Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/21—Ink jet for multi-colour printing
  • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
  • B41J2/211—Mixing of inks, solvent or air prior to paper contact
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
  • B41J3/407—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed for marking on special material
• • 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
• • 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
  • C09D11/02—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
  • C09D11/104—Polyesters
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

• the present invention relates to a pigment dispersion used for inkjet ink applications, an inkjet ink prepared using the pigment dispersion, and a printed matter subjected to inkjet printing using the inkjet ink.
• water-based inkjet inks have poorer blocking resistance and abrasion resistance that accompany set-off of printed patterns, and lamination strength when adhesive is applied to the printed surface and the film is laminated. There was a problem that it was still not enough. Moreover, these problems were more conspicuous when the base material was a film base material.
• Patent Document 1 discloses an inkjet ink that uses polycarbonate-based urethane resin particles having a minimum film-forming temperature of 25° C. or higher, and has good drying properties and abrasion resistance on nonporous substrates.
• Patent Document 1 no lamination strength test is performed, and further improvement in lamination strength is desired for development in package applications.
• the problems to be solved by the present invention are: a water-based inkjet ink excellent in blocking resistance, scratch resistance and lamination strength; a pigment dispersion capable of preparing the inkjet ink; Regarding printed matter.
• the binder (A) is a polyol (a1) containing a polyol (a1-1) having an acid group and a polyester polyol (a1-2) other than the polyol (a1-1), and a poly having a ring structure
• Some or all of the acid groups of the urethane resin (A1) are neutralized
• the “pigment dispersion for inkjet ink” (hereinafter sometimes simply referred to as “pigment dispersion” or “dispersion”) of the present invention comprises a binder (A), a pigment (B), and an aqueous medium (C). It contains Hereinafter, “binder (A)” may be referred to as “(A) component”, and other components may be referred to in the same way.
• the pigment dispersions of the invention are produced as intermediate products for inkjet inks and, after dilution, are used in inkjet printing as aqueous inkjet inks.
• the binder (A) contains a urethane resin (A1), and the urethane resin (A1) is a reaction product of polyol (a1) and polyisocyanate (a2).
• the urethane resin (A1) in the present invention is a resin obtained by reacting a polyol (a1) and a polyisocyanate (a2). It can be obtained by polymerizing components (a1) and (a2) in the presence of an arbitrary polymerization initiator using a known method such as radical polymerization.
• the resin (A1) having an acid group imparts hydrophilicity to the urethane resin (A1), making it possible to stably disperse the pigment (B) in water.
• the polyol (a1) in the present invention includes a polyol (a1-1) having an acid group and a polyester polyol (a1-2) other than the polyol (a1-1).
• the acid group includes a carboxyl group, a sulfonic acid group, a phosphoric acid group, a thiocarboxyl group and the like, and a carboxyl group or a sulfonic acid group is preferred.
• polyols having carboxyl groups include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Among them, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are preferred because of their good dispersion stability.
• a polyester polyol having a carboxyl group obtained by reacting a polyol having a carboxyl group with various polycarboxylic acids can also be used. These carboxyl group-containing polyols can be used alone or in combination of two or more.
• Examples of polyols having a sulfonic acid group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5-(4-sulfophenoxy)isophthalic acid, salts thereof, ethylene glycol and propylene.
• Polyester polyols obtained by reacting low-molecular-weight polyols such as glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and neopentyl glycol can be mentioned. These sulfonic acid group-containing polyols can be used alone or in combination of two or more.
• the polyol (a1-1) having an acid group is preferably used in a range in which the acid value of the urethane resin (A1) is 10 to 30 mgKOH/g, more preferably 10 to 28 mgKOH/g. .
• the acid value referred to in the present invention is a theoretical value calculated based on the amount of the acid group-containing compound such as the polyol (a1-1) having an acid group used in the production of the urethane resin (A1).
• the acid groups in the acid group-containing polyol (a1-1) are neutralized.
• Favorable water dispersibility can be expressed by partially or entirely neutralizing the acid groups.
• the method of neutralization is not particularly limited, examples thereof include neutralization using metals or organic amines.
• the metal used for neutralization is not particularly limited, but is preferably neutralized with metal ions such as sodium, potassium, calcium, copper and lithium to form a metal salt. Moreover, at least a part of the acid groups may be neutralized to form a metal salt.
