Gravure or flexographic ink

Abstract

To provide a gravure or flexographic ink excellent in storage stability, laminate strength and heat seal strength when laminated, and plate fogging properties and plate clogging properties during printing.SOLUTION: The gravure or flexographic ink contains a pigment, a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulosic resin, and an acidic compound, wherein the acidic compound contains a block copolymer having a structure derived from a polyether and / or a polyester.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a gravure or flexographic ink that is excellent in storage stability, lamination strength and heat seal strength when laminated, and plate fogging and plate clogging during printing. [Background technology]

[0002] In printing inks, paints, etc., finely dispersed pigments are used to impart vivid color tones, gloss, and other properties to printed or coated materials. Furthermore, stable dispersion of pigments improves the fluidity of printing inks and paints, improving printability, such as plate fogging, and printing effects, such as preventing plate clogging. White inks, in particular, contain a very high amount of pigment, so maintaining a stable dispersion is essential. Furthermore, stable dispersions generally also offer excellent storage stability and laminate strength. Furthermore, in lamination applications, heat sealing is expected after lamination, so lamination inks are required to have heat resistance in addition to plate fogging and storage stability. However, a product that satisfies all of these properties has yet to be developed, posing a challenge.

[0003] To solve these problems, various pigment dispersants have been developed. For example, the pigment derivatives disclosed in Patent Document 1 and the polyesters disclosed in Patent Documents 2 and 3 exhibit a certain degree of effectiveness as pigment dispersants, but their effectiveness is insufficient when finer pigments are used to obtain higher-quality printing inks and paints. Furthermore, due to the recent increase in environmental concerns, organic solvents used in printing inks and paints are shifting from those primarily composed of aromatic compounds such as toluene to those primarily composed of esters or alcohols, which is significantly disadvantageous for dispersing pigments. In such printing inks and paints, the effectiveness of the pigment dispersants described above has not been satisfactory.

[0004] Patent Document 4 also describes a phosphate ester containing polyether and / or polyester. However, it is stated that dispersibility is improved by using a basic functional group-containing organic dye derivative in combination, and a polyether and / or polyester-containing pigment dispersion is disclosed. The phosphate ester alone showed no effect.

[0005] Furthermore, Patent Document 5 discloses a white ink containing a phosphate ester having a polyalkylene ether structure, but does not describe heat seal strength, plate fogging, or plate clogging. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 41-2466 [Patent Document 2] Special Publication No. 54-34009 [Patent Document 3] Special Publication No. 63-30057 [Patent Document 4] Japanese Patent Application Laid-Open No. 2003-183562 [Patent Document 5] Patent Publication No. 2021-138785 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a gravure or flexographic ink that is excellent in storage stability, lamination strength and heat seal strength when laminated, and plate fogging and plate clogging during printing. [Means for solving the problem]

[0008] That is, the present invention relates to a method for producing a polyurethane resin comprising a pigment, a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulosic polymer. A gravure or flexographic ink containing a cellulose-based resin and an acidic compound, wherein the acidic compound is a block copolymer having a structure derived from polyether and / or polyester. The present invention relates to a gravure or flexographic ink, characterized in that it contains a mer.

[0009] The present invention also relates to the gravure or flexographic ink described above, wherein the pigment contains titanium oxide.

[0010] The present invention also relates to the gravure or flexographic ink described above, wherein the polyurethane resin contains a structure derived from a dibasic acid, and the dibasic acid contains sebacic acid.

[0011] The present invention also relates to the gravure or flexographic ink described above, wherein the content of sebacic acid is 50% by mass or more based on the total mass of dibasic acids.

[0012] The present invention also relates to the gravure or flexographic ink described above, wherein the polyurethane resin contains a structure derived from a polyisocyanate, and the polyisocyanate contains an aromatic polyisocyanate and an aliphatic polyisocyanate.

[0013] The present invention also relates to the gravure or flexographic ink described above, wherein the content of the aromatic polyisocyanate is 50% by mass or more based on the total mass of the polyisocyanate.

[0014] The present invention also relates to the gravure or flexographic ink described above, which further contains a fatty acid amide.

[0015] The present invention also relates to the above gravure or flexographic ink, which further contains a chlorinated polypropylene resin.

[0016] The present invention also relates to the gravure or flexographic ink described above, wherein the acidic compound has a phosphate group.

[0017] The present invention also relates to the gravure or flexographic ink described above, wherein the block copolymer contains a structure derived from a lactone.

[0018] The present invention also relates to a printed matter having a printed layer made of the above gravure or flexographic ink on a substrate 1.

