JP6573053B1 - Ink, inkjet recording ink and printed matter - Google Patents

Abstract

The problem to be solved by the present invention is that even when the ink jet printing method is adopted, it has excellent ejection stability and hardly absorbs the solvent contained in the ink, for example, various resin films, coated papers, etc. It is an object of the present invention to provide an ink that has excellent setting properties with respect to a non-ink-absorbing recording medium and a recording medium that is difficult to absorb ink, and that can be used for the production of high-gloss printed matter. The present invention relates to an ink comprising a medium saccharified and reduced candy and an aqueous medium.

Description

  The present invention relates to an ink that can be used in the production of printed matter.

  Ink jet printers are widely used in homes and offices for printing on plain paper.

  On the other hand, in the industry, a method of printing on packaging materials and advertising media using an ink jet printer is being studied. Examples of the packaging material and the advertising medium include non-ink-absorbing recording media made of a resin film such as an olefin resin film and a polyethylene terephthalate resin film, and difficult to be coated paper having a coating layer on the surface thereof. Absorbent recording media may be mentioned.

  However, since the non-ink-absorbing or hardly-absorbing recording medium hardly absorbs the solvent contained in the ink, unlike the plain paper, the conventional ink used for printing on the plain paper is used as the ink. Even when diverted to printing on a non-absorbing or hardly absorbing recording medium, a clear image may not be formed.

  Examples of the ink that can be used for printing on the non-absorbing or hardly-absorbing recording medium and that can reduce the environmental load caused by an organic solvent and the like include, for example, a pigment, an alkali-soluble resin, a wax emulsion, and a basic A water-based inkjet ink composition comprising a compound, an aqueous medium, and a surfactant, wherein the wax emulsion has an average particle diameter of 150 to 200 nm, and the wax emulsion has a solid content of aqueous. There is known an aqueous ink-jet ink composition that is 0.5 to 4% by mass in the ink-jet ink composition and in which the surfactant is an acetylenic diol surfactant (see, for example, Patent Document 1).

  However, when an ink composition is continuously printed on the non-absorbing or hardly absorbing recording medium to produce a printed material, the printed surface of the printed material and the back surface of another printed material come into contact with each other. The ink is transferred from the printing surface to the back surface, and as a result, the printed image may be peeled off or the recording medium may be broken. A printed matter having this problem is generally considered to have insufficient setability, and has been a big problem when continuously producing the above-described advertising media and the like.

  As a method for improving the setting property, a method is known in which an additive or the like for improving the drying property of the printing surface is used for the ink.

  However, depending on the type of the additive, there are cases where the ejection stability is lowered when the ink is ejected by the ink jet recording method, the gloss of the printed matter is lowered, and the like.

International publication 2015/111644 pamphlet

  The problem to be solved by the present invention is that it has excellent setting properties with respect to a recording medium which is difficult to absorb the solvent contained in the ink, for example, a non-ink-absorbing or hardly-absorbing recording medium such as various resin films and coated paper. It is another object of the present invention to provide an ink that can be used to produce a high-gloss printed matter.

  Further, the problem to be solved by the present invention is that, even when the ink jet printing method is adopted, it has excellent ejection stability and hardly absorbs the solvent contained in the ink, for example, various resin films and coatings. An object of the present invention is to provide an ink that has excellent setting properties for a non-ink-absorbing or hardly-absorbing recording medium such as paper and can be used for the production of high-gloss printed matter.

  The present inventor has solved the above problems with an ink characterized by containing medium saccharified and reduced candy and an aqueous medium.

  The ink of the present invention hardly absorbs the solvent contained in the ink, and does not easily absorb the solvent contained in the ink without impairing the excellent ejection stability even when the ink jet printing method is employed. It has excellent setting properties for non-ink-absorbing or hard-absorbing recording media such as films and coated papers, and can be used for the production of printed materials with high gloss.

  In addition, since the ink of the present invention can form a crosslinked coating film even when dried in a room temperature environment in the range of about 5 ° C. to 60 ° C., the ink may be deformed due to the influence of heat when drying the printed matter. Even when printing is performed on a recording medium such as a resin film that easily causes discoloration, it is possible to obtain a printed material with excellent setability and high gloss.

  The ink of the present invention is characterized by containing medium saccharified and reduced water candy and an aqueous medium.

  First, medium saccharification and reduction candy is explained.

  The medium saccharified and reduced candy is generally used for the purpose of improving the moisture retention and storage stability of foods and cosmetics. In the present invention, by containing the medium saccharified reduced starch candy in the ink, the moisture retention of the nozzle part when printing by the ink jet printing method is improved, and as a result, the discharge stability and the setability are excellent, and the high gloss Ink that can be used in the production of printed matter can be obtained.

  Reduced water candy refers to a product obtained by reducing (hydrogenating) glucose or the like contained in water candy.

  Examples of the reduced water candy include monosaccharide sugar alcohols obtained by reducing the terminal structure of glucose, disaccharide alcohols, trisaccharide alcohols, tetrasaccharide alcohols, polysaccharide sugar alcohols such as pentasaccharide or higher alcohols, and the like. In general, a mixture of two or more can be used.

  Reduced water candy is generally classified into high saccharified and reduced water candy, medium saccharified and reduced water candy, and low saccharified and reduced water candy according to the saccharification degree of the raw water candy. In the present invention, medium saccharified and reduced water candy is used.

  High saccharified and reduced candy is generally 80% by mass or more of monosaccharide alcohol and disaccharide alcohol based on the total amount of saccharified and reduced candy. The total of the sugar alcohols having 5 or more sugars is 50% by mass or more. Therefore, as the medium saccharified and reduced water candy, it is preferable to use one other than the above-mentioned high saccharified and reduced water candy.

  More specifically, as the medium saccharified and reduced water candy, the total content of monosaccharide alcohol and disaccharide alcohol with respect to the total amount of medium saccharified and reduced water candy is preferably 0.5% by mass or more and less than 80% by mass, more preferably 0%. The total content of sugar alcohols of 5 or more sugar sugars and 5 or more sugars is preferably 0.5 to 50% by weight, more preferably 0.5 to 40% by weight. % Or less.

  As the medium saccharified and reduced syrup, the content ratio of monosaccharide sugar alcohol to the total amount of saccharified and reduced syrup is preferably 0.1% by mass to 15% by mass, more preferably 0.1% by mass to 10% by mass. And the content rate of a disaccharide alcohol becomes like this. Preferably it is 0.1 to 65 mass%, More preferably, it is 0.1 to 60 mass%.

  The content ratio of the trisaccharide sugar alcohol to the total amount of the medium saccharified and reduced starch candy is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 55% by mass. The content ratio of the tetrasaccharide sugar alcohol to the total amount of the medium saccharified and reduced candy is preferably 0.1% by mass to 30% by mass, and more preferably 0.5% by mass to 13% by mass.