• Metal ions such as sodium, potassium, calcium, copper, and lithium that can be used for neutralizing acid groups include metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and sodium chloride. , metal chlorides such as potassium chloride, and metal sulfides such as copper sulfate.
• Organic amines used for neutralization include polyalkyleneimines, polyallylamines, (poly)ethylenepolyamines, alkanolamines and alkylamines. Among these, alkylamines are preferred from the viewpoint of pigment dispersibility.
• the polyalkyleneimine is preferably a polyalkyleneimine having an alkylene group having 2 to 5 carbon atoms, more preferably a polyalkyleneimine having an alkylene group having 2 to 4 carbon atoms, still more preferably polyethyleneimine or Polypropyleneimine, particularly preferably polyethyleneimine. These may be used alone or in combination of two or more.
• the number average molecular weight of the polyalkyleneimine is preferably 150 or more, more preferably 500 or more, still more preferably 800 or more, still more preferably 1000 or more, and preferably 10000 or less, more preferably 5000 or less, still more preferably 4000 or less.
• polyallylamine examples include polymers having amino groups in side chains, such as homopolymers or copolymers of allyl compounds such as allylamine and dimethylallylamine.
• the weight average molecular weight of polyallylamine is preferably 800 or more, more preferably 1000 or more, still more preferably 1500 or more, and preferably 10000 or less, more preferably 5000 or less, still more preferably 4000 or less.
• (Poly)ethylenepolyamines include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like. Among these, ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferred, and ethylenediamine is particularly preferred.
• the alkanolamine is preferably an alkanolamine having 2 or more and 9 or less carbon atoms.
• alkanolamines include primary alkanolamines such as monoethanolamine, monopropanolamine and monobutanolamine; monoalkanol secondary amines such as N-methylethanolamine and N-methylpropanolamine; diethanolamine and diisopropanolamine; Secondary alkanolamines such as dialkanol secondary amines of; - tertiary alkanolamines such as dialkanol tertiary amines such as ethyldiethanolamine, and trialkanol tertiary amines such as triethanolamine and triisopropanolamine.
• tertiary alkanolamines having 2 to 9 carbon atoms are preferred, and triisopropanolamine is particularly preferred.
• the alkylamine is preferably an alkylamine having 1 or more and 6 or less carbon atoms.
• alkylamines include primary amines such as propylamine, butylamine and hexylamine; secondary amines such as diethylamine and dipropylamine; and tertiary amines such as triethylamine.
• the polyester polyol (a1-2) is a polyester polyol that does not correspond to the above polyol (a1-1).
• the polarity and Tg value are controlled by the presence of ester groups in the structure.
• the urethane resin (A1) can be imparted with appropriate flexibility and adhesion to the substrate, and as a result, lamination strength and abrasion resistance can be improved.
• the polyester polyol (a1-2) is a reaction product (polycondensate) obtained by a reaction (eg, polycondensation reaction) of a polyhydric carboxylic acid and a polyhydric alcohol, and the polyester polyol is derived from a polyhydric carboxylic acid. It has structural units and structural units derived from polyhydric alcohols.
• polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, adipic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
• polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, and tetraethylene.
• Glycols such as glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol , 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2- glycols having a branched structure such as ethyl-1,6-
• the polyester polyol (a1-2) preferably has a number average molecular weight in the range of 500 to 8,000, more preferably in the range of 800 to 7,000, since it has good compatibility with the pigment (B) and the like. is more preferred, and a range of 900 to 6,000 is even more preferred.
• the number average and weight average molecular weights are values measured by gel permeation chromatography (GPC).
• the polyol (a1) may contain polyols other than the acid group-containing polyol (a1-1) and the polyester polyol (a1-2).
• polyether polyols, polycarbonate polyols, and polyols having ring structures other than the above may be included.
• Polyisocyanate (a2) includes polyisocyanate (a2-1) having a ring structure.
• ring structures include cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctyl ring, propylcyclohexyl ring, tricyclo[5.2.1.0.2.6]decyl skeleton, bicyclo[4.3 .0]-nonyl skeleton, tricyclo[5.3.1.1]dodecyl skeleton, propyltricyclo[5.3.1.1]dodecyl skeleton, norbornene skeleton, isobornyl skeleton, dicyclopentanyl skeleton, adamantyl skeleton, etc. and aromatic ring structures such as benzene ring and naphthalene ring.