[0019] The present invention also provides a printing method comprising at least a substrate 1 and the above-mentioned gravure or flexographic ink. The present invention relates to a laminate having a layer, a substrate 2, and a substrate 3 in this order. [Effects of the Invention]

[0020] The present invention has made it possible to provide a gravure or flexographic ink that is excellent in storage stability, lamination strength and heat seal strength when laminated, and plate fogging and plate clogging during printing. DETAILED DESCRIPTION OF THE INVENTION

[0021] The following describes in detail an embodiment of the present invention, but the following description of the constituent elements is one example (typical example) of an embodiment of the present invention, and the present invention is not limited to these details as long as it does not deviate from the gist of the invention. Also, "gravure or flexographic ink" may be simply referred to as "ink," but this has the same meaning.

[0022] The present invention relates to a pigment, a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulose-based resin, Acidic block copolymers containing polyether and / or polyester-derived structures The gravure or flexographic ink is characterized by containing a compound. In the present invention, the binder resin refers to a binding resin component in the gravure or flexographic ink, and polyurethane resin, vinyl chloride copolymer resin, and / or cellulose-based resin are binder resins. is.

[0023] In the present invention, polyurethane resin, vinyl chloride copolymer resin and / or cellulose resin, polyvinyl chloride copolymer resin and / or cellulose resin are used. The combination of an acidic compound containing a block copolymer having a structure derived from a polyether and / or polyester improves pigment dispersibility and storage stability. This is because the block copolymer portion of the acidic compound is compatible with the pigment or polyurethane resin, and the acid group portion is compatible with the vinyl chloride copolymer resin and / or cellulose-based resin, resulting in an interaction between the block copolymer portion and the acidic compound. It is presumed that the pigment dispersibility as an ink is significantly improved. As a result of the improvement in pigment dispersibility, there are effects of improving lamination strength, heat seal strength, plate fogging resistance, and plate clogging resistance. Furthermore, when the polyurethane resin contains a structure derived from a dibasic acid, and the total mass of the dibasic acid contains 50% by mass or more of sebacic acid, and the polyurethane resin contains a structure derived from a polyisocyanate, and the polyisocyanate contains both an aromatic polyisocyanate and an aliphatic polyisocyanate, the laminate strength and heat seal strength are improved. This is presumably due to the interaction between the hydrophobic structure derived from sebacic acid and the substrate, and the interaction between the structure derived from sebacic acid and the structure derived from isocyanate. Note that this explanation is based solely on speculation and does not limit the invention in any way.

[0024] (pigment) The pigments used in the gravure or flexographic ink of the present invention include inorganic pigments and organic pigments.

[0025] Examples of the inorganic pigment include zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, aluminum particles, mica, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine, Prussian blue, red iron oxide, yellow iron oxide, iron black, titanium oxide, and zinc oxide, and among these, titanium oxide is preferred.

[0026] The titanium oxide may have any of anatase, rutile, and brookite crystal structures. Among them, rutile titanium oxide is preferred because it has good pigment dispersibility. In the industrial production of titanium oxide, rutile ore or ilmenite ore (FeTiO3) is used as the raw material. There are two main production methods: the chloride method and the sulfuric acid method. It is also possible to use the following. Furthermore, in order to improve printability in gravure printing, it is preferable that the titanium oxide pigment is surface-treated, and in particular, that it is surface-treated with at least one metal selected from Si, Al, Zn, Zr, and oxides thereof.

[0027] Titanium dioxide pigment has an oil absorption of 14% by the measurement method specified in JIS K5101. Preferably up to 35ml / 100g, and 17-32ml / 100g It is more preferable that the average particle size (median particle size) measured by a transmission electron microscope is 0.2 to 0.3 μm. The total content of the titanium oxide pigment is It is preferably 10 to 60% by weight, more preferably 10 to 45% by weight, based on 100% by weight of the ink. It is more preferable that the titanium oxide pigment is a titanium dioxide pigment. From the viewpoints of white density, laminate strength, and residual solvent, the mass ratio of the titanium oxide pigment to the binder resin (titanium oxide / binder resin) is preferably 2.8 to 5. It is more preferably 3 to 4.5, and even more preferably 3.2 to 4.

[0028] Examples of the organic pigment include, but are not limited to, soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, perylene pigments (perylene red, perinone orange), perinone pigments, quinacridone pigments (quinacridone magenta, quinacridone red), thioindigo pigments (thioindigo bordeaux, thioindigo magenta), dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, indanthrone pigments, carbon black pigments, and aniline black pigments. Examples of commercially available product names include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, cromophtal yellow, cromophtal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments.