  More specifically, the medium saccharified and reduced water candy may use maltitol as a disaccharide alcohol, maltotriitol as a trisaccharide alcohol, maltotetriitol as a tetrasaccharide alcohol, or the like. it can.

  As the medium saccharified and reduced water candy, for example, the one having a large mass ratio of disaccharide alcohol and trisaccharide alcohol has the effect of achieving both the ability to set a hardly absorbable recording medium and the inkjet discharge stability. Particularly preferred.

  The medium saccharified and reduced water candy is preferably used in a range of 1% by mass to 10% by mass, and preferably used in a range of 3% by mass to 7% by mass with respect to the total amount of the ink. It is excellent in setting properties on a recording medium and ejection stability, and is more preferable for producing a high gloss printed matter.

(Aqueous medium)
The ink of the present invention uses an ink containing an aqueous medium as a solvent in addition to the medium saccharified and reduced water candy.

  As the aqueous medium, water alone or a mixed solvent of water and a water-soluble organic solvent described later can be used.

  Specifically, pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water can be used as the water.

  Examples of the water-soluble organic solvent include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-methoxy Alcohols such as ethanol; ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; dimethylformamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene Glycols such as glycol and polypropylene glycol; diols such as butanediol, pentanediol, hexanediol and diols of the same family; propylene laurate Glycol esters such as diethylene glycol; glycol ethers such as diethylene glycol monoethyl, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; methanol, ethanol, isopropyl alcohol , Alcohols such as 1-propanol, 2-propanol, butyl alcohol such as 1-butanol and 2-butanol, pentyl alcohol, and alcohols homologous thereto; sulfolane; lactones such as γ-butyrolactone; N- (2- Lactams such as hydroxyethyl) pyrrolidone can be used alone or in combination of two or more.

  In addition to the above-mentioned water-soluble organic solvents, the water-soluble organic solvent has a boiling point of 100 ° C. or higher and 200 ° C. or lower and a vapor pressure at 20 ° C. of 0.5 hPa or higher in order to improve the quick drying property of the ink. Organic solvents can be used.

  Examples of the water-soluble organic solvent having a boiling point and a vapor pressure in the above ranges include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, 4-methoxy-4-methyl-2-pentanone, ethyl lactate and the like, may be used in combination with one of the two or more.

Among the water-soluble organic solvents, HSP (Hansen Solubility) is used to maintain good dispersion stability of the ink and to suppress deterioration due to the influence of the solvent contained in the ink, for example, of the ink discharge nozzle provided in the ink jet apparatus. It is preferable to use a water-soluble organic solvent in which the hydrogen bond term δ _H of parameter) is in the range of 6-20.

  Specific examples of the water-soluble organic solvent having a hydrogen bond term of HSP in the above range include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol monomethyl ether, ethylene glycol mono Preferred are ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, more preferably 3 -Methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol.

  As an aqueous medium, in order to ensure good ejection stability when the ink of the present invention is printed by the ink jet printing method, glycerin, diglycerin and / or an organic solvent that is a derivative thereof includes glycerin, diglycerin, Polyglycerin, diglycerin fatty acid ester, polyoxypropylene (n) polyglyceryl ether represented by general formula (1), polyoxyethylene (n) polyglyceryl ether represented by general formula (2), and the like can be used. . Two or more of these may be used simultaneously. In the present invention, it is particularly preferable to select glycerin and polyoxypropylene (n) polyglyceryl ether of n = 8-15.

  M, n, o and p in the general formula (1) and the general formula (2) each independently represent an integer of 1 to 10.

  The ink of the present invention uses an ink containing a solvent (D) having a polarity term of Hansen solubility parameter of 7 or more and a hydrogen bond term of 15 or more as the aqueous medium. This is preferable because it is excellent in terms of good discharge stability at the level required in some cases.

  As the solvent (D), the polar term is preferably in the range of 7 to 15, more preferably in the range of 7 to 12, and the hydrogen bond term is preferably in the range of 15 to 30, more preferably in the range of 17 to 22. Is preferably used in order to obtain an ink having excellent level of ejection stability required when ejected by an inkjet method.

  Examples of the solvent (D) include 1,2-propanediol, 1,2-hexanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 3-methyl-1, One or a combination of two or more of 5-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, or 3-methyl-1,4-butanediol can be used. .

  Among these, as the solvent (D), 1,2-propanediol, 1,2-hexanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 3-methyl At least one selected from the group consisting of -1,5-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol and 3-methyl-1,4-butanediol; It is more preferable to use a combination of these in order to reduce damage to the ink jet head and improve the wettability of the ink to the recording medium, and as a result, to further improve the setability and adhesion.

  The solvent (D) is preferably included in the range of 15% by mass to 40% by mass, and preferably included in the range of 15% by mass to 25% by mass with respect to the total amount of the ink of the present invention. This is preferable because it is excellent in terms of good ejection stability at the level required for ejection.

  The aqueous medium such as the solvent (D) is preferably used in the range of 15% by mass to 50% by mass with respect to the total amount of the ink of the present invention, and is preferably used in the range of 15% by mass to 30% by mass. It is more preferable because it is excellent in setability, has a good ejection property required for ejection by an inkjet method, and can be used for production of a clear printed matter.

(Binder (A))
As the ink of the present invention, in addition to the medium saccharified and reduced candy and the aqueous medium, an ink containing a binder may be used as necessary.

  As said binder (A), an acrylic resin, a urethane resin, an epoxy resin, polyolefin, modified polyolefin, an amide resin etc. can be used, for example. Among them, it is preferable to use an acrylic resin as the binder (A) in order to increase the fastness of the printed matter.

  As the acrylic resin, for example, a water-dispersible acrylic resin, a water-soluble acrylic resin, or the like can be used. When the ink of the present invention is a water-based ink, it is possible to use a water-dispersible acrylic resin. It is preferable because good ejection stability can be imparted when the ink of the invention is applied to inkjet printing.

  As said acrylic resin, what is obtained by polymerizing a monomer component can be used, for example.

  Examples of the monomer include (meth) acrylic acid and alkali metal salts thereof, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate. , (Meth) acrylic acid ester monomers such as cyclohexyl (meth) acrylate, acrylic monomers having an amide group such as N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile Acrylic monomers such as 2-dimethylaminoethyl (meth) acrylate and glycidyl (meth) acrylate, aromatic vinyl compounds such as styrene, α-methylstyrene, p-tert-butylstyrene, vinylnaphthalene and vinylanthracene, Vinyl sulfonic acid, styrene sulfonic acid Vinyl sulfonic acid compounds such as 2-vinylpyridine, 4-vinylpyridine, vinylpyridine compounds such as naphthylvinylpyridine, vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like can be used.

