Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
  • B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

• This disclosure relates to a pretreatment liquid for inkjet inks, an ink set, an image recording method, a method for manufacturing a laminated body, an image recording material, and a laminated body.
• Patent Literature 1 discloses the following inkjet recording liquid set as an inkjet recording liquid set which has excellent image quality, substrate adhesion and ejection stability on a low-absorbency substrate or a non-absorbency substrate, and which has excellent hot water resistance on the image surface when formed into a coating film.
• the inkjet recording liquid set disclosed in Patent Document 1 is an inkjet recording liquid set including at least an inkjet ink and a pretreatment liquid, characterized in that the inkjet ink includes at least a pigment, an organic solvent, water, and a silicone-based surfactant, the pretreatment liquid includes at least water-insoluble resin fine particles and a pigment aggregating agent, and the silicone-based surfactant has a specific structure including an ethylene oxide group or the like.
• Patent document 1 JP 2021-042264 A
• a laminate is produced by applying an inkjet ink pretreatment liquid and an inkjet ink in this order onto a non-permeable substrate to record an image, and then laminating a substrate onto the image in the image recorded.
• boil resistance i.e., resistance to boiling treatment
• the inkjet ink pretreatment liquid is required to have storage stability.
• An object of one embodiment of the present disclosure is to provide a pretreatment liquid for inkjet ink that can improve the boil resistance of a laminate when a laminate is produced by applying a pretreatment liquid for inkjet ink and an inkjet ink in this order onto a non-permeable substrate to record an image, and then laminating a substrate for lamination onto the image in the obtained image recorded substrate, and that has excellent storage stability.
• Another problem to be solved by another embodiment of the present disclosure is to provide an ink set including the pretreatment liquid for an ink-jet ink, as well as an ink set, an image recording method, a method for producing a laminated body, an image recorded matter, and a laminated body, all of which use the pretreatment liquid for an ink-jet ink.
• a method for producing a flocculant comprising: at least one flocculant selected from the group consisting of an organic acid and a polyvalent metal compound; water; and a urethane resin;
• the urethane resin contains polyol units, polyisocyanate units, and -SO 3 - groups; the content of —SO 3 — groups relative to the total amount of the urethane resin is 2% by mass to 6% by mass;
• the —SO 3 — group is bonded to the end of the main chain of the urethane resin.
• Pretreatment liquid for inkjet ink ⁇ 2> The pretreatment liquid for ink-jet ink according to ⁇ 1>, in which the urethane resin contains a partial structure represented by the following formula (I):
• a 1 represents -NH- or -N(L 4 -Y 4 )-;
• Y 4 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, -OR 3 , -NH 2 , -NR 3 H, -NR 3 R 4 , or -C( ⁇ O)R 3 ;
• R3 and R4 each independently represent an alkyl group, an alkenyl group, an alkynyl group, or an aryl group;
• L1 represents an alkylene group having 1 to 4 carbon
• ⁇ 3> The pretreatment liquid for ink-jet ink according to ⁇ 1> or ⁇ 2>, in which the weight-average molecular weight of the urethane resin is 5,000 or more.
• ⁇ 4> The pretreatment liquid for ink-jet ink according to any one of ⁇ 1> to ⁇ 3>, in which the urethane resin has a glass transition temperature of -60°C to 40°C.
• ⁇ 5> The pretreatment liquid for ink-jet ink according to any one of ⁇ 1> to ⁇ 4>, in which a molar ratio of polyol units to polyisocyanate units in the urethane resin is 0.5 to 0.9.
• ⁇ 6> The pretreatment liquid for ink-jet ink according to any one of ⁇ 1> to ⁇ 5>, wherein the urethane resin contains a counter cation for the —SO 3 — group, and the pKa of the counter cation is 10.0 or more.
• ⁇ 7> The pretreatment liquid for ink-jet ink according to any one of ⁇ 1> to ⁇ 6>, wherein the urethane resin contains a counter cation for the —SO 3 — group, and the counter cation is an organic base cation.
• ⁇ 8> The pretreatment liquid for ink-jet ink according to any one of ⁇ 1> to ⁇ 7>, in which the polyol unit contains a polycarbonate diol unit.
• the ink set according to ⁇ 9> is used, applying a pretreatment liquid for an ink-jet ink onto a non-permeable substrate; applying an ink to the non-permeable substrate to which the inkjet ink pretreatment liquid has been applied by an inkjet recording method;
• An image recording method comprising: ⁇ 11> A step of obtaining an image recorded matter having a non-permeable substrate and an image disposed on the non-permeable substrate by the image recording method according to ⁇ 10>; A step of laminating a substrate for lamination onto the side of the image recorded product on which the image is disposed to obtain a laminate;
• a method for producing a laminate comprising the steps of: ⁇ 12>
• An image display device comprising: an impermeable substrate; and
• a pretreatment liquid for inkjet ink and an inkjet ink are applied in this order onto a non-permeable substrate to record an image, thereby obtaining an image recorded product, and a laminating substrate is laminated onto the image in the obtained image recorded product to produce a laminate product.
• This pretreatment liquid for inkjet ink is capable of improving the boil resistance of the laminate product and has excellent storage stability.
• an ink set including the pretreatment liquid for an ink-jet ink, as well as an ink set, an image recording method, a method for producing a laminated body, an image recorded article, and a laminated body, all of which use the pretreatment liquid for an ink-jet ink.
• the following provides a detailed explanation of the inkjet ink set for non-permeable substrates, the image recording method, the method for producing a laminate, the image recording material, and the laminate of the present disclosure.
• a numerical range indicated using “to” means a range that includes the numerical values before and after “to” as the minimum and maximum values, respectively.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in a certain numerical range.
• the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
• the amount of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified.
• a combination of two or more preferred aspects is a more preferred aspect.
• the term "process” includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• image refers to a film formed by applying a pretreatment liquid and an ink in this order
• image recording refers to the formation of an image (i.e., a film).
• image in this specification also includes a solid image.
• (meth)acrylate is a concept that encompasses both acrylate and methacrylate.
• (meth)acrylic is a concept that encompasses both acrylic and methacrylic.
• boiling treatment refers to a treatment in which an object (specifically, a laminate) is immersed in water at 60 to 100°C and heated for a certain period of time (e.g., 10 to 120 minutes).
• the pretreatment liquid for ink-jet ink (hereinafter, also simply referred to as the "pretreatment liquid") is
• the present invention comprises a flocculant which is at least one selected from the group consisting of an organic acid and a polyvalent metal compound, water, and a urethane resin,
• the urethane resin contains polyol units, polyisocyanate units, and -SO 3 - groups; the content of —SO 3 — groups relative to the total amount of the urethane resin is 2% by mass to 6% by mass;
• the —SO 3 — group is bonded to the end of the main chain of the urethane resin. This is a pretreatment liquid.
• the pretreatment liquid and an inkjet ink (hereinafter also simply referred to as "ink") are applied in this order onto a non-permeable substrate to record an image, thereby obtaining an image recorded matter, and when a lamination substrate is laminated onto the image in the obtained image recorded matter to produce a laminate body, the boil resistance of the laminate body can be improved. Furthermore, the pretreatment liquid according to the present disclosure has excellent storage stability.
• the pretreatment liquid contains a urethane resin, which improves the flexibility of the layer derived from the pretreatment liquid and the adhesion to non-permeable substrates. Furthermore, it is believed that the effect of improving the boil resistance of the laminated body described above is also due to the fact that the amount of -SO 3 - groups is 6 mass % or less relative to the total amount of urethane resin.
• the amount of -SO 3 - groups be 6 mass % or less relative to the total amount of urethane resin, the hydrophilicity of the urethane resin is prevented from becoming too high (i.e., hydrophobicity is maintained), and the urethane resin is prevented from swelling with water, which is believed to result in the prevention of a decrease in the boil resistance of the laminated body.