[0029] (Polyurethane resin) The polyurethane resin in the present invention functions as a binder resin, and the weight average molecular weight of the polyurethane resin is preferably 10,000 to 100,000, and more preferably 30,000 to 80,000. When the weight average molecular weight is within the range of 10,000 to 100,000, the laminate strength tends to be improved. The polyurethane resin content is preferably 1 to 25 mass % of the total mass of the ink, and more preferably 3 to 20 mass %.

[0030] The polyurethane resin in the present invention is preferably a polyurethane resin obtained by a condensation reaction between a polyol and a polyisocyanate, or a polyurethane resin (polyurethane urea resin) obtained by a reaction (called chain extension) between a urethane prepolymer having an isocyanate group at its terminal, which is a condensation reaction product between a polyol and a polyisocyanate, and a polyamine. The polyol preferably contains a polymer polyol, and the polymer polyol more preferably has a weight average molecular weight of 400 to 10,000.

[0031] Examples of polyols include polyester polyols, polyether polyols, polycaprolactone diols, polycarbonate polyols, polyolefin polyols, castor oil polyols, hydrogenated castor oil polyols, dimer diols, and hydrogenated dimer diols. Among these, polyester polyols are preferred. The polyester polyol content of the total mass of the raw material polyols is preferably 50 mass% or more, and more preferably 70 mass% or more.

[0032] (polyester polyol) Examples of polyester polyols include condensates obtained by esterification reaction of polybasic acids with diols. The polybasic acid preferably includes a dibasic acid, and the dibasic acid preferably includes sebacic acid, and more preferably includes 50% by mass or more, and particularly preferably 65% ​​by mass or more, of the total mass of the dibasic acids. In addition, the polybasic acid may further include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, suberic acid, glutaric acid, and 1,4-cyclohexyldicarboxylic acid. It is also preferable to use dibasic acids other than sebacic acid, such as dimer acids and hydrogenated dimer acids, in combination. As the dibasic acid to be used in combination with sebacic acid, adipic acid, succinic acid, etc. are more preferred.

[0033] The diol preferably contains a branched diol and a linear diol, which improves the laminate strength of the laminate. Here, the branched diol refers to a diol in which at least one hydrogen atom in the hydrocarbon group of an alkylene glycol is substituted with a non-hydrogen atom, and the linear diol refers to a diol having two or more atoms, such as alkylene glycol, dialkylene glycol, trialkylene glycol, or other diols.

[0034] The branched diols include 2-butyl-2-ethyl-1,3-propanediol (B EPG) and 2-methyl-1,3-propanediol (MPO) ), 3-methyl-1,5-pentanediol (also written as MPD), neopentylglycerin Coal (also written as NPG), 1,2-propylene glycol (also written as PG), 2,4-diethyl-1,5-pentanediol, 1,3-butanediol, dipropylene glycol Among them, at least one branched diol selected from MPO, MPD, BEPG, NPG, PG, and 2,4-diethyl-1,5-pentanediol is preferred, NPG and / or BEPG is more preferred, and NPG is particularly preferred.

[0035] The linear diol is preferably an alkylene glycol, and examples of such compounds include ethylene glycol (also referred to as EG), diethylene glycol, 1,3 -propanediol (also written as 1,3-PD), 1,4-butanediol (1,4-B D), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol Examples thereof include ethanediol, 1,9-nonanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, and triethylene glycol. Among these, linear diols having 8 or less carbon atoms, preferably 6 or less carbon atoms, are preferred, and examples thereof include EG, 1,3-PD, 1,4-BD, 1,5-pentanediol, 1,6-hexanediol, 1,8 -octanediol, etc. are preferred.

[0036] The polyisocyanate is preferably a diisocyanate, and various known aromatic, aliphatic, or alicyclic diisocyanates can be used as such compounds, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylsilyl methyl ether ... Representative examples include methylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate in which the carboxyl groups of dimer acid are converted to isocyanate groups. These can be used alone or in combination of two or more. Among these, it is preferable to use an aromatic isocyanate and an aliphatic isocyanate in combination, and it is preferable to use tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate as the aromatic isocyanate and isophorone diisocyanate as the aliphatic isocyanate. The aromatic isocyanate is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the polyisocyanate. The total mass of polyisocyanate in the total mass of the polyurethane resin raw material is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and even more preferably 1 to 10 mass%.

[0037] The polyamine is preferably an organic diamine, and examples of such diamines include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine. Also usable are amines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. These organic diamines can be used alone or in combination, with isophoronediamine being preferred. Furthermore, polyfunctional amines having three or more amino groups, such as diethylenetriamine, iminobispropylamine (IBPA, 3,3'-diaminodipropylamine), N-(3-aminopropyl)butane-1,4-diamine (spermidine), 6,6-iminodihexylamine, 3,7-diazanonane-1,9-diamine, and N,N'-bis(3-aminopropyl)ethylenediamine, can be used in combination with the above organic diamines. Can also be used in combination with Min.