  Examples of the polymerization method of the monomer include a solution polymerization method and an emulsion polymerization method, and it is preferable to employ an emulsion polymerization method.

  In addition, the ink of the present invention contains the binder (A) and a compound (B) to be described later in combination in order to obtain an ink having more excellent setting properties and adhesion to a recording medium. It is preferable to use an ink. At that time, as the binder (A), it is preferable to use a binder having a functional group capable of reacting with the compound (B), and it is more preferable to use a binder (a) having a carbonyl group. .

  Specific examples of the carbonyl group include an aldehyde group, a ketone group, an amide group, and a carboxyl group, and a ketone group is preferable.

  The carbonyl group reacts with the functional group of the compound (B) after the ink of the present invention is printed on the surface of the recording medium and the solvent in the ink volatilizes. Thereby, the ink provided with the outstanding set property and adhesiveness can be obtained.

  Examples of the binder (a) include an acrylic polymer having an aldehyde group, an acrylic polymer having a ketone group, an acrylic polymer having an amide group, an acrylic polymer having a carboxyl group, and the like. In general, it is preferable to use a polymer in order to impart even more excellent adhesion to a recording medium such as a hardly adherent polyolefin film or polyethylene film.

  When producing the binder (a), it is preferable to use a monomer having a carbonyl group as the monomer. Examples of the monomer having a carbonyl group include diacetone acrylamide and 2-acetoacetoxy. Ethyl methacrylate or the like can be used, and diacetone acrylamide is preferably used in order to further improve the adhesion to the recording medium.

  As the binder (A), a so-called core-shell type polymer can be used. As the core-shell type polymer, it is preferable to use a polymer having the carbonyl group in one or both of the core part and the shell part.

  As the core-shell type polymer, among the above-mentioned, it is more excellent to use the core-shell type polymer having a carbonyl group such as an amide group in the core part for the hard-to-adhere recording medium. It is preferable to obtain an ink having excellent adhesion and excellent ejection stability required when ejected by an inkjet method.

  More specifically, as the core-shell type polymer, a core-shell type acrylic polymer having a core part containing an acrylic polymer of a monomer component containing diacetone acrylamide and a shell part containing an arbitrary acrylic polymer Is preferably used in order to obtain an ink having an even higher level of ejection stability required for ejection by an inkjet method.

  As the binder (A), those having a glass transition temperature in the range of −12 ° C. to 25 ° C. are preferably used, and those having a glass transition temperature in the range of 8 ° C. to 25 ° C. are used. This is particularly preferable for obtaining an ink having much better adhesion to a medium and excellent ejection stability required when ejected by an inkjet method.

  The binder (A) is preferably used in the range of 1% by mass to 10% by mass, and preferably in the range of 3% by mass to 6% by mass, based on the total amount of the ink of the present invention. In particular, it is preferable to obtain an ink having more excellent adhesion to a recording medium having a high recording property.

(Compound (B))
As said compound (B), what has a structure which can react with the functional group including the carbonyl group which the said binder (A) has can be used.

  The ink containing the compound (B) is landed on the surface of the recording medium, and after the solvent such as an aqueous medium contained in the ink is volatilized, the carbonyl group of the binder (A) and the compound (B ) Are cross-linked by dehydration condensation or the like, and fixed on the surface of the recording medium. Thereby, the printed matter excellent in set property and adhesiveness can be obtained.

  Examples of the structure include a hydrazine structure, a hydrazino structure, and the like. A hydrazine structure is preferable in obtaining an ink having excellent adhesion to the recording medium and setability.

  Specific examples of the compound (B) include adipic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, isophthalic acid dihydrazide, salicylic acid dihydrazide, and the like. It is preferable for obtaining an ink having excellent adhesion.

  The compound (B) is preferably used in the range of 0.003% to 0.5% by weight, and in the range of 0.01% to 0.5% by weight, based on the total amount of the ink of the present invention. It is preferable to use it for further excellent adhesion to a substrate.

  Moreover, when using the said compound (B) in the range of 0.1 mass%-5 mass% with respect to the whole quantity of the said binder (A), there exists the further excellent adhesiveness to a base material. preferable.

  The mass ratio [binder (A) / compound (B)] of the binder (A) having a functional group such as a carbonyl group and the compound (B) should be used in a range of 20/1 to 1000/1. It is more preferable to use the ink in a range of 100/1 to 500/1 in order to obtain an ink having further excellent setability.

(Color material)
As the ink of the present invention, an ink containing a coloring material can be used as necessary.

  As the coloring material, pigments, dyes, and the like can be used. Among them, it is preferable to use a pigment in producing a printed matter excellent in weather resistance and the like.

  As the pigment, for example, an organic pigment or an inorganic pigment can be used.

  Further, as the pigment, non-acid-treated pigments, acid-treated pigments, and pigments coated with a resin can also be used.

  As the inorganic pigment, for example, iron oxide, carbon black produced by a method such as a contact method, a furnace method, or a thermal method can be used.

  Examples of the organic pigment include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), lake pigments (eg, basic dye-type chelates, acidic dye-type chelates), nitro pigments, nitroso pigments, aniline black, and the like can be used.

  Among the pigments, carbon black that can be used for black ink includes No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 960, no. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MA7, MA8, MA100, etc. are Columbia-made Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc., Cabot Regal 400R, Regal 330R, Regal 660R, Mulul 6000R , Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc., Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, P160 V, 1400U, Special Black 6, 5, 4, 4A, NIPEX 150, NIPEX 160, NIPEX 170, NIPEX 180, etc. can be used.

  Specific examples of pigments that can be used for yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.

  Specific examples of pigments that can be used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, 269, 282 Et al., C.I. I. Pigment violet 19 and the like.

  Specific examples of pigments that can be used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66, and the like.

  Specific examples of pigments that can be used in white ink include silicas such as alkaline earth metal sulfates, carbonates, finely divided silicic acid, synthetic silicates, calcium silicates, alumina, alumina hydrates, Examples thereof include titanium oxide, zinc oxide, talc, and clay. These may be surface-treated.

  In order for the pigment to be stably present in the ink, it is preferable to provide a means for satisfactorily dispersing in the aqueous medium.

Examples of the means include (i) a method of dispersing a pigment in an aqueous medium by a dispersion method described later together with a pigment dispersant (ii) a dispersibility-imparting group (hydrophilic functional group and / or salt thereof) on the surface of the pigment. And a method of dispersing and / or dissolving a self-dispersing pigment in which is bonded directly or indirectly through an alkyl group, an alkyl ether group, an aryl group or the like in an aqueous medium.