• the reason why the pretreatment liquid has excellent storage stability is believed to be that the urethane resin in the pretreatment liquid has -SO 3 - groups bonded to the main chain terminals as dispersing groups, and the amount of these -SO 3 - groups is 2 mass % or more based on the total amount of the urethane resin.
• the -SO 3 - group as a dispersing group is bonded to the main chain end of the urethane resin, the freedom of movement of the -SO 3 - group is ensured, and as a result, it is believed that the dispersion stability of the urethane resin in the pretreatment liquid is improved, and ultimately the storage stability of the pretreatment liquid is improved.
• the flocculant in the pretreatment liquid can act in a direction that reduces the dispersibility of the resin in the pretreatment liquid.
• the pretreatment liquid of the present disclosure is believed to have excellent storage stability despite being a pretreatment liquid that contains a flocculant and a resin.
• the pretreatment liquid of the present disclosure contains water.
• the water content is preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total amount of the pretreatment liquid.
• the upper limit of the water content although it depends on the amounts of other components, is preferably 90% by mass or less, and more preferably 80% by mass or less, based on the total amount of the pretreatment liquid.
• the pretreatment liquid of the present disclosure contains at least one flocculant selected from the group consisting of organic acids and polyvalent metal compounds.
• the aggregating agent in the pretreatment liquid contributes to improving image quality by aggregating the components in the inkjet ink when an image is recorded by applying the pretreatment liquid and the inkjet ink in this order onto a non-permeable substrate.
• Preferred examples of the flocculant include those described in paragraphs 0122 to 0130 of WO 2020/195360.
• Organic acids includes an organic compound having an acidic group.
• Acidic groups include phosphate groups, phosphonate groups, phosphinate groups, sulfate groups, sulfonic acid groups, sulfinic acid groups, and carboxy groups.
• the acidic group is preferably a phosphate group or a carboxy group, and more preferably a carboxy group.
• the acidic groups are at least partially dissociated in the pretreatment solution.
• Organic compounds having a carboxy group include (meth)acrylic acid, poly(meth)acrylic acid, acetic acid, formic acid, benzoic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, citric acid, tartaric acid, phthalic acid, 4-methylphthalic acid, lactic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, and nicotinic acid.
• the organic compound having a carboxy group is preferably a divalent or higher carboxylic acid (hereinafter also referred to as a polyvalent carboxylic acid), and more preferably a dicarboxylic acid.
• the polycarboxylic acid is preferably malonic acid, malic acid, maleic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, tartaric acid, 4-methylphthalic acid, or citric acid, and more preferably malonic acid, malic acid, tartaric acid, succinic acid, glutaric acid, pimelic acid, adipic acid, or citric acid.
• the organic acid preferably has a low pKa (for example, 1.0 to 5.0). This allows the surface charge of the pigment, resin particles, and other particles in the ink, which are stabilized in dispersion by weakly acidic functional groups such as carboxyl groups, to be reduced by contacting them with an organic acid with an even lower pKa, thereby decreasing the dispersion stability.
• pKa for example, 1.0 to 5.0
• the organic acid has a low pKa, high solubility in water, and a valence of 2 or more. It is also more preferable that the organic acid has a high buffering capacity in a pH range lower than the pKa of the functional group (e.g., carboxy group) that stabilizes the dispersion of the particles in the ink.
• the functional group e.g., carboxy group
• the polyvalent metal compound includes a polyvalent metal salt.
• the polyvalent metal salt includes organic acid polyvalent metal salts and inorganic acid polyvalent metal salts.
• organic acid polyvalent metal salt polyvalent metal salts of the above-mentioned organic acids (for example, formic acid, acetic acid, benzoic acid, etc.) are preferred.
• the inorganic acid polyvalent metal salt is preferably a polyvalent metal nitrate, a polyvalent metal hydrochloride, or a polyvalent metal thiocyanate.
• polyvalent metal salts examples include salts of alkaline earth metals of Group 2 of the periodic table (e.g., magnesium, calcium), salts of transition metals of Group 3 of the periodic table (e.g., lanthanum), salts of metals of Group 13 of the periodic table (e.g., aluminum), and salts of lanthanides (e.g., neodymium).
• a calcium salt, a magnesium salt, or an aluminum salt is preferable, and a calcium salt or a magnesium salt is more preferable.
• organic acid polyvalent metal salts are preferred, and organic acid calcium salts or organic acid magnesium salts are more preferred.
• the polyvalent metal compound is dissociated into polyvalent metal ions and counter ions in the pretreatment liquid.
• the content of the coagulant in the pretreatment liquid is preferably 0.1% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass, even more preferably 1% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass, based on the total amount of the pretreatment liquid.
• the flocculant contains an organic acid.
• the content of the organic acid in the total amount of the flocculant is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and further preferably 80% by mass to 100% by mass.
• the pretreatment liquid of the present disclosure contains a urethane resin that includes polyol units, polyisocyanate units, and an --SO.sub.3-- group.
• the content of the --SO 3 -- group relative to the total amount of the urethane resin is 2% by mass to 6% by mass.
• the —SO 3 — group is bonded to the end of the main chain of the urethane resin.
• a urethane resin containing polyol units, polyisocyanate units, and an -SO 3 - group is, in other words, a urethane resin that is a reaction product of at least a polyol, a polyisocyanate, and a compound for introducing an -SO 3 - group (hereinafter also referred to as a "compound for introducing a dispersing group").
• the urethane resin contains at least one type of polyisocyanate unit. Preferred embodiments of the polyisocyanate unit and preferred embodiments of the polyisocyanate for forming the polyisocyanate unit will be described below.
• the polyisocyanate may be a polyisocyanate containing two isocyanate groups (i.e., a diisocyanate (i.e., a bifunctional isocyanate)) or a polyisocyanate containing three or more isocyanate groups (i.e., a trifunctional or higher isocyanate).
• the polyisocyanate is preferably a difunctional to hexafunctional isocyanate.
• L1 include residues obtained by removing two isocyanate groups (NCO groups) from the bifunctional isocyanates according to the following specific examples.
• bifunctional isocyanates are as follows. However, bifunctional isocyanates are not limited to the following specific examples.
• the tri- or higher functional isocyanate is preferably a reaction product of at least one selected from the group consisting of bifunctional isocyanates and at least one selected from the group consisting of compounds containing three or more active hydrogen groups (e.g., tri- or higher functional polyol compounds, tri- or higher functional polyamine compounds, and tri- or higher functional polythiol compounds).
• the number of moles (number of molecules) of the bifunctional isocyanate to be reacted with the compound containing three or more active hydrogen groups is preferably 0.6 times or more, more preferably 0.6 to 5 times, even more preferably 0.6 to 3 times, and even more preferably 0.8 to 2 times the number of moles of the active hydrogen groups (the number of equivalents of the active hydrogen groups) in the compound containing three or more active hydrogen groups.
• Bifunctional isocyanates for forming trifunctional or higher isocyanates include the bifunctional isocyanates described in the specific examples above.
• Examples of compounds containing three or more active hydrogen groups for forming trifunctional or higher isocyanates include the compounds described in paragraphs 0057 to 0058 of WO 2016/052053.
• Examples of the tri- or higher functional isocyanate include adduct type tri- or higher functional isocyanates, isocyanurate type tri- or higher functional isocyanates, and biuret type tri- or higher functional isocyanates.
• Commercially available adduct-type trifunctional or higher isocyanates include Takenate (registered trademark) D-102, D-103, D-103H, D-103M2, P49-75S, D-110N, D-120N, D-140N, and D-160N (all from Mitsui Chemicals, Inc.), Desmodur (registered trademark) L75, UL57SP (from Sumika Bayer Urethane Co., Ltd.), and Coronate (
• Examples of the polyurethane elastomer include HL, HX, and L (registered trademarks) (Nippon Urethane Polymer Co., Ltd.), and P301-75E (Asahi Kasei Corporation).