[0038] In the present invention, the polyurethane resin preferably has an amino group. When the polyurethane resin has an amino group, the amine value is preferably 0.5 to 15 mgKOH / g, and more preferably 1 to 13 mgKOH / g. Within this range, the laminate strength to the substrate tends to be improved.

[0039] In the chain extension reaction using a polyamine, a monoamine may be used as a reaction terminator, such as dialkylamines such as dibutylamine, diethylamine, and dipropylamine, as well as amines having a hydroxyl group such as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, and tri(hydroxymethyl)aminomethane.

[0040] (Biomass-derived raw materials) Available biomass-derived raw materials include sebacic acid, succinic acid, dimer acid, EG, PG, 1,3-PD, 1,4-BD, NPG, ethanol, pentylene glycol, 1,10-decanediol, dimer diol, isosorbide, lactic acid, 1,5-pentamethylene diisocyanate, and dimer diisocyanate.

[0041] (Vinyl chloride copolymer resin and / or cellulose-based resin) In the present invention, in addition to the polyurethane resin, vinyl chloride copolymer resin and / or cellulose A cellulose-based resin is used in combination with the vinyl chloride copolymer resin. The total mass of the vinyl chloride copolymer resin and the cellulose-based resin is preferably 0.3 to 15 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 8 mass% of the total mass of the ink. From the viewpoint of pigment dispersibility, the mass ratio of the polyurethane resin mass to the total mass of the vinyl chloride copolymer resin and the cellulose-based resin (polyurethane resin mass:total mass of the vinyl chloride copolymer resin and the cellulose-based resin) is preferably 97:3 to 30:70, more preferably 95:5 to 50:50, and even more preferably 90:10 to 70:30. The total mass of the polyurethane resin, vinyl chloride copolymer resin, and cellulose-based resin is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more of the total mass of the binder resin.

[0042] (vinyl chloride copolymer resin) The vinyl chloride copolymer resin used in the present invention is not particularly limited as long as it contains structural units derived from vinyl chloride monomers and structural units derived from other monomers, and examples thereof include vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-acrylic copolymer resins, vinyl chloride-vinyl acetate-vinyl alcohol copolymer resins, etc. Among these, it is preferable to use vinyl chloride-vinyl acetate copolymer resins or vinyl chloride-acrylic copolymer resins.

[0043] (Vinyl chloride-vinyl acetate copolymer resin) Vinyl chloride-vinyl acetate copolymer resins are copolymers of vinyl chloride and vinyl acetate, and preferably have a weight-average molecular weight of 5,000 to 100,000, more preferably 20,000 to 70,000. Of the 100% by mass of solids content of the vinyl chloride-vinyl acetate copolymer resin, the vinyl acetate monomer-derived structure is preferably 1 to 30% by mass, and the vinyl chloride monomer-derived structure is preferably 70 to 99% by mass. Within these ranges, solubility in organic solvents is improved, and further, adhesion to substrates, film properties, laminate strength, etc. are improved. Furthermore, since the solubility in organic solvents is improved, it is more preferable that the vinyl alcohol-derived hydroxyl group is contained in the vinyl alcohol by saponification or copolymerization, and the hydroxyl value is preferably 20 to 200 mgKOH / g.The glass transition temperature is preferably 50 to 90°C.

[0044] (vinyl chloride-acrylic copolymer resin) The vinyl chloride-acrylic copolymer resin is primarily composed of a copolymer resin of vinyl chloride monomer and acrylic monomer. The acrylic monomer preferably contains a (meth)acrylic acid hydroxyalkyl ester, which improves adhesion to substrates and solubility in organic solvents. The acrylic monomer may be incorporated into the main chain of polyvinyl chloride in a block or random manner, or may be graft-polymerized onto the side chain of polyvinyl chloride. The vinyl chloride-acrylic copolymer resin preferably has a weight-average molecular weight of 10,000 to 100,000, more preferably 30,000 to 70,000. The hydroxyl value is preferably 20 to 200 mgKOH / g, and the glass transition temperature is preferably 50 to 90°C.

[0045] Furthermore, the vinyl chloride monomer-derived structure in the vinyl chloride-acrylic copolymer resin preferably accounts for 70 to 95 mass % of 100 mass % of the solid content of the vinyl chloride-acrylic copolymer resin, which improves solubility in organic solvents and further improves adhesion to substrates, film properties, laminate strength, etc.

[0046] The acrylic monomer preferably contains one having a hydroxyl group. Examples include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate; caprolactone-modified (meth)acrylate; and hydroxyethyl acrylamide. Among these, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl acrylate are more preferred because they improve solubility in solvents. These monomers can be used alone or in combination. Acrylic monomers other than those listed above may also be optionally added.

