物、オキサゾリン基含有化合物からなる群から選択される1種以上のカチオン性の架橋剤を含む、請求項1に記載の前処理組成物。
- 前記ブロック型イソシアネート基含有化合物の解離温度が120℃以上である、請求項2に記載の前処理組成物。
- 25℃における表面張力が35~60mN/mである、請求項1~3のいずれか一項に記載の前処理組成物。
- 請求項1~4のいずれか一項に記載の前処理組成物と、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有する水系インク組成物と、を含む印刷セット。
- 請求項1~4のいずれか一項に記載の前処理組成物を布帛に塗布し、湿潤したプレコート層を形成する前処理工程と、前記湿潤したプレコート層を形成した領域の少なくとも一部に対し、インクジェット方式により、水、顔料、樹脂エマルション、水溶性有機溶剤、界面活性剤を含有する水系インク組成物を塗布し、画像領域を形成する記録工程と、を有するインクジェット捺染方法。
- 上記前処理工程後、上記布帛に塗布した前処理組成物の残存量が、上記前処理工程における塗布量の総量に対し、20質量%以上の状態で、上記記録工程を有する、請求項6に記載のインクジェット捺染方法。
- 請求項1~4のいずれか一項に記載の前処理組成物を塗布した布帛に、前記水系インク組成物が印刷されてなる印刷物。
- 水、カチオン性ポリマー、架橋剤、を含む前処理組成物と、
水、白色顔料、ウレタン樹脂、水溶性有機溶剤、を含む水系の白色インク組成物と、を有する印刷セットであって、
上記前処理組成物中の上記カチオン性ポリマーの含有量が、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満であり、上記架橋剤の含有量が、前処理組成物全質量に対して、0.1質量%以上、かつ、2.7質量%未満である、前処理組成物と水系の白色インク組成物の印刷セット。 - 上記カチオン性ポリマーが、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかの構造単位を含むポリマーである、請求項9に記載の印刷セット。
- 前記架橋剤が、ブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物、オキサゾリン基含有化合物からなる群から選択される1種以上のカチオン性の架橋剤を含む、請求項9又は10に記載の印刷セット。
- 上記ブロック型イソシアネート基含有化合物の解離温度が120℃以上である、請求項11に記載の印刷セット。
- 上記前処理組成物の25℃における表面張力が、35~60mN/mである、請求項9~12のいずれか一項に記載の印刷セット。
- 上記ウレタン樹脂が、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂からなる群から選択される少なくともいずれかを含む、請求項9~13のいずれか一項に記載の印刷セット。
- 上記ウレタン樹脂のガラス転移温度が、0℃以下である請求項9~14のいずれか一項に記載の印刷セット。
- 上記水系の白色インク組成物が、更に塩基を含む、請求項9~15のいずれか一項に記載の印刷セット。
- 水、顔料、高分子分散剤を含む水系インク組成物をさらに有する、請求項9~16のいずれか一項に記載の印刷セット。
- 上記水系インク組成物が、更にウレタン樹脂、スチレン-ブタジエン樹脂、アクリル樹脂からなる群から選択される少なくともいずれかを含む、請求項17又は18に記載の印刷セット。
- 布帛に、請求項9~19のいずれか一項に記載の印刷セットに含まれる前処理組成物を塗布し、湿潤したプレコート層を形成する前処理工程と、該前処理工程後に上記布帛を乾燥することなく、上記湿潤したプレコート層の一部又は全部の領域に、請求項9~19のいずれか一項に記載の印刷セットに含まれる水系の白インク組成物をインクジェット方式により吐出して画像を形成する工程と、を有する、インクジェット捺染方法。