• isocyanurate-type isocyanates include Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N (all from Mitsui Chemicals, Inc.), Sumidur N3300, Desmodur (registered trademark) N3600, N3900, Z4470BA (all from Sumika Bayer Urethane Co., Ltd.), Coronate (registered trademark) HX, HK (all from Nippon Urethane Polymer Co., Ltd.), Duranate (registered trademark) TPA-100, TKA-100, TSA-100, TSS-100, TLA-100, TSE-100 (all from Asahi Kasei Co., Ltd.), and the like.
• biuret-type trifunctional or higher isocyanates include Takenate (registered trademark) D-165N and NP1100 (both manufactured by Mitsui Chemicals, Inc.), Desmodur (registered trademark) N3200 (manufactured by Sumika Bayer Urethane Co., Ltd.), and Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Corporation).
• the urethane resin contains at least one type of polyol unit. Preferred embodiments of the polyol unit and preferred embodiments of the polyol for forming the polyol unit will be described below.
• the polyol may be a polyol containing two hydroxy groups (i.e., a diol) or a polyol containing three or more hydroxy groups.
• the polyol unit preferably contains the following structural unit (P0):
• L0 represents a divalent organic group
• * represents a bonding site
• the divalent organic group represented by L0 may be a group consisting of carbon atoms and hydrogen atoms, or may be a group containing carbon atoms and hydrogen atoms and also containing a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.).
• the divalent organic group represented by L 0 may contain at least one of a hydrophilic group and a polymerizable group. Specific examples of L 0 include residues obtained by removing hydrogen atoms from each of the two hydroxy groups in the diols exemplified below.
• diols that are preferred embodiments of polyols are shown, but the polyols are not limited to the following specific examples.
• the polyol unit in the urethane resin preferably contains a polycarbonate diol unit, which further improves the boil resistance of the laminate.
• the proportion of the polycarbonate diol units in the total amount of the polyol units is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and further preferably 80% by mass to 100% by mass.
• the polycarbonate diol for forming the polycarbonate diol unit is, for example, the above-mentioned compound (18) PC.
• a commercially available product may be used as the polycarbonate diol.
• Commercially available products include Duranol T5651 (manufactured by Asahi Kasei Corporation), Duranol T5652 (manufactured by Asahi Kasei Corporation), Duranol T6002 (manufactured by Asahi Kasei Corporation), Duranol T6001 (manufactured by Asahi Kasei Corporation), BENEBiOL HS0830B (manufactured by Mitsubishi Chemical Corporation), BENEBiOL HS0840H (manufactured by Mitsubishi Chemical Corporation), BENEBiOL NL1010DB (manufactured by Mitsubishi Chemical Corporation), and BENEBiOL NL2010DB (manufactured by Mitsubishi Chemical Corporation). etc.
• the molar ratio of the polyol unit to the polyisocyanate unit (hereinafter also referred to as the molar ratio [OH/NCO]) is preferably 0.4 to 1.0, more preferably 0.5 to 0.9, and even more preferably 0.6 to 0.8.
• the molar ratio [OH/NCO] is 0.4 or more, the boiling resistance of the laminate is further improved.
• the molar ratio [OH/NCO] is 1.0 or less, the storage stability of the pretreatment liquid is further improved.
• the urethane resin contains —SO 3 — groups.
• the —SO 3 — group functions as a dispersing group for dispersing the urethane resin in the pretreatment liquid.
• the —SO 3 — group is bonded to the end of the main chain of the urethane resin, which ensures the mobility of the —SO 3 — group as a dispersing group, thereby improving the dispersion stability of the urethane resin and the storage stability of the pretreatment liquid.
• the content of the —SO 3 — group relative to the total amount of the urethane resin is from 2% by mass to 6% by mass.
• the content of —SO 3 — groups relative to the total amount of the urethane resin is 2 mass % or more, the effect of improving the storage stability of the pretreatment liquid can be obtained.
• the content of the —SO 3 — group relative to the total amount of the urethane resin is preferably 3% by mass to 5% by mass.
• the urethane resin preferably contains a partial structure represented by the following formula (I) as a partial structure containing an SO 3 — group.
• a 1 represents -NH- or -N(L 4 -Y 4 )-;
• Y 4 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, -OH, -OR 3 , -NH 2 , -NR 3 H, -NR 3 R 4 , or -C( ⁇ O)R 3 ;
• R3 and R4 each independently represent an alkyl group, an alkenyl group, an alkynyl group, or an aryl group;
• L1 represents an alkylene group having 1 to 4 carbon
• the counter cation represented by Z + may or may not be bonded to the -SO3- group (ie, it may be dissociated). Preferred counter cations are described below.
• the alkylene group in L4 preferably has 1 to 4 carbon atoms.
• the alkenylene group in L4 preferably has 2 to 4 carbon atoms.
• the alkynylene group in L4 preferably has 2 to 4 carbon atoms.
• the arylene group in L4 preferably has 6 to 12 carbon atoms.
• the alkyl group for Y4 preferably has 1 to 4 carbon atoms.
• the alkenyl group for Y4 preferably has 2 to 4 carbon atoms.
• the alkynyl group for Y4 preferably has 2 to 4 carbon atoms.
• the aryl group for Y4 preferably has 6 to 12 carbon atoms.
• the halogen atom in Y4 is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• the alkyl group in each of R3 and R4 preferably has 1 to 4 carbon atoms.
• the alkenyl group for each of R3 and R4 preferably has 2 to 4 carbon atoms.
• the alkynyl group for each of R 3 and R 4 preferably has 2 to 4 carbon atoms.
• the aryl group in each of R3 and R4 preferably has 6 to 12 carbon atoms.
• the —SO 3 — group can be introduced into the urethane resin by using a compound for introducing an —SO 3 — group as one of the raw materials in producing the urethane resin.
• the compound for introducing a —SO 3 — group includes a compound containing a —SO 3 — group and an active hydrogen group.
• the active hydrogen group include an amino group (-NH 2 ), a secondary amino group (-NHR-; R is a substituent, for example, the "L 4 -Y 4 " group in formula (I)), a hydroxy group, etc.
• L1 and Z + have the same meanings as L1 and Z + in formula (I), respectively.
• R is a hydrogen atom or the "L 4 -Y 4 " group in formula (I).
• the urethane resin may contain a counter cation for the --SO 3 -- group.
• the counter cation for the -SO 3 - group hereinafter also simply referred to as "counter cation"
• Z + the cation represented by Z + in the above formula (I).
• the molecular weight of the organic base cation is preferably 73 to 600, more preferably 73 to 400, and even more preferably 73 to 200.
• the pKa of the counter cation is preferably 9.0 or more, and more preferably 10.0 or more.
• the upper limit of the pKa of the counter cation is, for example, 32.0, preferably 20.0, and more preferably 15.0.
• pKa means the value determined by neutralization titration at 25°C.
• the counter cation for the —SO 3 — group can be introduced into the urethane resin by using a compound for introducing a counter cation as one of the raw materials in producing the urethane resin.
• Examples of the compound for introducing a counter cation include a compound in which one proton (H + ) has been removed from a counter cation.
• examples of the counter cation include a cation obtained by adding one proton (H + ) to a compound for introducing a counter cation.
• Preferred embodiment of urethane resin Preferred embodiments of the urethane resin in the pretreatment liquid will be described below.
• the weight average molecular weight of the urethane resin is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more.
• the weight average molecular weight of the urethane resin is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. From the above viewpoint, a preferred range of the weight average molecular weight of the urethane resin is 5,000 to 50,000.
• the weight average molecular weight is measured by gel permeation chromatography (GPC).
• GPC uses HLC-8220GPC (manufactured by Tosoh Corporation), and three columns, TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, and TSKgel SuperHZ2000 (all trade names manufactured by Tosoh Corporation), are connected in series, and THF (tetrahydrofuran) is used as the eluent.