[0047] (cellulose-based resin) Examples of cellulose-based resins include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, and carboxyalkyl cellulose. The alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and hexyl groups, and the alkyl groups may further have a substituent. Among these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferred. The mass-average molecular weight of the cellulose resin is preferably 5,000 to 200,000, more preferably 10,000 to 10,000, and even more preferably 15,000 to 80,000. The glass transition temperature of the cellulose resin is preferably 120°C to 180°C, and more preferably 130 to 170°C. By using the above-mentioned polyurethane resin in combination with a cellulose-based resin, plate fogging resistance, plate clogging resistance, blocking resistance, etc. are improved.

[0048] (nitrocellulose) Nitrocellulose is preferably obtained as a nitric acid ester by reacting native cellulose with nitric acid to replace three hydroxyl groups in the six-membered ring of the anhydroglucopyranose group in the native cellulose with nitric acid groups, and the nitrogen content is preferably 10.5 to 12.5% ​​by mass.

[0049] In addition to the polyurethane resin, vinyl chloride copolymer resin and / or cellulose-based resin, various other resins can be used in the ink of the present invention depending on the application and substrate. Examples of the resin include chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, cellulose resin, nitrocellulose resin, acrylic resin, polyester resin, alkyd resin, rosin resin, rosin-modified maleic acid resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, polybutyral, petroleum resin, and modified resins thereof. Among these, chlorinated polypropylene resin is preferred, as it improves lamination strength and heat seal strength. These resins can be used alone or in combination of two or more, and the content thereof is preferably 1 to 6% by mass of the total mass of the ink.

[0050] (Acidic compounds containing block copolymers) In the present invention, the acidic compound has a structure derived from polyether and / or polyester. When the structure derived from polyether is designated as A and the structure derived from polyester is designated as B, it is preferable that the structure is AB, ABA, or BAB.

[0051] In the present invention, examples of the monomer used to form the polyether-derived structure include polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, polytetramethylene glycol monomethyl ether, polybutylene glycol monomethyl ether, etc. Among these, it is preferable to use polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether.

[0052] Examples of monomers used to form polyester-derived structures include polymers of propiolactone, valerolactone, caprolactone, or mixtures thereof, and polymers of aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, or lower alcohol esters thereof with ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexane glycol, diethylene glycol, neopentyl glycol, or an ethylene oxide adduct of bisphenol A, or mixtures thereof. Among these, valerolactone and caprolactone are preferred, and ε-caprolactone and ε-valerolactone are particularly preferred.

[0053] In the present invention, examples of block copolymers having a polyether-derived structure include those using polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether, those using polyethylene glycol monomethyl ether and polytetramethylene glycol monomethyl ether, and those using polyethylene glycol monomethyl ether and polybutylene glycol monomethyl ether. Block copolymers having a structure derived from polyether and polyester include those using polyethylene glycol monomethyl ether and ε-caprolactone, and those using polypropylene glycol monomethyl ether and ε-caprolactone. polyethylene glycol monomethyl ether and ε-caprolactone, polyethylene Glycol monomethyl ether, polypropylene glycol monomethyl ether and ε-caprylic acid those using prolactone, polyethylene glycol monomethyl ether and ε-valero those using lactone, polypropylene glycol monomethyl ether and ε-valerol those using polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether and ε-valerolactone; and those using methyl alcohol monomethyl ether, ε-caprolactone, and ε-valerolactone.

[0054] In the present invention, examples of the acid group possessed by the acidic compound include a phosphate group, a carboxy group, and a sulfo group, with a phosphate group being preferred.

[0055] From the viewpoint of pigment dispersibility, the content of the acidic compound in the ink solids of the present invention is preferably 0.01 to 3 mass %, more preferably 0.1 to 1 mass %, and the mass ratio of the acidic compound to the pigment (acidic compound:pigment) is preferably 0.1:99.9 to 1:99, more preferably 0.1:99.9 to 0.5:99.5.

[0056] (fatty acid amides) The fatty acid amide is not particularly limited as long as it is one that is commonly used in the field. The fatty acid amide is dissolved or dispersed in the ink, but after ink printing, it is thought to be oriented on the surface of the printed film and improve the blocking resistance of the substrate that is overlapped by the printing roll. In addition, a portion of the fatty acid amide bonds with the block copolymer moiety of the acidic compound and / or the sebacic acid moiety of the sebacic acid-based polyester polyol in the urethane resin, improving pigment dispersibility and storage stability, which is believed to result in improved substrate adhesion, lamination strength, and heat seal strength. The content of the fatty acid amide in the ink of the present invention is preferably 0.02 to 2 mass %, more preferably 0.04 to 1.7 mass %, and even more preferably 0.1 to 1.5 mass %, based on the ink solids.