• polyisocyanate (a2-1) having an alicyclic structure examples include cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and the like.
• polyisocyanate (a2-1) having an aromatic ring structure examples include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene.
• polyisocyanates (a2-1) can be used alone or in combination of two or more.
• the polyisocyanate (a2) may contain an isocyanate compound (a2-2) other than the polyisocyanate (a2-1) having a ring structure.
• an isocyanate compound (a2-2) other than (a2-1) polyols having no ring structure, such as aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate, can be used in combination.
• the isocyanate (a2) is mixed and reacted at a reaction temperature of about 50°C to 150°C.
• the equivalent ratio of the isocyanate groups of the polyisocyanate (a2) to the hydroxyl groups of the polyol (a1) is in the range of 0.8 to 2.5. is preferably carried out in the range of 0.9 to 1.5.
• the urethane resin (A1) of the present invention necessarily has a ring structure derived from the polyisocyanate (a2-1) having a ring structure in the resin structure. Moreover, when the polyol (a1) has a polyol having a ring structure, the alicyclic structure derived therefrom also constitutes the urethane resin (A1). The urethane resin (A1) having an alicyclic structure can improve scratch resistance.
• the ring structure is preferably present in the range of 500 to 5000 mmol/kg, more preferably 600 to 4000 mmol/kg, still more preferably 800 to 3500 mmol/kg, and 800 to 2000 mmol/kg relative to the entire urethane resin (A1). /kg is particularly preferred.
• the ratio of the alicyclic structure contained in the urethane resin (A1) to the entire urethane resin (A1) referred to in the present invention is the polyol (a1) or polyisocyanate used in the production of the urethane resin (A1). It is a theoretical value calculated based on the total mass of all raw materials such as (a2) and the amount of the ring-structured substance contained in the ring-structure-containing compound used in the production of the urethane resin (A1).
• a chain extender can be used as needed.
• the chain extender include polyamines, hydrazine compounds, and other compounds having active hydrogen atoms. These chain extenders can be used alone or in combination of two or more.
• polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- diamines such as dimethyl-4,4′-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. Among these, piperazine or ethylenediamine is preferred.
• hydrazine compound examples include hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, and ⁇ -semicarbazide.
• hydrazine is preferred.
• Examples of other compounds having active hydrogen include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, glycols such as saccharose, methylene glycol, glycerin and sorbitol; Water etc. are mentioned.
• organic solvents examples include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetic acid ester solvents such as ethyl acetate and butyl acetate; nitrile solvents; amide solvents such as dimethylformamide and N-methylpyrrolidone; These organic solvents can be used alone or in combination of two or more.
• ketone solvents such as acetone and methyl ethyl ketone
• ether solvents such as tetrahydrofuran and dioxane
• acetic acid ester solvents such as ethyl acetate and butyl acetate
• nitrile solvents such as ethyl acetate and butyl acetate
• amide solvents such as dimethylformamide and N-methylpyrrolidone
• the glass transition temperature (Tg) of the urethane resin (A1) is 70°C or lower, preferably 50°C or lower, more preferably 40°C or lower. A Tg within this range provides good anti-blocking properties.
• the minimum film-forming temperature (MFT) of the urethane resin (A1) is preferably 40° C. or lower, more preferably 35° C. or lower, and 33° C. or lower from the viewpoint of lowering the drying temperature during the production of printed matter and improving energy efficiency. More preferred.
• the organic solvent is partially or wholly removed, for example, by distillation under reduced pressure during or after the production of the urethane resin (A1).
• the urethane resin (A1) obtained by the above method preferably has a mass average molecular weight in the range of 5,000 to 500,000, because it can express the durability of printed matter. It is more preferred to use those with weight average molecular weights in the range of 000, and even more preferred to use weight average molecular weights in the range of 20,000 to 100,000.