  As the self-dispersing pigment, for example, a pigment obtained by subjecting a pigment to a physical treatment or a chemical treatment and binding (grafting) an active species having a dispersibility-imparting group or a dispersibility-imparting group to the surface of the pigment is used. be able to. Examples of the self-dispersing pigment include a vacuum plasma treatment, an oxidation treatment with hypohalous acid and / or hypohalite, or an oxidation treatment with ozone, or a wet oxidation method in which the pigment surface is oxidized with an oxidizing agent in water. Alternatively, it can be produced by a method in which a carboxyl group is bonded via a phenyl group by bonding p-aminobenzoic acid to the pigment surface.

  Since the water-based ink containing the self-dispersing pigment does not need to contain the pigment dispersant, there is almost no foaming due to the pigment dispersant, and it is easy to prepare an ink excellent in ejection stability. In addition, water-based inks containing self-dispersing pigments are easy to handle and can contain a larger amount of pigments because of the significant increase in viscosity caused by the pigment dispersant, making it possible to produce printed matter with high print density. Can be used for

  Commercially available products can be used as the self-dispersing pigment. Examples of such commercially available products include Microjet CW-1 (trade name; manufactured by Orient Chemical Industries, Ltd.), CAB-O-JET200, CAB-O-JET300 (above, trade name: manufactured by Cabot Corporation) may be mentioned.

  The colorant is preferably used in the range of 1% by mass to 20% by mass, and preferably in the range of 2% by mass to 10% by mass with respect to the total amount of the ink. It is preferable for further improving the dispersion stability of the coloring material.

(Pigment dispersant)
The pigment dispersant can be suitably used when a pigment is used as the color material.

  Examples of the pigment dispersant include acrylic resins such as polyvinyl alcohols, polyvinyl pyrrolidones, and acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-methacrylic acid. -Styrene-acrylic resins such as acrylate copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer A polymer, a styrene-maleic anhydride copolymer, a vinyl naphthalene-acrylic acid copolymer aqueous resin, and a salt of the aqueous resin can be used. Examples of the pigment dispersant include Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BASF EFKA series, Nippon Lubrizol Corporation SOLPERSE series, Evonik Co., Ltd. The TEGO series can be used.

  As the pigment dispersant, a block polymer or a random polymer can be used. Moreover, what was manufactured by the living anion polymerization method or the living radical method can be used as said block polymer. Specifically, it is preferable to use those represented by the general formula 1.

  Specifically, the polymer produced by living anionic polymerization is a polymer represented by the general formula (3).

In General Formula (3), A ¹ represents an organolithium initiator residue, A ² represents a polymer block of a monomer having an aromatic ring or a heterocyclic ring, A ³ represents a polymer block containing an anionic group, n Represents an integer of 1 to 5, and B represents an aromatic group or an alkyl group.

In the general formula (3), A ¹ represents an organic lithium initiator residues. Specific examples of the organic lithium initiator include methyl lithium, ethyl lithium, propyl lithium, butyl lithium (n-butyl lithium, sec-butyl lithium, iso-butyl lithium, tert-butyl lithium, etc.), pentyl lithium, hexyl lithium, Alkyllithium such as methoxymethyllithium and ethoxymethyllithium; phenylalkylenelithium such as benzyllithium, α-methylstyryllithium, 1,1-diphenyl-3-methylpentyllithium, 1,1-diphenylhexyllithium and phenylethyllithium Alkenyl lithium such as vinyl lithium, allyl lithium, propenyl lithium, butenyl lithium; ethynyl lithium, butynyl lithium, pentynyl lithium, hexynyl lithium, etc. Alkylithium such as phenyllithium and naphthyllithium; Heterocyclic lithium such as 2-thienyllithium, 4-pyridyllithium and 2-quinolyllithium; Alkyl such as tri (n-butyl) magnesiumlithium and trimethylmagnesiumlithium Examples include lithium magnesium complex.

In the general formula (3), A ² represents a polymer block having a hydrophobic group. A ² is preferably a group having high adsorption to the pigment when it comes into contact with the pigment, in addition to the purpose of balancing an appropriate balance of solubility as described above, and A ² has an aromatic ring or a heterocyclic ring. A monomer polymer block is preferred.
Specifically, the polymer block of a monomer having an aromatic ring or a heterocycle refers to homopolymerization or copolymerization of a monomer having an aromatic ring such as a styrene monomer or a monomer having a heterocycle such as a vinylpyridine monomer. It is a polymer block of the homopolymer or copolymer obtained in this way.

  Examples of the monomer having an aromatic ring include styrene, p-tert-butyldimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-tert-butoxystyrene, m-tert-butoxystyrene, Styrene monomers such as p-tert- (1-ethoxymethyl) styrene, m-chlorostyrene, p-chlorostyrene, p-fluorostyrene, α-methylstyrene, p-methyl-α-methylstyrene, and vinylnaphthalene And vinyl anthracene.

  Moreover, as a monomer which has a heterocyclic ring, vinyl pyridine-type monomers, such as 2-vinyl pyridine and 4-vinyl pyridine, can be used individually or in combination of 2 or more types, for example.

In the general formula (3), A ³ represents a polymer block containing an anionic group. A ³ is another object to provide a described above moderate solubility, there is a purpose of imparting dispersion stability in water when a pigment dispersion.
Examples of the anionic group in the polymer block A ³ include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Of these, a carboxyl group is preferred because of its preparation and the availability of monomer varieties. Two carboxyl groups may be acid anhydride groups obtained by dehydration condensation within a molecule or between molecules.

  In addition to the above components, the ink of the present invention includes a binder having no carbonyl group, a wetting agent (drying inhibitor), a penetrating agent, an antiseptic, a viscosity adjusting agent, a pH adjusting agent, a chelating agent, as necessary. What contains other additives, such as a plasticizer, antioxidant, and an ultraviolet absorber, can be used.

  Examples of the binder having no carbonyl group include polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, polyolefin resin, acrylic resin, urethane resin, dextran, dextrin, color ginan (κ, ι, λ, etc.), agar, Pullulan, water-soluble polyvinyl butyral, hydroxyethyl cellulose, carboxymethyl cellulose and the like can be used alone or in combination of two or more.

  The wetting agent can be used for preventing the ink from being dried and fixed by an ink discharge nozzle. The wetting agent is preferably 3% by mass to 50% by mass with respect to the total amount of the ink of the present invention.

  Examples of the wetting agent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, dipropylene glycol, tripropylene glycol, mesoerythritol, pentaerythritol, urea, ethylene urea, 2-hydroxyethyl urea, and the like. It is done.

  Examples of the penetrant 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 is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably substantially not contained with respect to the total amount of the ink of the present invention.

  The surfactant can be used to improve the leveling property of the ink by, for example, reducing the surface tension of the ink of the present invention.