[0057] Examples of fatty acid amides include bisamides, monoamides, substituted amides, methylol amides, and ester amides. At least one selected from the group consisting of bisamides, monoamides, and substituted amides is preferred because it improves blocking resistance.

[0058] <Monoamide> The monoamide is represented by the following general formula (1). General formula (1) R1-CONH2 (In the formula, R1 represents the residue obtained by removing COOH from a fatty acid.) Examples of monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, and erucic acid amide. Examples include Do.

[0059] <Substituted Amide> The substituted amide is represented by the following general formula (2). General formula (2) R2-CONH-R3 (In the formula, R2 and R3 represent residues obtained by removing COOH from fatty acids, and may be the same or different.) Examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl erucic acid amide.

[0060] <Bisamide> The bisamide is represented by the following general formula (3) or (4). General formula (3) R4-CONH-R5-HNCO-R6 General formula (4) R7-NHCO-R8-CONH-R9 (In the formula, R4, R6, R7, and R9 represent a residue obtained by removing COOH from a fatty acid and may be the same or different, and R5 and R8 represent an alkylene group or an arylene group having 1 to 10 carbon atoms.) Examples of bisamides include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N,N'-distearyl adipamide, N,N'-distearyl sebacic acid amide, N,N'-dioleyl adipamide, N,N'-dioleyl sebacate amide and the like.

[0061] The arylene group is preferably at least one selected from the group consisting of a phenylene group, a toluylene group, and an m-xylylene group.

[0062] The melting point of the fatty acid amide is preferably 50° C. to 150° C. Examples of such monoamides include lauric acid amide (melting point 87° C.), palmitic acid amide (melting point 100° C.), stearic acid amide (melting point 101° C.), behenic acid amide (melting point 110° C.), hydroxystearic acid amide (melting point 107° C.), oleic acid amide (melting point 75° C.), and erucic acid amide (melting point 81° C.). Examples of substituted amides include N-oleyl palmitic acid amide (melting point 68°C), N-stearyl stearic acid amide (melting point 95°C), N-stearyl oleic acid amide (melting point 67°C), N-oleyl stearic acid amide (melting point 74°C), and N-stearyl erucic acid amide (melting point 69°C). Examples of bisamides include methylene bisstearic acid amide (melting point 142°C), ethylene bisstearic acid amide (melting point 145°C), ethylene bishydroxystearic acid amide (melting point 145°C), ethylene bisbehenic acid amide (melting point 142°C), hexamethylene bisstearic acid amide (melting point 140°C), hexamethylene bisbehenic acid amide (melting point 142°C), hexamethylene hydroxystearic acid amide (melting point 135°C), ethylene bisoleic acid amide (melting point 119°C), ethylene biserucic acid amide (melting point 120°C), Examples include hexamethylene bisoleamide (melting point 110°C), N,N'-distearyl adipamide (melting point 141°C), N,N'-distearyl sebacamide (melting point 136°C), N,N'-dioleyl adipamide (melting point 118°C), and N,N'-dioleyl sebacamide (melting point 113°C). Among the above, those that maintain laminate strength are Therefore, the weight average molecular weight is preferably 200 to 800, and more preferably 250 to 700.

[0063] Furthermore, the fatty acids constituting the fatty acid amide are preferably saturated fatty acids having 12 to 20 carbon atoms and / or unsaturated fatty acids having 16 to 25 carbon atoms, and more preferably saturated fatty acids having 16 to 18 carbon atoms and / or unsaturated fatty acids having 18 to 22 carbon atoms. Particularly preferred saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, and hydroxystearic acid, and particularly preferred unsaturated fatty acids are oleic acid and erucic acid. Fatty acid amides composed of at least one fatty acid selected from the group consisting of palmitic acid, stearic acid, behenic acid, hydroxystearic acid, oleic acid, and erucic acid are most preferred.

[0064] (organic solvent) The ink of the present invention preferably contains an organic solvent as a liquid medium. The organic solvent used is preferably a mixed solvent, and known organic solvents can be used, such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, and alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol. Among these, organic solvents that do not contain aromatic organic solvents such as toluene and xylene (non-toluene organic solvents) are more preferred. Even more preferred are organic solvents that do not contain aromatic organic solvents and / or ketone organic solvents such as methyl ethyl ketone (hereinafter also referred to as MEK), and preferably contain an ester organic solvent as the main component (50% by mass or more of the total mass of the organic solvent). Organic solvents containing an ester organic solvent and an alcohol organic solvent are particularly preferred.