• the measurement of the weight average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) in the present invention was performed under the following conditions using an HLC8220 system manufactured by Tosoh Corporation. Separation column: 4 TSKgelGMHHR-N manufactured by Tosoh Corporation Mobile bed: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml/min. Sample concentration: 0.4% by mass Sample injection volume: 100 microliters. Detector: Differential Refractometer
• the mass-average molecular weight is 5,000 or more, not only is the durability of printed matter improved, but various problems such as blocking due to poor drying tend not to occur. In particular, it is preferable because problems such as a decrease in ink ejection property are unlikely to occur.
• the content (solid content) of the binder (A) is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 15% by mass, based on the total amount of the pigment dispersion.
• the binder (A) may consist of only the urethane resin (A1), or may contain other resins.
• the pigment (B) is not particularly limited as long as it can be dispersed well in the dispersion, but it is preferable to use one that can be dispersed with an average particle size of about 10 to 400 nm (details will be described later) ).
• organic pigments, inorganic pigments, and dyes used in general inks, paints, and recording agents can be used.
• organic pigments examples include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, ditopyrrolopyrrole, and isoindoline pigments. pigments. Copper phthalocyanine is preferably used for the indigo ink from the viewpoint of cost and light resistance.
• Inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, and mica (mica).
• a bright pigment Metalashine; Nippon Sheet Glass Co., Ltd. obtained by coating a metal or metal oxide on a base material of glass flakes or massive flakes can also be used. From the viewpoint of cost and coloring power, it is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for gold and silver inks, and mica for pearl ink.
• the pigment is preferably dispersed with a volume average particle diameter of 10 to 400 nm.
• the average particle size of the pigment can be measured by a known method such as a dynamic light scattering method in a state in which the pigment is uniformly dispersed in the dispersion after preparing the dispersion.
• the volume average particle size of the dispersion is preferably 10 to 300 nm, more preferably 50 to 200 nm, still more preferably 50 to 150 nm, and particularly preferably 50 nm or more and less than 100 nm.
• the volume average particle diameter is 50 nm or more, aggregation of the pigment during storage of the pigment dispersion can be suppressed.
• the volume average particle diameter is 400 nm or less (particularly preferably 100 nm or less), the ink jettability is improved.
• the content of the pigment in the dispersion is not particularly limited, it is preferably 10 to 30% by mass based on the total amount of the dispersion. If it is less than 10% by mass, there is a risk that sufficient ink coloring power cannot be obtained in an inkjet ink prepared by diluting the dispersion. If the amount is more than 30% by mass, the pigment may aggregate during transportation or storage of the dispersion, depending on the type of pigment. In addition, depending on the degree of dilution, there is a concern that the ink jettability may deteriorate.
• the pigment concentration is preferably 10 to 30 mass %, more preferably 10 to 25 mass % when the pigment is an organic pigment or carbon black.
• the pigment when an inkjet ink is prepared by dilution adjustment, it is possible to favorably achieve both ink coloring power and ink jettability.
• the pigment when the pigment is an inorganic pigment, it is preferably 25 to 60% by mass, more preferably 30 to 50% by mass.
• the pigment dispersion of the present invention further contains an aqueous medium in order to adjust the viscosity to suitable for pumping the dispersion and filtering the dispersion.
• the aqueous medium (C) include water, organic solvents miscible with water, and mixtures thereof.
• water-miscible organic solvents examples include alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of; and lactam solvents such as N-methyl-2-pyrrolidone.
• alcohol solvents such as methanol, ethanol, n-propanol and isopropanol
• ketone solvents such as acetone and methyl ethyl ketone
• polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol
• alkyl ethers of alkyl ethers of
• lactam solvents such as N-methyl-2-pyrrolidone.
• aqueous medium (C) water alone or a mixture of water and an organic solvent miscible with water is prefer
• the pigment dispersion of the present invention contains other optional components in addition to the above components (A), (B), and water (C) within a range that does not impair the effects of the present invention. good too.
• Other components include, for example, an amine compound having a boiling point of 100° C. or higher, resins other than the above components, surfactants, waxes, low surface tension organic solvents, wetting agents, penetrants, dispersants other than the above, antifoaming agents, Preservatives, viscosity modifiers, pH modifiers, chelating agents, plasticizers, antioxidants, UV absorbers and the like are included.
• Such amine compounds include polyalkyleneimines, polyallylamines, (poly)ethylenepolyamines, alkanolamines and alkylamines. Among these, alkanolamine is preferable from the viewpoint of pigment dispersibility, odor and re-solubility.