• the conditions are a sample concentration of 0.45% by mass, a flow rate of 0.35 ml/min, a sample injection amount of 10 ⁇ l, a measurement temperature of 40° C., and a differential refractive index detector.
• the calibration curve is prepared from eight samples of "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", “F-20”, “F-4", "F-1", "A-5000”, “A-2500”, "A-1000", and "n-propylbenzene”.
• the glass transition temperature of the urethane resin is preferably -60°C to 40°C, more preferably -55°C to 20°C, even more preferably -55°C to 10°C, and even more preferably -55°C to 0°C.
• the glass transition temperature is measured using a differential scanning calorimeter, for example, a product named "DSC-60" manufactured by Shimadzu Corporation.
• the urethane resin may be a water-soluble urethane resin or a water-insoluble urethane resin (i.e., urethane resin particles).
• the urethane resin is preferably urethane resin particles.
• water-soluble means the property of dissolving 1 g or more in 100 g of water at 25°C.
• water-insoluble refers to the property of dissolving less than 1 g in 100 g of water at 25°C.
• the average particle size of the urethane resin particles is preferably 1 nm to 200 nm, more preferably 3 nm to 200 nm, and even more preferably 50 nm to 150 nm.
• the average particle size is determined by measuring the volume average particle size by dynamic light scattering using a particle size distribution measuring device, for example, a product name "Nanotrac UPA-EX150” manufactured by Nikkiso Co., Ltd.
• the content of the urethane resin in the pretreatment liquid is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass, based on the total amount of the pretreatment liquid.
• the pretreatment liquid of the present disclosure may contain at least one organic solvent.
• organic solvent is not limited, and examples thereof include: Monoalcohols having 1 to 4 carbon atoms; Diols such as 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, and 4-methyl-1,2-pentanediol; Triols such as glycerin, 1,2,6-hexanetriol, and trimethylolpropane; Alkylene glycols such as ethylene glycol and propylene glycol; Alkylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether; polyalkylene glycols
• the content of the organic solvent is preferably 1% to 20% by mass, and more preferably 3% to 10% by mass, based on the total amount of the pretreatment liquid.
• the pretreatment liquid of the present disclosure may contain at least one surfactant.
• the type of surfactant is not particularly limited, and may be any of anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants.
• surfactants include acrylic surfactants, fluorine-based surfactants, and silicone-based surfactants.
• the surfactant content is preferably 0.1% to 5% by mass, and more preferably 0.2% to 1% by mass, based on the total amount of the pretreatment liquid.
• the pretreatment liquid of the present disclosure may contain other components in addition to those described above, as necessary.
• Other components that can be contained in the pretreatment liquid include known additives such as a solid wetting agent, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, antifungal agents, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymer compounds (for example, the water-soluble polymer compounds described in paragraphs 0026 to 0080 of JP2013-001854A).
• the pH of the pretreatment liquid is preferably 2.0 to 7.0, and more preferably 2.0 to 4.0.
• the pH is measured at 25° C. using a pH meter, for example, a pH meter manufactured by Toa DKK Corporation (model number "HM-31").
• the viscosity of the pretreatment liquid is preferably 0.5 mPa ⁇ s to 10 mPa ⁇ s, and more preferably 1 mPa ⁇ s to 5 mPa ⁇ s.
• the viscosity is a value measured at 25° C. using a viscometer.
• the viscosity is measured at 25° C. using a viscometer, for example, a TV-22 type viscometer manufactured by Toki Sangyo Co., Ltd.
• the surface tension of the pretreatment liquid is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, and even more preferably 30 mN/m to 45 mN/m.
• the surface tension is a value measured at a temperature of 25°C.
• the surface tension is measured at 25°C using a surface tensiometer, for example, an automatic surface tensiometer (product name "CBVP-Z”) manufactured by Kyowa Interface Science Co., Ltd., using the plate method.
• the ink set of the present disclosure comprises: The pretreatment liquid of the present disclosure described above, an inkjet ink containing water, a pigment, and a urethane resin; Includes.
• the ink set of the present disclosure contains the pretreatment liquid of the present disclosure described above, and therefore has the same effects as the pretreatment liquid of the present disclosure described above.
• the ink set of the present disclosure includes inks that are ink-jet inks that contain water, pigment, and a urethane resin.
• the ink set of the present disclosure may contain only one type of ink, or two or more types of ink.
• the ink contains water.
• the water content is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more, based on the total amount of the ink.
• the upper limit of the water content relative to the total amount of the ink is appropriately determined depending on the contents of other components, but is, for example, 99% by mass, preferably 95% by mass, and more preferably 90% by mass.
• the ink contains at least one type of urethane resin.
• the ink may contain one type of urethane resin, or two or more types of urethane resin.
• the urethane resin in the ink and the urethane resin in the pretreatment liquid may be the same type of urethane resin or different types of urethane resin.
• the urethane resin in the ink is preferably a polyester-based urethane resin having an ester bond in the main chain, a polycarbonate-based urethane resin having a carbonate bond in the main chain, or a polyether-based urethane resin having an ether bond in the main chain.
• the urethane resin in the ink may be a water-soluble urethane resin, or a water-insoluble urethane resin (i.e., urethane resin particles).
• the urethane resin is preferably urethane resin particles.
• the weight average molecular weight (Mw) of the urethane resin in the ink is not particularly limited, but is preferably from 1,000 to 300,000, more preferably from 2,000 to 200,000, and even more preferably from 10,000 to 150,000.
• the weight average molecular weight of the urethane resin in the ink can be measured in the same manner as the weight average molecular weight of the urethane resin in the pretreatment liquid.
• the urethane resin in the ink may be a commercially available product.
• commercially available products include the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., the Permarin UA series and U-coat series manufactured by Sanyo Chemical Industries, Ltd., the Takelac series manufactured by Mitsui Chemicals, Inc., and the PUE series manufactured by Murayama Chemical Laboratory.
• the content of the urethane resin in the ink is preferably 1% to 20% by mass, more preferably 2% to 15% by mass, and even more preferably 2% to 10% by mass, based on the total amount of the ink.
• the ink contains at least one pigment.
• the pigment contained in the ink may be a white pigment or a colored pigment.
• the ink may be a white ink containing a white pigment, or a colored ink containing a colored pigment.
• color pigment means a chromatic pigment or a black pigment.
• colored ink means chromatic ink (e.g., cyan ink, magenta ink, yellow ink, etc.) or black ink.
• the ink is preferably a white ink containing a white pigment.
• the concealing property of an image means the property of covering and concealing the surface on which the image is recorded (for example, the surface of a non-permeable substrate, the surface of an image formed as a base, etc.).
• white pigments examples include inorganic pigments such as titanium dioxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearls.
• the average primary particle size of the white pigment is preferably 150 nm or more, and more preferably 200 nm or more, and from the viewpoint of ink ejection properties, the average primary particle size of the white pigment is preferably 400 nm or less, and more preferably 350 nm or less.
• the average primary particle diameter of the white pigment is a value measured using a transmission electron microscope (TEM). Specifically, 50 randomly selected white pigment particles present within the field of view observed with the TEM are measured and averaged to obtain the primary particle diameters of the 50 particles.
• TEM transmission electron microscope
• a 1200EX transmission electron microscope manufactured by JEOL Ltd. can be used as the transmission electron microscope.
• the content of the white pigment is preferably 2% by mass to 25% by mass, more preferably 5% by mass to 25% by mass, and even more preferably 10% by mass to 20% by mass, based on the total amount of ink.
• the ink may contain a color pigment in addition to, or instead of, a white pigment.
• a color pigment the type and content of the color pigment can be found in the section on the second ink described below.
• the ink may contain at least one pigment dispersing resin.