[0065] (Other additives) The ink of the present invention may also contain additives such as a leveling agent, an antifoaming agent, a wax, a silane coupling agent, a plasticizer, a light stabilizer, silica particles, an infrared absorber, an ultraviolet absorber, a fragrance, a flame retardant, and a curing agent, as necessary.

[0066] (Ink manufacturing method) The ink of the present invention can be produced, for example, by mixing titanium oxide, a binder resin containing a polyurethane resin, an organic solvent, etc. in advance using a stirring mixer, and then dispersing the pigment in the mixture using a disperser such as a bead mill, and then adding and mixing the binder resin, various additives, organic solvent, etc. to the obtained dispersion. The dispersing machine may be a commonly used one, such as a roller mill, ball mill, pebble mill, attritor, sand mill, etc. The particle size distribution of the pigment in the pigment dispersion can be adjusted by appropriately adjusting the size of the grinding media in the dispersing machine, the packing ratio of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, etc.

[0067] The viscosity of the ink of the present invention is preferably in the range of 10 mPa·s or more at 25°C to prevent pigment sedimentation and ensure adequate dispersion, and 1000 mPa·s or less to improve workability during ink production and printing. A viscosity of 20 to 500 mPa·s is even more preferable. The viscosity can be measured at 25°C using a Tokimec B-type viscometer.

[0068] (hardening agent) The ink of the present invention is preferably used as a two-component ink by adding a curing agent to improve the lamination strength. As the curing agent, it is preferable to use a polyisocyanate, for example, tolylene diisocyanate (hereinafter also referred to as TDI), diphenylmethane diisocyanate (hereinafter also referred to as MDI), hexamethylene diisocyanate (hereinafter also referred to as H Suitable examples of polyisocyanates include adduct polyisocyanates (also referred to as HDI), biuret polyisocyanates (biuret), and isocyanurate polyisocyanates (isocyanurate). Suitable examples include an adduct obtained from the reaction of 1 mole of trimethylolpropane with 3 moles of HDI, a biuret obtained from the reaction of 1 mole of water with 3 moles of HDI, and an isocyanurate obtained from the cyclotrimerization reaction of HDI. When used as a two-component ink, the amount of polyisocyanate curing agent added is preferably 0.5 to 10% by mass, and more preferably 0.5 to 5% by mass, based on the total amount of the ink of the present invention.

[0069] (Gravure or flexographic ink printing) The ink of the present invention is suitable for printing by gravure printing or flexographic printing. In gravure printing, the ink is diluted with a diluting solvent to a viscosity and concentration suitable for printing, and is supplied to each printing unit either alone or in a mixture.

[0070] (gravure printing) When the ink of the present invention is gravure printed, it is printed using a gravure plate. In the present invention, the gravure plate is a cylindrical metal plate, and recesses of each color are created by engraving, etching, or laser. There are no restrictions on the engraving and laser that can be used, and they can be set arbitrarily to suit the pattern. A line count of 100 to 300 lines per inch is appropriately used, and the higher the line count, the more precise the printing. (gravure printing machine) A suitable printing press is one equipped with the gravure plate. Typically, a printing unit is installed for each color, and each unit is equipped with a doctor blade that scrapes off the ink as the gravure plate rotates. The substrate passes through each printing unit, is intaglio printed, and then is wound into a film. Depending on the circumstances, a furnisher roll can be used for the gravure plate. Each unit is also equipped with a drying oven, through which the printed substrate passes to dry. The drying temperature is typically around 40 to 60°C.

[0071] (Flexographic printing) The plates used for flexographic printing in this invention include photosensitive resin plates that utilize ultraviolet curing using a UV light source and elastomer material plates that use a direct laser engraving method. Regardless of the method for forming the image area of ​​the flexographic plate, plates with a screening line count of 75 lpi or more are used. Any sleeve or cushion tape can be used to attach the plate. (Flexographic printing machine) Flexographic printing presses include CI type multicolor flexographic printing presses and unit type multicolor flexographic printing presses, and ink supply methods include the chamber method and the two-roll method.

[0072] (base material) The ink of the present invention is printed on substrate 1 to produce a printed matter. It is also preferable to form a laminate having substrate 1, a printed layer comprising the ink of the present invention, and substrate 2, in this order, by the method described below. Examples of substrate 1 include polyethylene, polypropylene, and other polyolefin substrates, polycarbonate substrates, polyester substrates (such as polyethylene terephthalate and polylactic acid), polystyrene substrates, polystyrene-based substrates such as AS resin and ABS resin, polyamide substrates, polyvinyl chloride substrates, various polyvinylidene chloride substrates, cellophane substrates, paper substrates, and aluminum foil substrates, as well as film or sheet substrates made from composite materials of these. Among these, polyester substrates and polyamide substrates, which have high glass transition temperatures, are preferably used.