  The surfactant is not particularly limited, and includes various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Of these, nonionic surfactants and nonionic surfactants are preferred.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol ether. Sulfate salts and sulfonates of the above, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples include dodecylbenzene sulfonate, isopropyl naphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfate. , And the like salts.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Polyethylene glycol polypropylene glycol block copolymer, etc. Among them, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid Preferred are alkylolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymer. Of these, acetylene glycol and an oxyethylene adduct of acetylene glycol are more preferable because the contact angle of the ink droplets with respect to the recording medium can be reduced and a good printed matter can be obtained.

  Other surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. Agents: Biosurfactants such as spicrispolic acid, rhamnolipid, and lysolecithin can also be used.

  These surfactants can be used alone or in combination of two or more. In consideration of the dissolution stability of the surfactant, the HLB is preferably in the range of 7-20.

  The surfactant is preferably used in the range of 0.001% by mass to 2% by mass, more preferably in the range of 0.001% by mass to 1.5% by mass, based on the total mass of the ink. The use in the range of 0.01% by mass to 1% by mass is more preferable for obtaining an ink capable of producing a printed matter having much more excellent setting properties and wear resistance.

(Ink production method)
In the ink of the present invention, the medium saccharified and reduced water candy and the aqueous medium are mixed with optional components such as a binder (A), the compound (B), a solvent (D), a colorant, and a pigment dispersant as necessary. Can be manufactured by.

  In the mixing, for example, a disperser such as a bead mill, 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 disper mat, an SC mill, or a nanomizer can be used.

  In addition, as a method for producing the ink, for example, <1> a colorant is contained at a high concentration by mixing the pigment dispersant, a colorant such as the pigment, and a solvent (D) as necessary. Step of producing a colorant dispersion a, <2> A composition b is produced by mixing the medium saccharified and reduced water candy, the binder (A), the compound (B), and a solvent (D) as necessary. <3> mixing the composition b with the aqueous medium and the like to produce a composition c, and <4> mixing the colorant dispersion a and the composition c. The method of manufacturing by this is mentioned.

  The ink obtained by the above method is preferably subjected to a centrifugal separation treatment or a filtration treatment as necessary in order to remove impurities mixed in the ink.

(Ink physical properties)
The ink of the present invention has a viscosity at 32 ° C. of preferably 2.0 mPa · s or more, more preferably 3.0 mPa · s or more, and even more preferably 5.0 mPa · s or more. Further, from the viewpoint of improving the storage stability and dischargeability of the ink, it is preferably 20 mPa · s or less, more preferably 12 mPa · s or less, more preferably 9.0 mPa · s or less, and even more preferably 7.0 mPa · s or less. It is. If the ink has a viscosity in the above range, it is possible to maintain good ejection stability, for example, when ejecting ink by an inkjet method.

  The pH of the ink of the present invention improves the storage stability and ejection properties of the ink, and improves the dot diameter spread, print density, and scratch resistance when printed on non-ink-absorbing or hard-absorbing recording media. In order to make it preferable, it is 7.0 or more, More preferably, it is 7.5 or more, More preferably, it is 8.0 or more. The upper limit of the pH of the ink suppresses deterioration of members (for example, ink discharge nozzles, ink flow paths, etc.) constituting the ink application or discharge device, and reduces the influence when the ink adheres to the skin. In doing so, it is preferably 11.0 or less, more preferably 10.5 or less, and even more preferably 10.0 or less.

(Recording medium)
The ink of the present invention has a recording medium excellent in ink absorbability, such as copy paper (PPC paper) generally used in a copying machine, a recording medium having an ink absorption layer, and completely absorbs ink. It is possible to print on a non-absorbable recording medium that does not have, or a recording medium with low water absorbency and poor absorption. In particular, the ink of the present invention can provide a printed matter excellent in setability and wear resistance even when printed on a non-ink-absorbing or hardly-absorbing recording medium.

As the non-absorbable or hardly absorbable recording medium, a recording medium in which the water absorption amount of the recording medium at a contact time of 100 msec between the recording medium and pure water is 10 g / m ² or less is described in the present invention. It is preferable to use the ink in combination with the above ink in order to obtain a printed matter having even more excellent abrasion resistance.

  In addition, the water absorption amount described above was measured at a pure water contact time of 100 ms under the conditions of 23 ° C. and 50% relative humidity using an automatic scanning absorption meter (manufactured by Kumagai Riki Kogyo Co., Ltd., KM500win). The amount of transfer was measured, and the amount of water absorption was 100 ms. The measurement conditions are shown below.

[Spiral Method]
Contact Time: 0.010 to 1.0 (sec)
Pitch: 7 (mm)
Length per sampling: 86.29 (degree)
Start Radius: 20 (mm)
End Radius: 60 (mm)
Min Contact Time: 10 (ms)
Max Contact Time: 1000 (ms)
Sampling Pattern: 50
Number of sampling points: 19
[Square Head]
Slit Span: 1 (mm)
Width: 5 (mm)

Art paper such as printing main paper, coated paper, lightweight coated paper, fine coated paper, and the like can be used as a recording medium having low water absorption of ink and low absorbability. These hardly-absorptive recording media are coated with a coating material on the surface of high-quality paper, neutral paper, etc. that are generally not surface-treated, mainly cellulose, and are provided with a coating layer. ) “OK Everlight Coat” manufactured by Nippon Paper Industries Co., Ltd., “Aurora S” manufactured by Nippon Paper Industries Co., Ltd., “OK Coat L” manufactured by Oji Paper Co., Ltd., and “Aurora” manufactured by Nippon Paper Industries Co., Ltd. Lightweight coated paper (A3) such as “L”, “OK Top Coat + (basis weight 104.7 g / m ² , water absorption amount at a contact time of 100 milliseconds (the following water absorption amount is the same)) manufactured by Oji Paper Co., Ltd. 9 g / m ² ) ”,“ Aurora Coat ”manufactured by Nippon Paper Industries Co., Ltd., Finese Gloss manufactured by UPM (manufactured by UPM, 115 g / m ² , water absorption 3.1 g / m ² ) and Fines Matt (115 g / m ^2, the water absorption amount 4.4g m ²⁾ coated paper such as (A2, B2), Oji Paper Co., Ltd. of "OK Kinfuji +" and Mitsubishi Paper Mills Co., Ltd. of art paper such as "Tokubishi Art" (A1), and the like.