• a pigment dispersing resin means a resin having a function of dispersing a pigment.
• the pigment dispersing resin may be a random copolymer or a block copolymer.
• the pigment dispersing resin may have a crosslinked structure.
• the ink may be prepared using a pigment dispersion that contains a pigment and a pigment dispersing resin.
• the hydrophobic monomer preferably includes a monomer having a hydrocarbon group with 4 or more carbon atoms, more preferably includes an ethylenically unsaturated monomer having a hydrocarbon group with 4 or more carbon atoms, and even more preferably includes a (meth)acrylate having a hydrocarbon group with 4 or more carbon atoms.
• the hydrocarbon group may be any of a linear hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
• the number of carbon atoms in the hydrocarbon group is more preferably 6 or more, and even more preferably 10 or more.
• the upper limit of the number of carbon atoms in the hydrocarbon group is, for example, 20.
• Examples of (meth)acrylates having a chain hydrocarbon group with 4 or more carbon atoms include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.
• the number of carbon atoms in the chain hydrocarbon group is more preferably 6 or more, even more preferably 8 or more, and particularly preferably 12 or more.
• the ethylenically unsaturated monomer having a chain hydrocarbon group with 4 or more carbon atoms is preferably lauryl (meth)acrylate or stearyl (meth)acrylate.
• Examples of (meth)acrylates having an alicyclic hydrocarbon group having 4 or more carbon atoms include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octa
• Examples of (meth)acrylates having an aromatic hydrocarbon group with 4 or more carbon atoms include 2-naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate. Of these, benzyl (meth)acrylate is preferred as an ethylenically unsaturated monomer having an aromatic hydrocarbon group with 4 or more carbon atoms.
• the hydrophobic monomer may further include a (meth)acrylate having a hydrocarbon group having 1 to 3 carbon atoms.
• the structural units derived from hydrophobic monomers contained in the pigment dispersion resin preferably include structural units derived from (meth)acrylates having a chain-like hydrocarbon group with 4 or more carbon atoms, and structural units derived from (meth)acrylates having an aromatic hydrocarbon group with 4 or more carbon atoms.
• the anionic group is preferably a carboxy group or a salt of a carboxy group.
• Carboxy group-containing monomers include, for example, (meth)acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, and crotonic acid.
• the anionic group-containing monomer is preferably (meth)acrylic acid or ⁇ -carboxyethyl acrylate, and more preferably (meth)acrylic acid.
• the ratio of the white pigment content to the pigment dispersion resin content is preferably 1:0.04 to 1:3, more preferably 1:0.05 to 1:1, and even more preferably 1:0.05 to 1:0.5, by mass.
• the acid value of the pigment dispersing resin is preferably 100 mgKOH/g or more, and more preferably 120 mgKOH/g or more.
• the acid value of the pigment dispersing resin is preferably 300 mgKOH/g or less, and more preferably 230 mgKOH/g or less.
• the ink preferably contains an organic solvent. This improves the ejection stability.
• the organic solvent contained in the color ink may be one type or two or more types.
• the organic solvent may be the same as the organic solvent contained in the pretreatment liquid. From the viewpoint of ejection stability, the organic solvent preferably contains at least one selected from the group consisting of alkylene glycols and alkylene glycol monoalkyl ethers.
• the organic solvent content is preferably 10% to 40% by mass, and more preferably 15% to 30% by mass, relative to the total amount of the ink.
• the ink may contain additives such as surfactants, water-soluble resins, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and basic compounds, as necessary.
• additives such as surfactants, water-soluble resins, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and basic compounds, as necessary.
• the pH of the ink (25° C.) is preferably from 7 to 10, and more preferably from 7.5 to 9.5.
• the pH of the color ink can be measured in the same manner as the pH of the pretreatment liquid.
• the viscosity of the ink (30°C) is preferably 0.5 mPa ⁇ s to 30 mPa ⁇ s, more preferably 2 mPa ⁇ s to 20 mPa ⁇ s, more preferably 2 mPa ⁇ s to 15 mPa ⁇ s, and even more preferably 3 mPa ⁇ s to 10 mPa ⁇ s.
• the viscosity of the colored ink can be measured in the same manner as the viscosity of the pretreatment liquid.
• the surface tension of the ink is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, and even more preferably 30 mN/m to 45 mN/m.
• the surface tension can be measured in the same manner as in the pretreatment liquid.
• the ink set of the present disclosure comprises:
• the white ink (hereinafter also referred to as the "first ink”) is an ink-jet ink containing water, a white pigment, and a urethane resin.
• a color ink (hereinafter also referred to as "second ink”) which is an ink-jet ink containing water, a color pigment, and a urethane resin; may include:
• the ink set may include two or more types of white ink, and may also include two or more types of colored ink (for example, a combination of cyan ink, magenta ink, yellow ink, and black ink, etc.).
• a pretreatment liquid according to the present disclosure a pretreatment liquid according to the present disclosure; a first ink as a white ink, which is an ink-jet ink containing water, a white pigment, and a resin having a carboxy group; a second ink as a color ink, which is an ink-jet ink containing water, a color pigment, and a resin having a carboxy group;
• a first ink as a white ink, which is an ink-jet ink containing water, a white pigment, and a resin having a carboxy group
• a second ink as a color ink which is an ink-jet ink containing water, a color pigment, and a resin having a carboxy group
• the color pigment may be any of organic and inorganic pigments that are commonly available on the market. Examples of color pigments include those described in "Encyclopedia of Pigments” edited by Seijiro Ito (published in 2000), “Industrial Organic Pigments” by W. Herbst and K. Hunger, and JP-A Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.
• the color pigment may be a water-insoluble pigment that can be dispersed in water by the aid of a dispersant, or may be a self-dispersing pigment.
• a self-dispersing pigment is a pigment that can be dispersed in water without the use of a dispersant.
• the self-dispersing pigment is a compound in which at least one type selected from the group consisting of hydrophilic groups such as a carbonyl group, a hydroxyl group, a carboxyl group, a sulfo group, and a phosphate group, and salts thereof, is chemically bonded to the surface of the pigment directly or via another group.
• the type of color pigment is not particularly limited, and examples include cyan pigments, magenta pigments, yellow pigments, and black pigments.
• the content of the color pigment is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 1% by mass to 10% by mass, relative to the total amount of the second ink.
• the image recording method of the present disclosure includes: A step of applying a pretreatment liquid of the present disclosure onto a non-permeable substrate (hereinafter also referred to as a "pretreatment liquid application step”); a step of applying an ink containing water, a pigment, and a urethane resin (i.e., an inkjet ink; the same applies below) to an area of the non-permeable substrate to which the pretreatment liquid has been applied, by an inkjet recording method (hereinafter, also referred to as an "ink application step”); Includes.
• the image recording method of the present disclosure may be carried out using the ink set of the present disclosure described above.
• the ink used in the ink application step is the same as the ink described in the section on the ink set of the present disclosure, and the preferred embodiments are also the same. From the viewpoint of the concealing property of the image, the ink used in the ink application step is preferably a white ink containing a white pigment.
• the pretreatment liquid application step is a step of applying the pretreatment liquid in the ink set of the present disclosure (i.e., the pretreatment liquid of the present disclosure) onto a non-permeable substrate.
• non-permeable substrate examples include glass, metals (e.g., aluminum, zinc, copper, etc.) and resins (e.g., polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, nylon, acrylic resin, etc.).
• metals e.g., aluminum, zinc, copper, etc.
• resins e.g., polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, nylon, acrylic resin, etc.
• the material of the non-permeable substrate is polypropylene, polyethylene, polyethylene terephthalate, nylon, acrylic resin, or polyvinyl chloride.
• the thickness of the non-permeable substrate is preferably 0.1 ⁇ m to 1,000 ⁇ m, and more preferably 0.1 ⁇ m to 1,000 ⁇ m. It is more preferable that the thickness is from 1 ⁇ m to 800 ⁇ m, and further preferably from 1 ⁇ m to 500 ⁇ m.