- 布帛に、請求項9~19のいずれか一項に記載の印刷セットに含まれる前処理組成物を塗布し、湿潤したプレコート層を形成する前処理工程と、該前処理工程後に上記布帛を乾燥することなく、上記湿潤したプレコート層の一部又は全部の領域に、請求項9~19のいずれか一項に記載の印刷セットに含まれる水系の白色インク組成物をインクジェット方式により吐出して画像を形成する工程と、上記水系の白色インク組成物を吐出して画像を形成した領域の一部又は全部に、請求項17~19のいずれか一項に記載の印刷セットに含まれる水系インク組成物をインクジェット方式により吐出して画像を形成する工程と、を有する、インクジェット捺染方法。
- 上記布帛が、ポリエステル、又は、ポリエステルを含む混紡である、請求項20又は21に記載のインクジェット捺染方法。
- 上記水系インク組成物を付与する工程後、画像を形成した布帛を130℃以下で乾燥する工程を含む、請求項22に記載のインクジェット捺染方法。
- 上記布帛が、綿、又は、綿を含む混紡である、請求項20又は21のいずれか一項に記載のインクジェット捺染方法。
- 上記前処理工程後、上記湿潤したプレコート層を形成した領域に圧力を加える加圧工程を有する、請求項24に記載のインクジェット捺染方法。
- 水、カチオン性ポリマー、架橋剤、を含む前処理組成物と、
少なくとも1種の水系インク組成物と、を用い、布帛に対して画像を形成するインクジェット捺染方法であって、
上記布帛に上記前処理組成物を塗布し、湿潤したプレコート層を形成する前処理工程と、該前処理工程後に上記布帛を乾燥することなく、上記湿潤したプレコート層の領域に、上記少なくとも1種の水系インク組成物を付与する工程と、を有し、上記布帛における前処理組成物の単位面積当たりの塗布量が0.035g/cm2を超え、かつ、0.070g/cm2未満であり、かつ、上記前処理組成物中の上記カチオン性ポリマーの含有量が、前処理組成物全質量に対して、1.4質量%を超え、かつ、10.5質量%未満であり、上記架橋剤の含有量が、前処理組成物全質量に対して、0.1質量%以上、かつ、2.7質量%未満であり、上記水系インク組成物が水、顔料、樹脂エマルション、水溶性有機溶剤及び界面活性剤を含有する、インクジェット捺染方法。 - 上記樹脂エマルションが、ウレタン樹脂、スチレン-ブタジエン樹脂、アクリル樹脂からなる群から選択される少なくともいずれかを含む、請求項26に記載のインクジェット捺染方法。
- 上記水系インク組成物が、さらに、高分子分散剤を含む、請求項26又は27に記載のインクジェット捺染方法。
- 上記顔料が、白色顔料である、請求項26~29のいずれか一項に記載のインクジェット捺染方法。
- 上記ウレタン樹脂が、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂からなる群から選択される少なくともいずれかを含む、請求項27~30のいずれか一項に記載のインクジェット捺染方法。
- 前記カチオン性ポリマーが、アリルアミン構造単位、ジアリルアミン構造単位、ジアリルアンモニウム構造単位、エピハロヒドリン構造単位からなる群から選択される少なくともいずれかの構造単位を含むポリマーである、請求項26~31のいずれか一項に記載のインクジェット捺染方法。
- 上記架橋剤が、ブロック型イソシアネート基含有化合物、カルボジイミド基含有化合物、オキサゾリン基含有化合物からなる群から選択される1種以上のカチオン性の架橋剤を含む、請求項26~32のいずれか一項に記載のインクジェット捺染方法。
- 上記ブロック型イソシアネート基含有化合物の解離温度が120℃以上である、請求項33に記載のインクジェット捺染方法。
- 上記前処理組成物の25℃における表面張力が、35~60mN/mである、請求項26~34のいずれか一項に記載のインクジェット捺染方法。
- 上記布帛が、ポリエステル、又は、ポリエステルを含む混紡である、請求項26~35のいずれか一項に記載のインクジェット捺染方法。
- 上記水系インク組成物を付与する工程後、画像を形成した布帛を130℃以下で乾燥する工程を含む、請求項36に記載のインクジェット捺染方法。
- 上記布帛が、綿、又は、綿を含む混紡である、請求項26~35のいずれか一項に記載のインクジェット捺染方法。
- 上記前処理工程後、上記湿潤したプレコート層を形成した領域に圧力を加える加圧工程を有する、請求項26~38のいずれか一項に記載のインクジェット捺染方法。
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