As the non-water-absorbing recording medium having no ink absorbability, for example, a plastic film such as one used for food packaging materials can be used.
Examples of the plastic film include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films such as nylon, polystyrene films, polyvinyl alcohol films, polyvinyl chloride films, polycarbonate films, and polyacrylonitrile. Examples include films and polylactic acid films. Especially, as said plastic film, it is preferable to use especially a polyester film, a polyolefin film, and a polyamide-type film, and it is preferable to use a polyethylene terephthalate, a polypropylene, and nylon. As the plastic film, a film having gas barrier properties can be used. For example, a film having a layer containing polyvinylidene chloride or the like on one or both sides of the plastic film, a metal such as aluminum, silica or alumina. A film having a vapor-deposited layer containing a metal oxide such as can be used.

  As the plastic film, an unstretched film can be used, and a film stretched in a uniaxial or biaxial direction can be used. As the plastic film, it is preferable to use a film having a surface subjected to various treatments for improving adhesion such as corona discharge treatment, ozone treatment, low temperature plasma treatment, flame treatment, glow discharge treatment and the like.

  As the plastic film, a film having an arbitrary thickness can be used depending on the application. For example, when used in a flexible packaging application, the plastic film maintains good flexibility, durability and curl resistance. Therefore, it is preferable to use a material having a thickness of 10 μm to 100 μm, and it is more preferable to use a material having a thickness of 10 μm to 30 μm. Examples of the plastic film include Pyrene and Espet (both are registered trademarks) of Toyobo Co., Ltd.

  Examples of the ink-absorbing recording medium include plain paper, cloth, cardboard, and wood. Further, examples of the recording medium having an absorption layer include inkjet dedicated paper, and specific examples thereof include, for example, Pictrico Pro Photo Paper from Pictorico Co., Ltd.

  The ink of the present invention can be used for producing a printed matter by printing on the surface of the recording medium as described above.

  The ink can be applied to, for example, an ink jet method, a screen printing method, a flexographic printing method, a gravure printing method, and the like, but can be preferably used as an ink for ink jet printing.

  As the printed matter using the ink, for example, the ink is brought into contact with the surface of a recording medium by the inkjet method or the like and then dried, whereby the carbonyl group of the binder (A) contained in the ink, A printed material in which the structure represented by the following chemical formula (1) is formed by reacting with the hydrazine structure of the compound (B) is exemplified.

  The drying is performed within the range where the surface temperature of the recording medium is in the range of 5 to 60 ° C. Even when a recording medium that is relatively weak against heat is used, deformation due to the influence of heat of the recording medium is performed. Or discoloration is preferable.

  Specifically, the structure represented by the general formula (1) is formed when the carbonyl group of the binder (A) is a ketone group and the structure of the compound (B) is a hydrazine structure. Is the structure. By forming the above structure on the coating film of the printed matter, it is possible to exhibit excellent adhesion and setability with respect to the hardly adherent recording medium.

  By the way, when the ink of the present invention is printed on the recording medium by the ink jet printing method, the surface of the recording medium is uneven, or the recording medium is large and has distortion or warpage. In such a case, there is a concern that the inkjet head and the recording medium come into contact with each other. As a method of avoiding the contact, a distance (gap) from a surface (x) having an ink discharge port of the inkjet head to a position (y) where the perpendicular of the surface (x) and the recording medium intersect is preferably Is preferably 1 mm or more, more preferably 2 mm or more, and still more preferably 3 mm or more.

  The distance from the surface (x) to the position (y) where the perpendicular perpendicular to the surface (x) intersects the recording medium is large even if the recording medium is large and warps easily. Prevents the surface of the recording medium from coming into contact with the ink discharge port, effectively preventing ink discharge failure due to damage to the ink discharge port or a decrease in the water repellent function often included in the ink discharge port. In addition, even when the distance between the surface of the recording medium and the inkjet head is long, the lower limit of the distance is preferably 3 mm or more in producing printed matter having no streaks, The upper limit of the distance is preferably 10 mm or less, and particularly preferably 5 mm or less.

Therefore, as a method for producing a printed matter using the ink of the present invention and avoiding contact between the inkjet head and the recording medium, specifically, from the surface (x) having the ink discharge port of the inkjet head, After the ink for ink jet printing of the present invention is brought into contact with the surface of the recording medium in the ink jet recording system in which the distance to the position (y) where the perpendicular of the surface (x) intersects the recording medium is set to 1 mm or more The surface temperature of the recording medium is maintained within the range of 5 ° C. to 60 ° C. and dried, whereby the carbonyl group of the binder (A) contained in the ink and the hydrazine structure of the compound (B) It is preferable to produce a printed material by a method of forming a structure represented by the following chemical formula (1) by reacting

  Hereinafter, the present invention will be described in more detail by way of examples.

(Preparation of styrene- (meth) acrylic acid copolymer)
Isopropyl in the reaction vessel of an automatic polymerization reaction device (polymerization tester DSL-2AS type, manufactured by Sakai Sangyo Co., Ltd.) having a reaction vessel equipped with a stirring device, a dropping device, a temperature sensor, and a reflux device having a nitrogen introduction device at the top. 1,200 parts by mass of alcohol was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature in the reaction vessel to 80 ° C. while maintaining a nitrogen atmosphere, 75.0 parts by mass of 2-hydroxyethyl methacrylate, 260.8 parts by mass of methacrylic acid, 400.0 parts by mass of styrene, methacrylic acid from the dropping device. 234.2 parts by mass of benzyl, 30.0 parts by mass of glycidyl methacrylate, and “Perbutyl (registered trademark) O” (active ingredient t-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation) 80.0 parts by mass Was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was further continued at the same temperature for 15 hours, and then a part of isopropyl alcohol was distilled off under reduced pressure, and the solid content was adjusted to 42.5% by mass, whereby an acid value of 170 mgKOH / g. A styrene- (meth) acrylic acid copolymer (X) solution was obtained.

(Preparation of pigment dispersion)
In a mixing tank provided with a cooling jacket, 360 parts by mass of carbon black (Mitsubishi Chemical Corporation CI Pigment Black 7) and 170 parts by mass of a styrene- (meth) acrylic acid copolymer (X) solution, 61 mass parts of 25 mass% potassium hydroxide aqueous solution, 83 mass parts of isopropyl alcohol, and 1000 mass parts of ion-exchange water were prepared, and it stirred and mixed with the three one motor for 1 hour.

  The obtained mixed liquid is passed through a dispersion apparatus (SC mill SC100 / 32 type, manufactured by Mitsui Mining Co., Ltd.) filled with zirconia beads having a diameter of 0.3 mm, and the circulation system (mixed liquid discharged from the dispersion apparatus) Was returned to the mixing vessel and again supplied to the disperser) to obtain a dispersion. The dispersion treatment was performed for 4 hours with the rotor peripheral speed of the dispersion device fixed at 11.25 m / sec. Further, during the dispersion treatment, the temperature of the mixed liquid was controlled to be kept at 30 ° C. or less by passing cold water through the cooling jacket.