• the non-permeable substrate may be subjected to a hydrophilization treatment.
• hydrophilization treatments include, but are not limited to, corona treatment, plasma treatment, frame treatment, heat treatment, abrasion treatment, light irradiation treatment (e.g., UV treatment), and flame treatment.
• Corona treatment can be performed, for example, using a Corona Master (product name "PS-10S", manufactured by Shinko Electric Measuring Instruments).
• the conditions for the corona treatment may be appropriately selected depending on the type of non-permeable substrate, etc.
• the non-permeable substrate is a transparent non-permeable substrate
• the pretreatment liquid the second ink as a colored ink
• the first ink as a white ink
• it is easy to view a colored image e.g., a pattern image such as letters, figures, etc.
• a white image e.g., a solid image
• the method for applying the pretreatment liquid is not particularly limited, and examples thereof include known methods such as a coating method, a dipping method, and an inkjet recording method.
• coating methods include known coating methods using a bar coater, extrusion die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, etc.
• Methods for heating and drying the pretreatment liquid include, for example, a method of applying heat with a heater or the like from the side opposite to the side of the non-permeable substrate to which the pretreatment liquid has been applied, a method of applying warm or hot air to the side of the non-permeable substrate to which the pretreatment liquid has been applied, a method of applying heat with an infrared heater to the side of the non-permeable substrate to which the pretreatment liquid has been applied or the side opposite to the side to which the pretreatment liquid has been applied, and a combination of these methods.
• the heating temperature during the heating and drying of the pretreatment liquid is preferably 35°C or higher, and more preferably 40°C or higher. There is no particular upper limit to the heating temperature, but 100°C is preferred, 90°C is more preferred, and 70°C is even more preferred.
• the heating and drying time is not particularly limited, but is preferably 0.5 to 60 seconds, more preferably 0.5 to 20 seconds, and even more preferably 0.5 to 10 seconds.
• the ink application step is a step of applying ink by an inkjet recording method onto the non-permeable substrate to which the pretreatment liquid has been applied.
• the components in the ink are aggregated on the non-permeable substrate by the action of the aggregating agent in the pretreatment liquid, thereby forming an image.
• ink ejection method used in inkjet recording
• any of the well-known methods such as a charge control method that utilizes electrostatic attraction to eject ink, a drop-on-demand method (pressure pulse method) that utilizes the vibration pressure of a piezoelectric element, an acoustic inkjet method in which an electric signal is converted into an acoustic beam and irradiated onto the ink to eject ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method in which ink is heated to form bubbles and the resulting pressure is utilized.
• a charge control method that utilizes electrostatic attraction to eject ink
• drop-on-demand method pressure pulse method
• acoustic inkjet method in which an electric signal is converted into an acoustic beam and irradiated onto the ink to eject ink using radiation pressure
• thermal inkjet Bubble Jet (registered trademark)
• JP-A-54-59936 As an inkjet recording method, in particular, the method described in JP-A-54-59936 can be effectively used, in which ink subjected to the action of thermal energy undergoes a sudden change in volume, and the ink is ejected from the nozzles by the action force caused by this state change.
• the method described in paragraphs 0093 to 0105 of JP-A-2003-306623 can also be used.
• Ink is applied to a non-permeable substrate using the inkjet recording method by ejecting the ink from the nozzles of an inkjet head.
• Inkjet head methods include the shuttle method, in which a short serial head is scanned across the width of the recording medium to perform recording, and the line method, which uses a line head in which recording elements are arranged to cover the entire area of one side of the recording medium.
• an image can be recorded on the entire surface of the recording medium by scanning the recording medium in a direction intersecting the arrangement direction of the recording elements.
• the line method does not require a transport system such as a carriage that scans a short head as in the shuttle method. Also, compared to the shuttle method, the line method does not require complex scanning control of the carriage movement and the recording medium, and only the recording medium moves. Therefore, the line method achieves faster image recording speeds than the shuttle method.
• the ink be applied using an inkjet head with a resolution of 300 dpi or more (more preferably 600 dpi or more, and even more preferably 800 dpi or more).
• dpi stands for dots per inch, and 1 inch is 2.54 cm.
• the amount of ink ejected is preferably 1 pL (picoliter) to 10 pL, and more preferably 1.5 pL to 6 pL.
• the amount of ink applied to the area of the non-permeable substrate to which the pretreatment liquid has been applied is preferably 3.0 g/m 2 to 15.0 g/m 2 , and more preferably 5.0 g/m 2 to 12.0 g/m 2 .
• the ink application step includes applying an ink by an inkjet method onto the non-permeable substrate to which the pretreatment liquid has been applied; Heating and drying the applied ink; may include:
• the method of heat drying is not particularly limited, but examples thereof include infrared (IR) drying, hot air drying, and drying by heating using a heating device (for example, a heater, a hot plate, a heating furnace, etc.).
• IR infrared
• the heat drying method may be a combination of two or more of these methods.
• the heat drying can be carried out by heating the ink from at least one of the image recording surface side and the non-image recording surface side of the non-permeable substrate.
• the heating temperature in the heat drying of the ink is preferably 35° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, and even more preferably 60° C. or higher.
• the upper limit of the heating temperature is not particularly limited, but is preferably 100°C, and more preferably 90°C.
• the heating time for heating and drying the ink is not particularly limited, but is preferably 1 to 180 seconds, more preferably 1 to 120 seconds, and even more preferably 1 to 60 seconds.
• An example of the image recording method of the present disclosure in the case of using ink of two or more colors is the image recording method using the first ink (i.e., white ink) and the second ink (i.e., colored ink) described above.
• the image recording method according to this embodiment includes the steps of: applying a pretreatment solution of the present disclosure onto a non-permeable substrate; applying the first ink (i.e., white ink) and the second ink (i.e., colored ink) described above to the region of the non-permeable substrate to which the pretreatment liquid has been applied by an inkjet recording method; Includes.
• the process of applying the pretreatment liquid onto the non-permeable substrate is as described above.
• a multi-color image can be recorded using a first ink (i.e., white ink) and a second ink (i.e., colored ink).
• a multi-color image is a colored image (such as a pattern image of characters, figures, etc.) against a white image (such as a solid image) as a background.
• the order in which the first ink (i.e., white ink) and the second ink (i.e., colored ink) are applied may not matter. For example, when the image is viewed from the image recording surface side, the first ink (i.e., white ink) and the second ink (i.e., colored ink) are applied in this order.
• the second ink i.e., colored ink
• the first ink i.e., white ink
• the method for producing a laminate according to the present disclosure includes: A step of obtaining an image recorded matter comprising a non-permeable substrate and an image disposed on the non-permeable substrate by the image recording method of the present disclosure described above; A step of laminating a substrate for lamination onto the side of the image recorded product on which the image is disposed to obtain a laminate; Includes.
• the method for producing a laminated body of the present disclosure includes the image recording method of the present disclosure described above, and therefore has the same effects as the image recording method of the present disclosure described above. Specifically, a laminated body with excellent boil resistance can be obtained.
• the step of obtaining a laminate is a step of obtaining a laminate by laminating a substrate for lamination onto the side of the image recorded product on which the image is disposed.
• the lamination can be performed by, for example, a method of laminating a substrate on the side of the image recorded product on which the image is disposed via another layer (e.g., an adhesive layer), or a method of laminating a substrate on the side of the image recorded product on which the image is disposed, with the substrate being passed through a laminator to be laminated, etc. In the latter case, a commercially available laminator can be used.
• the lamination temperature when laminating is not particularly limited.
• the temperature may be in the range of 20°C or higher.
• the temperature of the laminating rolls may be in the range of 20°C to 80°C.
• the pressure of the laminating roll pair may be appropriately selected according to need.