• the polyalkyleneimine is preferably a polyalkyleneimine having an alkylene group having 2 or more and 5 or less carbon atoms.
• the polyalkyleneimine is preferably a polyalkyleneimine in which the alkylene group has 2 or more and 4 or less carbon atoms, more preferably polyethyleneimine or polypropyleneimine, and still more preferably polyethyleneimine. These may be used alone or in combination of two or more.
• the number average molecular weight of the polyalkyleneimine is preferably 150 or more, more preferably 500 or more, still more preferably 800 or more, still more preferably 1,000 or more, and preferably 10,000 or less, more preferably 5,000 or more. 000 or less, more preferably 4,000 or less.
• the molecular weight value is determined by the method described in Examples.
• polyallylamine examples include polymers having amino groups in side chains, such as homopolymers or copolymers of allyl compounds such as allylamine and dimethylallylamine.
• the weight average molecular weight of polyallylamine is preferably 800 or more, more preferably 1,000 or more, still more preferably 1,500 or more, and preferably 10,000 or less, more preferably 5,000 or less, and still more preferably is 4,000 or less.
• polyethylene polyamine (polyethylene polyamine)
• Polyethylenepolyamines include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferred.
• alkanolamine is preferably an alkanolamine having 2 to 9 carbon atoms.
• alkanolamines include primary alkanolamines such as monoethanolamine, monopropanolamine and monobutanolamine; monoalkanol secondary amines such as N-methylethanolamine and N-methylpropanolamine; diethanolamine and diisopropanolamine; Secondary alkanolamines such as dialkanol secondary amines of; - tertiary alkanolamines such as dialkanol tertiary amines such as ethyldiethanolamine, and trialkanol tertiary amines such as triethanolamine and triisopropanolamine.
• tertiary alkanolamines having 2 to 9 carbon atoms are preferred, and triisopropanolamine is particularly preferred.
• alkylamine is preferably an alkylamine having 1 to 6 carbon atoms.
• alkylamines include primary amines such as propylamine, butylamine and hexylamine; secondary amines such as diethylamine and dipropylamine.
• resins may be aqueous resins suitable for preparing pigment dispersions, and preferred examples include acrylic resins such as polyvinyl alcohols, polyvinylpyrrolidones, acrylic acid-acrylic acid ester copolymers, and styrene.
• Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. Among these, anionic surfactants or nonionic surfactants is preferred.
• anionic surfactants include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfuric acid ester salts of higher fatty acid esters, sulfonates of higher fatty acid esters, and higher alcohol ethers. Sulfuric acid ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.
• Specific examples thereof include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, and dibutylphenylphenoldisulfonate.
• nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and glycerin fatty acid esters.
• polyoxyethylene glycerin fatty acid ester polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, alkylphenol ethoxylates, etc., among which polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ether , polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol,
• surfactants include silicon-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. spiculisporic acid, rhamnolipids, biosurfactants such as lysolecithin, and the like can also be used.
• surfactants can be used singly or in combination of two or more. Further, considering the dissolution stability and the like of the surfactant, the HLB is preferably in the range of 7-20.
• fluorosurfactants include Novec FC-4430, FC-4432 (manufactured by Sumitomo 3M), Zonyl FSO-100, FSN-100, FS-300, FSO (manufactured by DuPont), Ftop EF- 122A, EF-351, 352801, 802 (manufactured by Jemco), Megafac F-470, F-1405, F474, F-444 (manufactured by DIC), Surflon S-111, S-112, S-113, S121, S131 , S132, S-141, S-145 (manufactured by Asahi Glass), Futergent series (manufactured by Neos), Fluorad FC series (manufactured by Minnesota Mining and Manufacturing Company), Monflor (Imperial ⁇ chemical industry), Licowet VPF series (manufactured by Parkwerke Hoechst).
• silicone surfactants examples include KF-351A, KF-642, Olfine PD-501, Olfine PD-502, Olfine PD-570 (manufactured by Shin-Etsu Chemical), BYK347, and BYK348 (manufactured by BYK-Chemie Japan).