  The dispersion obtained by the method was extracted from the mixing tank. Next, 1500 parts by mass of water is supplied to the mixing tank, the flow path of the mixing tank and the dispersion device is washed, and a mixture of the water used for washing and the dispersion is mixed with the mill dispersion. did.

  Next, the mill dispersion was put into a glass distillation apparatus, and the whole amount of isopropyl alcohol and a part of water contained in the mill dispersion were distilled off. The mill dispersion after the distillation is allowed to cool to room temperature, and then 2% by mass hydrochloric acid is added dropwise with stirring to adjust the pH to 3.5. The solid content contained in the mill dispersion is filtered with a Nutsche filter and washed with water. This was used as a wet cake.

  Taking the wet cake into a container and adding a 25% by weight aqueous potassium hydroxide solution to adjust the pH to 9.0, redispersed with Disper (TK Homo Disper 20 type, manufactured by Tokushu Kika Kogyo Co., Ltd.) After centrifugal separation (6000 G, 30 minutes), ion-exchanged water was added to obtain an aqueous pigment dispersion (K) having a solid content of 18% by mass.

(Preparation of water-based ink)
(Example 1 Preparation method of water-based ink)
40.00 parts by mass of the aqueous pigment dispersion (K), a binder which is a core-shell type acrylic polymer having composition A (having a ketone group as a carbonyl group) derived from diacetone acrylamide in the core part, and , A mixture of adipic acid dihydrazide, nonvolatile content 48 mass%, volume average particle diameter of the core-shell acrylic polymer 50 nm, glass transition temperature 25 ° C. of the core-shell acrylic polymer, 12.5 parts by mass, PG (Asahi Glass Co., Ltd.) 10.00 parts by mass, 1,2-propanediol), S57 (manufactured by Food Science Co., Ltd., medium saccharified and reduced water candy, active ingredient 70% by mass) 10.00 parts by mass, ion-exchanged water 29 .32 parts by mass, 0.20 parts by mass of triethanolamine, ACTICIDE MV4 (a preservative made by So Japan Co., Ltd.) 0.10 parts by mass and 1.00 parts by mass of SURFYNOL 420 (Evonik's acetylene alcohol-based surfactant) were added and stirred to prepare a black aqueous ink (J1).

(Examples 2 to 12 and Comparative Examples 1 to 5 Preparation method of water-based ink)
Aqueous inks (J2) to (J12) and aqueous inks (H1) to (H5) were obtained in the same manner as in Example 1 except that the composition of the ink was changed to the composition described in Tables 1 to 5. It was.

TEA: Triethanolamine MV4: manufactured by So Japan Co., Ltd., preservative ACTICIDE MV4
SF440: SURFYNOL 440 manufactured by Evonik
Water: Ion exchange water

S57: Product of Food Science Co., Ltd., medium saccharified reduced water candy, active ingredient 70% by mass
Sweet OL: Product Food Science Co., Ltd., medium saccharified and reduced water candy, active ingredient 70% by mass
H-70: Mitsubishi Chemical Foods Co., Ltd., medium saccharified and reduced water candy “Oligotose H-70”, active ingredient 70% by mass
S600: Product made by Bussan Food Science Co., Ltd., high saccharified reduced starch syrup, active mass 70% by mass
Sweet NT: Product Food Science Co., Ltd., low saccharified reduced starch syrup, active ingredient 70% by mass
Sorbitol: monosaccharide alcohol Maltitol: disaccharide alcohol

Composition A: A binder which is a core-shell type acrylic polymer having a structure derived from diacetone acrylamide (having a ketone group as a carbonyl group) in the core part, and a mixture of adipic acid dihydrazide, nonvolatile content of 48% by mass, the core-shell type The volume average particle diameter of the acrylic polymer is 50 nm, and the glass transition temperature of the core-shell type acrylic polymer is 25 ° C.
Composition B: urethane dispersion not containing adipic acid dihydrazide corresponding to the compound (B), non-volatile content 35% by mass

(Evaluation of water-based ink)
The characteristics of the water-based inks obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 5-7.

[Evaluation of ejection stability (intermittent ejection performance by inkjet printing method)]
By filling the ink-jet head KJ4B-YH manufactured by Kyocera Corporation with the water-based inks obtained in the examples and comparative examples, the water head difference of the ink sub-tank from the head nozzle plate surface is set to +35 cm and the negative pressure is −5.0 kPa. The supply pressure was adjusted. As a recording medium, an OPP film (Pyrene P2161; biaxially stretched polypropylene film manufactured by Toyobo Co., Ltd., single-sided corona treatment) was used. The gap between the inkjet head and the corona-treated surface of the OPP film was set to 1.2 mm. The head drive conditions were the standard voltage and temperature of the inkjet head, the droplet size was set to 18 pL, and a grid-like nozzle check pattern was printed at 20 kHz. After leaving for 30 minutes, the nozzle check pattern was printed again, the state of the printed matter was confirmed, and the intermittent ejection property was judged.

(Double-circle): It has printed without missing a check pattern.
◯: Printing is missing at the printing start position, but printing is possible without any chipping thereafter.
Δ: There is a chip from the printing start position to the second and third lines, but after that, printing is possible without any chipping.
X: The check pattern is randomly chipped or not printed.

[Evaluation of setability]
Inkjet printing in which ink jet heads KJ4B-YH manufactured by Kyocera Corporation were filled with the water-based inks obtained in Examples and Comparative Examples, respectively, and the water head difference of the ink sub-tank from the head nozzle plate surface was set to +35 cm and negative pressure -5.0 kPa. Use a machine to print a 100% solid solid image on the corona-treated surface of an OPP film (Pyrene P2161; biaxially stretched polypropylene film manufactured by Toyobo Co., Ltd.) and dry it with a 60 ° C hot air dryer for 1 minute. A print was obtained.

  The gap between the inkjet head and the OPP film was set to 1.2 mm. The head drive conditions were the standard voltage and standard temperature of the inkjet head, and the ink droplet size was set to 18 pL.

  The printed matter is taken out from the hot air dryer and allowed to stand at room temperature for 1 minute. Then, the printed surface of the printed matter is overlaid with a non-corona-treated surface of an OPP film different from the above, and a weight is applied so that the load becomes 100 g / cm 2. Set and let stand for 1 minute.

  After 1 minute, the weight is removed, the OPP film overlaid on the printed material is peeled off, the printed surface of the printed material is read with a scanner, and the 100% density image before the OPP film is overlaid is used as a reference. The image density ratio (color residual ratio) after peeling off the OPP film was analyzed with image analysis software “ImageJ”.

A: The color remaining rate of the printed material is 90% or more. O: The color remaining rate of the printed material is 70% or more and less than 90%. X: The color remaining rate of the printed material is less than 70%.