• the substrate for lamination is preferably a resin substrate.
• the resin substrate is not particularly limited, but examples thereof include substrates made of thermoplastic resins.
• the resin substrate is a substrate obtained by molding a thermoplastic resin into a sheet shape.
• the resin substrate preferably comprises polypropylene, polyethylene terephthalate, nylon, polyethylene, or polyimide.
• the shape of the resin substrate is not particularly limited, but a sheet-shaped resin substrate is preferable.
• the thickness of the resin substrate is preferably 10 ⁇ m to 200 ⁇ m, and more preferably 10 ⁇ m to 100 ⁇ m.
• the lamination substrate may be laminated directly onto the side of the image recording material on which the image is disposed, or may be laminated via another layer (e.g., an adhesive layer).
• lamination When laminating a substrate directly onto the side of an image recording material on which an image is placed, lamination can be performed by known methods such as heat compression bonding or heat fusion bonding.
• the lamination can be performed, for example, by a method in which an adhesive is applied to the side of the image recording material on which the image is disposed, the substrate for lamination is placed thereon, and then the image recording material and the substrate for lamination are attached to each other.
• the lamination can also be performed by a method such as extrusion lamination (i.e., sandwich lamination).
• the adhesive layer preferably contains an isocyanate.
• the adhesive layer contains an isocyanate, the adhesion between the adhesive layer and the image is improved, and the boil resistance can be further improved.
• the image recording of the present disclosure is a non-permeable substrate; and an image disposed on the non-permeable substrate;
• the image is a pretreatment layer disposed on an impermeable substrate, the pretreatment layer including a flocculant selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex, and a urethane resin; an ink layer disposed on the pretreatment layer and containing a pigment (e.g., at least one of a white pigment and a colored pigment) and a urethane resin; Including,
• the urethane resin in the pretreatment layer contains polyol units, polyisocyanate units, and polyalkylene glycol monoalkyl ether units.
• the image recorded matter of the present disclosure can be produced by the image recording method of the present disclosure. Therefore, a laminate having excellent boil resistance can be produced.
• the components in the pretreatment layer and the ink layer the components of the pretreatment liquid, the components of the first ink, and the components of the second ink described above can be referenced as appropriate.
• the laminate of the present disclosure is The image recording material of the present disclosure described above; a lamination substrate laminated onto an image of an image recording material; Equipped with.
• the laminate of the present disclosure can be produced by the method for producing the laminate of the present disclosure. Therefore, it has excellent boil resistance.
• the preferred embodiments of the substrate for lamination are as described above.
• Example 2 Preparation of Aqueous Dispersion of Urethane Resin Particles for Pretreatment Liquid>
• Isophorone diisocyanate (IPDI) (26.6 g)
• Duranol T5651 Adahi Kasei Corporation, polycarbonate diol; hereinafter, also referred to as T5651
• ethyl acetate 74.9 g
• 0.1 g of Neostan U-600 manufactured by Nitto Kasei Co., Ltd., inorganic bismuth catalyst; hereinafter, also referred to as U-600 was added, and the mixture was stirred at 70° C.
• urethane A solvent: mixed solvent of methanol and ethyl acetate
• Distilled water (100 g) was added to the resulting 30% by mass solution (100 g) of urethane A, and the mixture was emulsified at room temperature for 30 minutes at 7,000 rpm using a homogenizer to obtain an emulsion.
• the resulting emulsion was heated to 50° C. and stirred at 50° C. for 5 hours to distill off ethyl acetate from the liquid.
• the liquid from which ethyl acetate had been distilled off was diluted with distilled water so that the solid content was 25% by mass, thereby obtaining an aqueous dispersion of urethane resin particles (solid content: 25% by mass).
• the dispersing group is a -SO 3 - group
• the counter cation is an organic ammonium cation consisting of one diazabicycloundecene molecule and one proton (H + ).
• Table 1 shows the type of polyol (hereinafter also referred to as "OH”), the type of polyisocyanate (hereinafter also referred to as “NCO”), the molar ratio [OH/NCO], the type of compound for introducing dispersing groups, the type of dispersing groups, the positions of the dispersing groups, the amount of -SO 3 - , and the type of compound for introducing counter cations, used in the preparation of the above-mentioned aqueous dispersion of urethane resin particles, and the weight average molecular weight of the urethane resin in the urethane resin particles.
• the molar ratio [OH/NCO] means the molar ratio of polyol units to polyisocyanate units.
• a pretreatment liquid with the following composition was prepared using the above aqueous dispersion of urethane resin particles and the following components other than the urethane resin particles.
• Solution 1 was added dropwise to the three-neck flask over 4 hours, and solution 2 was added dropwise over 5 hours. After the dropwise addition was completed, the reaction was allowed to proceed for an additional 2 hours, and then the temperature was raised to 95° C. and the mixture was heated and stirred for 3 hours to react all of the unreacted monomers. The disappearance of the monomers was confirmed by a nuclear magnetic resonance ( 1 H-NMR) method.
• the resulting reaction solution was heated to 70° C., and 12.0 g of dimethylethanolamine was added thereto, followed by the addition of propylene glycol and stirring to obtain a 30% by mass solution of pigment dispersion resin 1.
• the structural unit of the obtained pigment dispersion resin 1 was confirmed by 1 H-NMR.
• the weight average molecular weight (Mw) determined by GPC was 28,000.
• the acid value of the pigment dispersing resin 1 was 200 mg KOH/g.
• Pigment dispersion 1 was prepared using a Ready Mill Model LSG-4U-08 (manufactured by Imex Corporation). Into a zirconia container, 45 parts by mass of titanium dioxide particles (average primary particle size: 210 nm, product name "PF-690", manufactured by Ishihara Sangyo Kaisha, Ltd.) as a white pigment, 15 parts by mass of a 30% by mass solution of the above-mentioned pigment dispersion resin 1, and 40 parts by mass of ultrapure water were added. Furthermore, 40 parts by mass of 0.5 mm ⁇ zirconia beads (manufactured by TORAY, Toraceram beads) were added and mixed lightly with a spatula.
• TORAY Toraceram beads
• the zirconia container containing the obtained mixture was placed in a ready mill and dispersed for 5 hours at a rotation speed of 1000 rpm (revolutions per minute). After completion of dispersion, the beads were removed by filtration using a filter cloth, and pigment dispersion 1 having a white pigment concentration of 45% by mass was obtained.
• a white ink having the following composition was prepared using Pigment Dispersion Liquid 1 and the components listed below other than Pigment Dispersion Resin 1 and the white pigment.
• An image was recorded using the pretreatment liquid and white ink.
• An inkjet recording apparatus was prepared, which was equipped with a transport system for continuously transporting a long substrate, a wire bar coater for applying a pretreatment liquid to the substrate, and an inkjet head for applying ink.
• a substrate a polyethylene terephthalate (PET) substrate ("FE2001” manufactured by Futamura Chemical Co., Ltd., thickness 12 ⁇ m, width 780 mm, length 4000 m; hereinafter referred to as "non-permeable substrate A”) was prepared.
• PET polyethylene terephthalate
• the above pretreatment liquid was applied to the non-permeable substrate A by a wire bar coater so as to be about 1.7 g/m 2 , and then dried at 50° C. for 2 seconds.
• a white ink was ejected from an inkjet head and applied in the form of a solid image onto the surface of the non-permeable substrate A to which the pretreatment liquid had been applied.
• the applied white ink was dried with hot air at 80° C. for 30 seconds to record a solid image, thereby obtaining an image record.
• Inkjet head 1200 dpi/30 inch width piezo full line head
• Ink ejection volume from inkjet head 3.0 pL (picoliters)
• Driving frequency 41 kHz (substrate conveying speed: 50 m/min)
• the viscosity of the pre-treatment liquid that had been prepared and then allowed to stand at 25° C. for 1 hour (hereinafter referred to as “viscosity before storage”), and the viscosity of the pre-treatment liquid that had been prepared and then stored in a sealed state at 60° C. for 14 days (hereinafter referred to as “viscosity after storage”) were measured.