• Polyoxyethylene alkyl ether surfactants include BT series (Nikko Chemicals), Nonipor series (Sanyo Kasei), D-, P-series (Takemoto Oil), Emalex DAPE series (Nippon Emulsion), Pegnol series ( Toho Chemical Industry). Pegnol (Toho Kagaku Kogyo Co., Ltd.) is exemplified as a polyethylene glycol alkyl ester type.
• acetylene glycol-based surfactants examples include Olphine E1010, STG, Y (manufactured by Nissin Chemical Co., Ltd.), Surfynol 104, 82, 420, 440, 465, 485, and TG (manufactured by Air Products and Chemicals Inc.). mentioned.
• Waxes include, for example, plant and animal waxes such as carnauba wax, candy wax, beeswax, rice wax, and lanolin; mineral waxes such as montan wax and ozokerite; paraffin wax, which is so-called petroleum wax; carbon wax, Hoechst wax. , polyolefin wax, silicone wax, synthetic waxes such as stearic acid amide, natural and synthetic wax emulsions such as ⁇ -olefin/maleic anhydride copolymer, and waxes such as blended waxes. These waxes have the effect of imparting slip properties to the surface of the printed matter and improving the scratch resistance. These waxes can be used singly or in combination. Among these, silicone wax, polyolefin wax, paraffin wax and the like are preferably used.
• silicone waxes include, for example, SM8706EX, SM7036EX, SM7060EX, SM7025EX, SM490EX, SM8701EX, SM8709SR, SM8716SR, IE-7045, IE-7046T, SH7024, BY22-744EX, BY8FZ-X5, FZ-X5, FZ-8Z44E 4634EX, FZ-4602 (trade names, manufactured by Dow Corning Toray Co., Ltd.), POLON-MF-14, POLON-MF-14EC, POLON-MF-23 POLON-MF-63, POLON-MF-18T, POLON-MF -56, POLON-MF-49, POLON-MF-33A, POLON-MF-55T, POLON-MF-28T, POLONMF-50, POLON-MK-206, POLON-SR-CONC, KM-9771, KM-9774
• polyolefin waxes examples include waxes produced from olefins such as ethylene, propylene and butylene, or derivatives thereof, and copolymers thereof, specifically polyethylene waxes, polypropylene waxes, polybutylene waxes, and the like.
• Polyolefin waxes can be used singly or in combination of two or more.
• polyethylene-based waxes are preferable from the viewpoint of being less likely to react with the crosslinkable groups of the urethane resin particles having the above-mentioned crosslinkable groups and having excellent ejection stability.
• polyolefin waxes include, for example, AQUACER513 (polyethylene wax, average particle size 100 nm or more and 200 nm or less, melting point 130°C, solid content 30%), AQUACER507, AQUACER515, AQUACER840, AQUACER1547 (all trade names, BYK-Chemie Japan Co., Ltd.
• Paraffin wax is a so-called petroleum wax.
• paraffin means an alkane having 20 or more carbon atoms
• paraffin wax is mainly composed of linear paraffinic hydrocarbons having 20 or more and 30 or less carbon atoms, and a small amount of isoparaffin.
• the recorded matter is imparted with slipperiness and water repellency, thereby improving scratch resistance.
• Commercially available products of paraffin wax include, for example, AQUACER537 and AQUACER539 (both trade names, manufactured by BYK-Chemie Japan).
• the wax is preferably contained in the pigment dispersion in the form of fine particles, that is, in the form of emulsion or suspension. This makes it easier to adjust the viscosity of the ink so that it falls within an appropriate range for ejection using an inkjet head, and to ensure ejection stability and intermittent ejection characteristics during recording.
• low surface tension organic solvents such as glycol ether compounds
• diethylene glycol mono(alkyl having 1 to 8 carbon atoms) ether triethylene glycol mono(alkyl having 1 to 8 carbon atoms) ether
• propylene glycol mono(1 to 8 carbon atoms) C-6 alkyl) ethers dipropylene glycol mono(C 1-6 alkyl) ethers can be mentioned, and these can be used singly or as a mixture of two or more.
• ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl.