[Glossiness (Evaluation of coating film appearance)]
Inkjet printing in which ink jet heads KJ4B-YH manufactured by Kyocera Corporation were filled with the water-based inks obtained in Examples and Comparative Examples, respectively, and the water head difference of the ink sub-tank from the head nozzle plate surface was set to +35 cm and negative pressure -5.0 kPa. Use a machine to print a 100% solid solid image on the corona-treated surface of an OPP film (Pyrene P2161; biaxially stretched polypropylene film manufactured by Toyobo Co., Ltd.) and dry it with a 60 ° C hot air dryer for 1 minute. A print was obtained.

  The gap between the inkjet head and the OPP film was set to 1.2 mm. The head drive conditions were the standard voltage and standard temperature of the inkjet head, and the ink droplet size was set to 18 pL.

  The printed matter was taken out from the hot air dryer and allowed to stand at room temperature overnight, and then the appearance of the coating film was visually confirmed and evaluated.

○: There is no deposit on the printed surface, and a glossy black coating film is obtained.
X: A white deposit is observed on the printing surface, and it is a dull black coating film.

[Adhesion evaluation]
Inkjet printing in which ink jet heads KJ4B-YH manufactured by Kyocera Corporation were filled with the water-based inks obtained in Examples and Comparative Examples, respectively, and the water head difference of the ink sub-tank from the head nozzle plate surface was set to +35 cm and negative pressure -5.0 kPa. A 100% density solid image was printed on the corona-treated surface of an OPP film (Pyrene P2161; biaxially stretched polypropylene film manufactured by Toyobo Co., Ltd., single-sided corona treatment) using an apparatus. A printed matter was obtained by drying for a minute.

  The gap between the inkjet head and the PET film was set to 1.2 mm. The head drive conditions were the standard voltage and standard temperature of the inkjet head, and the ink droplet size was set to 18 pL.

  Next, after strongly pressing the cellophane adhesive tape to the printing surface of the printed matter, the cellophane adhesive tape was pulled in a direction of 90 ° with respect to the printing surface.

The printed surface (x) after the cellophane adhesive tape is peeled off and the printed surface (y) to which the cellophane adhesive tape is not applied are read with a scanner, and the printed surface (x) for the color of the printed surface (x) ( The color ratio (color residual ratio) of y) was analyzed with image analysis software “ImageJ”.
A: Color remaining ratio is 70% or more. B: Color remaining ratio is 50% or more and less than 70%. X: Color remaining ratio is less than 50%.

[Evaluation of streaks of printed matter]
The ink jet head KJ4B-YH manufactured by Kyocera Corporation is filled with the water-based ink obtained in Examples and Comparative Examples, respectively, and the water head difference of the ink sub-tank from the head nozzle plate surface is set to +35 cm and the negative pressure is −5.0 kPa. The supply pressure was adjusted with. Further, the distance (gap) from the surface (x) having the ink discharge port of the ink jet head to the position (y) where the perpendicular perpendicular to the surface (x) and the recording medium intersect was set to 3 mm. . As the recording medium, a corrugated cardboard having a thickness of about 2 mm having a white colored layer was used. The driving conditions of the head were the standard voltage and standard temperature of the inkjet head, the droplet size was set to 18 pL, and 100% solid printing was performed to obtain a printed matter.

  The printed matter was read by a scanner, and the ratio (streaks) of the portion where ink was not applied was calculated by image analysis software “ImageJ”.

◎: Streaks ratio of printed matter less than 3% ○: Streaks ratio of printed matter between 3% and less than 5% △: Streaks ratio of printed matter between 5% and less than 10% ×: Streaks ratio of printed matter of 10% or more

  In the water-based inks of Examples 1 to 12, it was confirmed that the ejection stability was good. In particular, the inks of Examples 1 to 9 using a medium saccharified reduced starch candy, an acrylic emulsion binder, and a solvent having a Hansen solubility parameter having a polar term of 7 to 12 and a hydrogen bond term of 15 to 30 are set with ejection stability. It was excellent in properties.

  On the other hand, in the inks of Comparative Examples 1 and 2, white precipitates were observed on the coating film, and the coating film appearance was poor. In Comparative Example 3, the ink containing the highly saccharified and reduced water candy had poor setting properties. The ink containing the reduced saccharified reduced starch candy of Comparative Example 4 was poor in ejection stability. The ink containing glycerin as the humectant of Comparative Example 5 had poor setability.

Claims (14)

Medium saccharified reduced candy, an aqueous medium, a binder (A), and a compound (B) having a structure capable of reacting with a functional group of the binder (A), and the binder (A) is an acrylic resin Characteristic ink. The ink according to claim 1, wherein the medium saccharified and reduced candy is contained in a range of 1% by mass to 10% by mass with respect to the total amount of the ink. The ink according to claim 1 or 2, further comprising a pigment and a pigment dispersant. The ink according to claim 3, wherein the pigment dispersant is a styrene-acrylic resin. The ink according to claim 4, wherein the acrylic resin is a water-dispersible acrylic resin. The ink according to any one of claims 1 to 5, wherein the binder (A) is a binder (a) having a carbonyl group. The ink according to claim 6 , wherein the binder (A) is a core-shell polymer, and the core portion of the core-shell polymer has a carbonyl group. The ink according to claim 6 or 7 , wherein the compound (B) is a compound having a hydrazine structure. The ink according to any one of Claims 1 to 8 , wherein the aqueous medium contains a solvent (D) having a Hansen solubility parameter having a polar term of 7 or more and a hydrogen bond term of 15 or more. The solvent (D) is 1,2-propanediol, 1,2-hexanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 3-methyl-1,5- The pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, or 3-methyl-1,4-butanediol according to any one of claims 9 to 10. Ink. The solvent (D) is 1,2-propanediol, 1,2-hexanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 3-methyl-1,5. -One or more types selected from the group consisting of pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol and 3-methyl-1,4-butanediol. Item 11. The ink according to Item 10 . Inkjet printing ink comprising an ink according to any one of claims 1 to 11. After the ink according to any one of claims 1 to 12 contacts the surface of the recording medium, a carbonyl group that the binder (a) contained in the ink has, and a hydrazine structure that the compound (B) has Which has reacted to form a structure represented by the following chemical formula (1).

From the surface (x) having ink discharge ports of the ink jet head, the ink jet recording method in which a perpendicular line and the distance to the recording medium intersect position (y) is set to more than 1mm of the surface (x), in claim 12 After the ink for ink jet printing described above is brought into contact with the surface of the recording medium, the surface temperature of the recording medium is maintained within a range of 5 ° C. to 60 ° C. and dried, whereby the binder (A ) And a hydrazine structure of the compound (B) are reacted to form a structure represented by the following chemical formula (1).