• the viscosity before and after storage was measured using a VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) at 25° C. and 100 rpm (revolutions per minute).
• a sealed state refers to a state in which the contents are sealed in a container, and when the contents are stored at 50°C for 14 days, the amount of weight loss of the contents is less than 1% by weight.
• the viscosity increase rate was calculated by subtracting the viscosity before storage from the viscosity after storage. The smaller the degree of increase in viscosity, the more excellent the storage stability.
• the evaluation criteria are as follows:
• the resulting laminate was aged at 40° C. for 48 hours. Two sample pieces, each 200 mm long and 200 mm wide, were cut out from the aged laminate. The cut out sample pieces were overlapped and heat sealed on three sides to obtain a bag. The obtained bag was filled with pure water and then heat sealed.
• the sealed bag was placed in an autoclave (small sterilizer) for retort foods (product name "SR-240", manufactured by Tommy Seiko Co., Ltd.) and boiled at 95°C for 40 minutes. After the boiling treatment, the bag was taken out and the condition of the bag was visually observed. Specifically, the boiling resistance was evaluated based on the presence or absence of deformation of the bag and lifting of the laminate. The evaluation criteria are as follows: The term "laminate lifting" refers to a state in which lifting occurs due to peeling of an image or a laminate substrate.
• Examples 1 and 3 to 20, and Comparative Examples 1 to 4 The same operations as in Example 2 were performed, except that at least one of the types of the flocculant in the pretreatment liquid, the raw materials of the urethane resin particles (specifically, the type of polyol, the type of polyisocyanate, the molar ratio [OH/NCO], the type of compound for introducing a dispersing group, the amount of -SO 3 - , and the type of compound for introducing a counter cation), and the weight average molecular weight of the urethane resin in the urethane resin particles was changed as shown in Table 1. The weight average molecular weight of the urethane resin in the urethane resin particles was changed by changing the reaction time.
• the types of the flocculant in the pretreatment liquid specifically, the type of polyol, the type of polyisocyanate, the molar ratio [OH/NCO], the type of compound for introducing a dispersing group, the amount of -SO 3 -
• IPDI isophorone diisocyanate
• HMDI hexamethylene diisocyanate
• HXDI 1,3-bis(isocyanatomethyl)cyclohexane
• PCD polycarbonate diol (trade name: Duranol T5651 (manufactured by Asahi Kasei Corporation), molecular weight 1000) ⁇ PPG...
• PTMG Polytetramethylene glycol (product name PTMG1000 (manufactured by Mitsubishi Chemical Corporation), molecular weight 1000)
• TCD Tricyclo[5.2.1.0 2,6 ]decane dimethanol
• DMPA Dimethylolpropionic acid
• BES N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid
• SSNa Sodium styrenesulfonate
• DBU Diazabicycloundecene NEt 3 : Triethylamine
• the molar ratio [OH/NCO] (ie, the molar ratio of polyol units to polyisocyanate units) was adjusted by adjusting the molar ratio of the charged polyol to the charged polyisocyanate.
• the amount of --SO 3 -- (dispersing group) was adjusted by adjusting the amount of the compound for introducing a dispersing group.
• Example 21 The same procedure as in Example 2 was carried out except that the urethane resin particles in the white ink were changed to acrylic resin particles.
• the white ink of Example 21 was prepared using Movinyl 972 (manufactured by Japan Coating Resins Co., Ltd.), which is an aqueous dispersion of acrylic resin particles.
• Comparative Example 5 The same procedure as in Example 2 was carried out except that the urethane resin particles in the pretreatment liquid were changed to acrylic resin particles.
• the acrylic resin particles used in the pretreatment liquid of Comparative Example 5 were prepared as follows. Distilled water (256.1 g), Olfine E1020 (0.9 g), sodium persulfate (NPS) (1.6 g), and sodium hydrogen carbonate (0.6 g) were placed in a three-neck flask and heated to 85° C. under a nitrogen atmosphere.
• a solution 3 containing NPS (1.0 g), distilled water (24.0 g), and sodium bicarbonate (0.6 g) were prepared respectively.
• SSNa sodium styrenesulfonate
• a solution 3 containing NPS 1.0 g
• sodium bicarbonate 0.6 g
• Comparative Example 4 in which a pretreatment liquid in which the —SO 3 — group was bonded to a side chain of the urethane resin instead of to the end of the main chain was used, the storage stability of the pretreatment liquid decreased.
• Comparative Example 5 in which a pretreatment liquid containing an acrylic resin instead of a urethane resin was used, the boil resistance of the laminate was reduced.
• Example 2 shows that when the weight average molecular weight of the urethane resin in the pretreatment liquid is 5,000 or more (Example 2), the boil resistance of the laminate is further improved.
• Example 13 shows that when the molar ratio [OH/NCO] (i.e., the molar ratio of polyol units to polyisocyanate units) is 0.5 or more (Example 13), the boil resistance of the laminate is further improved.
• the results of Examples 2 and 6 show that when the molar ratio [OH/NCO] is 0.9 or less (Examples 2 and 13), the storage stability of the pretreatment liquid is further improved.
• Example 101 Evaluation of multi-color images
• Colored inks (specifically, cyan ink, magenta ink, yellow ink, and black ink) having the compositions shown in Table 2 were prepared.
• each component indicates its content (mass %) in the corresponding ink, and the "balance" which is the amount of water indicates the remaining amount to make the total 100 mass %.
• the details of the components after PG (1,2-propanediol) are the same as those of the white ink described above.
• APD4000C etc. in Table 2 are pigment dispersions, and the details are as follows.
• the amount of pigment dispersion is shown as the solid content (total amount of pigment and pigment dispersant).
• ⁇ APD4000C Project Cyan APD4000 (FUJIFILM Imaging Colorants, cyan pigment dispersion, pigment concentration: 20% by weight APD4000M ...
• Projet Magenta APD4000 (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 20% by mass)
• APD1000R Projet Red APD1000 (manufactured by FUJIFILM Imaging Colorants, red pigment dispersion, pigment concentration: 16% by mass)
• APD4000Y Projet Yellow APD4000 (manufactured by FUJIFILM Imaging Colorants, yellow pigment dispersion, pigment concentration: 20% by mass)
• APD4000K Projet Black APD4000 (manufactured by FUJIFILM Imaging Colorants, black pigment dispersion, pigment concentration: 15% by mass)
• Image recording A Image recording is carried out in the order of application of a pretreatment liquid, drying, application of a cyan ink, application of a white ink, and drying.
• Image recording B Image recording is carried out in the order of application of a pretreatment liquid, drying, application of cyan ink, application of magenta ink, application of yellow ink, application of black ink, application of white ink, and drying.
• Image recording C Image recording is performed in the order of application of a pretreatment liquid, drying, application of a cyan ink, drying, application of a white ink, and drying.
• Image recording D Image recording carried out in the order of application of a pretreatment liquid, drying, application of a cyan ink, application of a magenta ink, application of a yellow ink, application of a black ink, drying, application of a white ink, and drying.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Ink Jet (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=92904695

Family Applications (1)

Country Status (5)

Citations (20)

• 2024
  • 2024-03-14 WO PCT/JP2024/010123 patent/WO2024203413A1/ja not_active Ceased
  • 2024-03-14 JP JP2025510480A patent/JPWO2024203413A1/ja active Pending
  • 2024-03-14 CN CN202480020381.1A patent/CN120981353A/zh active Pending
  • 2024-03-14 EP EP24779542.0A patent/EP4691788A1/en active Pending
• 2025
  • 2025-09-18 US US19/332,202 patent/US20260015517A1/en active Pending

Patent Citations (20)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events