• Glycol ethers, surfactants, etc. can be used as surface tension modifiers to adjust the surface tension of the ink. Specifically, it can be added appropriately so that the surface tension of the ink is 15 mN/m to 30 mN/m or less, and the amount of the surfactant added is in the range of about 0.1 to 10% by mass with respect to the aqueous pigment dispersion. It is preferably 0.3 to 2% by mass, more preferably 0.3 to 2% by mass. More preferably, the surface tension is in the range of 16-28, most preferably in the range of 18-25.
• the wetting agent is not particularly limited, it is preferable to use a wetting agent that is miscible with water and that can prevent clogging of the ink jet printer head.
• a wetting agent that is miscible with water and that can prevent clogging of the ink jet printer head.
• glycerin ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,2-butane Diol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, 1, Diol compounds such as 2-heptanediol, 1,2-n
• penetrants examples include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether.
• the content of the penetrant in the pigment dispersion is preferably 0.01 to 10 mass %.
• the method for producing the pigment dispersion in the present invention is not limited at all.
• Components (A) to (C) and optionally added optional components may be dispersed to form a pigment dispersion, or a part of components (A), (B) and (C) may be prepared in advance.
• a pigment-dispersed millbase liquid having a high pigment concentration may be prepared using a medium or the like, optionally added with optional components, and diluted with an aqueous medium such as component (C) to obtain a pigment dispersion for preparing an aqueous inkjet ink.
• An aqueous pigment dispersion in which a pigment is dispersed with a desired volume average particle size can be easily obtained by preparing a pigment dispersion millbase liquid in advance by dispersing the pigment using a stirring/dispersing device and then preparing the pigment dispersion. be able to.
• the latter method of preparing a pigment-dispersed millbase liquid and then converting it into a pigment dispersion will be described below.
• Examples of the method for producing the pigment-dispersed millbase liquid include the following methods. (1) A method of adding a pigment to an aqueous medium containing a pigment dispersant as necessary, and then dispersing the pigment in the aqueous medium using a stirring/dispersing device to prepare a pigment-dispersed millbase liquid. (2) A pigment and, if necessary, a pigment dispersant are kneaded using a kneader such as a two-roll kneader or a mixer, the resulting kneaded product is added to an aqueous medium, and the pigment is dispersed using a stirring/dispersing device. A method for preparing a dispersed millbase liquor.
• stirring/dispersing device examples include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a Dyno mill, a dispermat, an SC mill, a nanomizer, and the like. may be used alone, or two or more types of devices may be used in combination.
• the pigment dispersion of the present invention is used and diluted with an aqueous medium so that the pigment content is 1 to 30% by mass to prepare an aqueous inkjet ink.
• This aqueous medium may be water, similar to component (C), a mixture of water and an organic solvent, or an organic solvent alone.
• the organic solvent is not particularly limited as long as it is miscible with water, and examples thereof include those mentioned above as optional components as the "solvent other than water”.
• optional components of the pigment dispersion for example, surfactants, preservatives, surface tension modifiers, etc.
• the inkjet ink of the present invention has excellent printing properties on various substrates, it is possible to suitably produce a printed material having a plastic substrate and a printed layer formed by the inkjet ink.
• plastic substrates include polyamide resins such as Ny6, nylon 66, and nylon 46; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; Polyhydroxycarboxylic acids such as polylactic acid; biodegradable resins typified by aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate); polyolefin resins such as polypropylene and polyethylene; Examples include plastic substrates made of thermoplastic resins such as polyimide resins, polyarylate resins, or mixtures thereof, and laminates thereof. Among them, substrates made of polyester, polyamide, polyethylene, polypropylene, and polyvinyl chloride are preferred. Available.
• the plastic substrate may be a plastic film.
• the plastic film may be either an unstretched film or a stretched film, and its production method is not limited.
• the thickness of the film is not particularly limited, but it is usually in the range of 1 to 500 ⁇ m.
• the printing surface of the film is subjected to a corona discharge treatment.
• silica, alumina, or the like may be vapor-deposited on the printed surface.
• the printed matter of the present invention has good printability on plastic substrates and can be produced by inkjet printing, so it can be suitably used as a packaging material.
• it is excellent in designability and on-demand printability, so it can be used particularly preferably for food packaging.
• the inkjet ink of the present invention is excellent in abrasion resistance, it can be used as a surface-printed matter in which the surface to be the front surface is subjected to inkjet printing.
• part means “mass part”
• % means “mass%” unless otherwise specified.
• Binders (1) to (3) and comparative binders (1) to (5) used in this example are shown below.
• aqueous pigment dispersion for preparation of aqueous inkjet ink Various water-based pigment dispersions were obtained according to the following composition by adjusting the pigment concentration in the water-based pigment dispersion to 30% by weight.
• the binder the binder of each example described above was used in an amount such that the solid content of each binder was 10.5% by mass based on the total amount of the pigment dispersion.
• Pigment kneaded meat base 50.0 parts
• Aqueous medium (B) 10.0 parts Water balance
• ⁇ Blocking resistance evaluation> Cut the film into 4 cm x 4 cm size so that the printed surface and the non-printed surface of the printed matter are in contact with each other, stack them, apply a load of 5 kgf/cm 2 , leave them in an environment of 50 ° C for 24 hours, and then remove the film.
• the state of ink transfer (set-off) to the non-printed surface when peeled off was visually evaluated based on the area ratio (%) of the set-off portion.
• x Transfer due to set-off of 10% or more is observed.
• Laminate evaluation was performed according to JIS Z 1707:2019. Specifically, it is as follows.
• OPP film A heat-sealing adhesive was formulated by mixing aromatic-ether adhesives (LX401 and SP60, both manufactured by DIC) and diluting with ethyl acetate to a non-volatile content of 25%. Adhesive was applied to the printed surface of the OPP film so as to be 2 g/m 2 , and a CCP film (pylen film-CT P1128, manufactured by Toyobo Co., Ltd.) was laminated with a heated roller lamination tester set at 40 ° C. . After that, curing was performed at 40° C.
• a test piece having a width of 10.0 ⁇ 0.1 mm and a developed length of 100 mm or more in a perpendicular direction was taken from the produced laminate film.
• the test piece was opened at 180° with the laminated part of the test piece in the center, and both ends of the test piece were attached to the grips of a constant-speed elongation type tensile tester with an interval of 50 mm or more between the grips.
• a tensile load was applied until the laminate was broken, and the maximum load (N/10 mm) during that period was determined, and the laminate strength was evaluated according to the criteria shown below.
• ⁇ Scratch resistance> In accordance with JIS K5701-1:2000, the abrasion resistance of the printed OPP film was evaluated using a Gakushin type rubbing fastness tester (manufactured by Tester Sangyo Co., Ltd., AB-301). The printed matter was set in the tester, and the dry friction test was performed using PPC paper as the friction paper, a load of 200 g, and 100 reciprocations. The test was conducted under the conditions of After the test, the degree of ink peeling on the printed matter was visually evaluated according to the following evaluation criteria. A: No peeling occurred in both the dry friction test and the wet friction test. ⁇ : Less than 1% of peeling occurred in either the dry friction test or the wet friction test, whichever is worse.
• ⁇ 1% or more and less than 5% of peeling occurred in either the dry rubbing test or the wet rubbing test, whichever is worse.
• x 5% or more and less than 10% of peeling occurred in either dry friction test or wet friction test, whichever is worse.
• ⁇ Storage stability evaluation> Particle size/viscosity change
• Each ink was stored in a constant temperature bath at 70° C. for 5 days and subjected to an accelerated storage stability test.
• the ink before and after the accelerated storage stability test was measured with a nanoparticle size measuring device (Nanotrac wave II Ex150, manufactured by Microtrac Bell Co., Ltd.), and the average particle size before and after the accelerated storage stability test was compared.
• the inks before and after the accelerated storage stability test were measured with an E-type viscometer (TVE-25L model, manufactured by Toki Sangyo Co., Ltd.), the viscosities before and after the accelerated storage stability test were compared, and evaluated on a three-grade scale from A to C.
• a grade of B or above is acceptable.
• the inkjet inks of Examples 1 to 3 according to the present invention are excellent in blocking resistance and abrasion resistance to plastic substrates, and are excellent in lamination when an adhesive is applied to the printed surface and the film is laminated. It was confirmed that the strength was exhibited.
• the water-based inkjet inks of Comparative Examples 1-5 were inferior in any of the properties, unlike the inks of Examples 1-3. Therefore, it was confirmed that the pigment dispersion of the present invention can be suitably used for water-based inkjet inks.

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