[0073] The substrate 1 is coated with a metal oxide or the like by vapor deposition on its surface and / or coated with polyvinyl alcohol. Examples include GL-AE manufactured by Toppan Printing Co., Ltd., in which aluminum oxide is vapor-deposited onto the substrate surface, and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd. Furthermore, if necessary, those treated with additives such as antistatic agents and ultraviolet inhibitors, and those whose surfaces have been subjected to corona treatment or low-temperature plasma treatment can also be used.

[0074] The base material 2 may be the same as or different from the base material 1. The base material 2 is preferably a thermoplastic base material (sometimes called a sealant), and is preferably an unstretched polyethylene base material, an unstretched polypropylene base material, an unstretched polyester base material, or the like.

[0075] (Laminate) The laminate of the present invention is obtained by providing an adhesive layer on the print layer of a gravure or flexographically printed material, and then laminating the resulting material with a substrate 2. Typical examples of lamination include extrusion lamination, dry lamination, and non-solvent lamination. Extrusion lamination is a method in which an anchor coating agent is applied to the print layer of a printed material, and then molten polyethylene resin, molten polypropylene resin, or the like is extruded onto the layer, simultaneously laminating the material with the substrate. Dry lamination and non-solvent lamination are methods in which an adhesive is applied to the print layer of a printed material, dried, and then laminated with a sealant by thermocompression. The difference between dry lamination and non-solvent lamination is whether or not an organic solvent or other volatile medium is used.

[0076] (adhesive layer) The adhesive layer is made of a composition capable of bonding the ink to the substrate, and examples thereof include a layer formed from molten polyethylene resin, molten polypropylene resin, a urethane adhesive, a layer formed from an acrylic adhesive, and an anchor coat layer. For example, it can be obtained by applying and drying a urethane adhesive. Suitable urethane adhesives include two-component adhesives made from a mixture of polyol and an isocyanate curing agent, and examples of polyols include polyester-based and polyether-based adhesives. Specific examples include TM-250HV / CAT-RT86L-60, TM-550 / CAT-RT37, and TM-314 / CAT-14B manufactured by Toyo-Morton Co., Ltd. [Example]

[0077] The present invention will be described in detail below with reference to examples, but the following embodiments are merely examples of the present invention and the present invention is not limited to these examples. In the present invention, parts and % represent parts by mass and % by mass unless otherwise noted.

[0078] <Method for measuring amine value> The amine value was determined by the following method in accordance with JIS K0070, in terms of the equivalent amount of hydrochloric acid required to neutralize the amino groups contained in 1 g of resin and the equivalent amount of potassium hydroxide in mg. 0.5 to 2 g of sample was precisely weighed out (sample solid content: S g). 50 mL of a 60 / 40 (mass ratio) mixed solution of methanol and methyl ethyl ketone was added to dissolve the precisely weighed sample. Bromophenol blue was added to the resulting solution as an indicator, and the resulting solution was titrated with 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was set as the endpoint, and the titer (A mL) at this point was used to calculate the amine value according to the following (Equation 1). (Equation 1) Amine value = (A × f × 0.2 × 56.108) / S [mg KOH / g]

[0079] <Method for measuring number average molecular weight (Mn) and mass average molecular weight (Mw)> The number average molecular weight (Mn) and mass average molecular weight (Mw) were measured using Showa Denko's GPC (gel permeation chromatography) "Shodex GPC System-21." GPC is a liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in their molecular size. The solvent was tetrahydrofuran, and the molecular weight was determined in terms of polystyrene.

[0080] <Method for measuring hydroxyl value> It was determined according to the method described in JIS K0070.

[0081] <Method for measuring acid value> It was determined according to the method described in JIS K0070.

[0082] <Glass transition temperature> The glass transition temperature was determined from the peak value of the main dispersion of the loss tangent (tanδ) obtained from the temperature dispersion measurement of dynamic viscoelasticity, which was measured using a viscoelasticity measuring device, Viscoelasticity Spectrometer DVA-200 (manufactured by IT Measurement & Control Co., Ltd.), at a frequency of 10 Hz, a heating rate of 10°C / min, and a temperature range of -70 to 200°C.

[0083] <Lamination strength> The printed portion of the laminate was cut to a width of 15 mm, and the ink surface was peeled off from the substrate surface, after which the peel strength (laminate strength) was measured using an Intesco 201 universal tensile tester. Peeling mode: 90° peeling, pulling speed: 300 mm / min

[0084] <Heat seal strength> The printed portion of the laminate was cut out to a size of 15 mm x 100 mm, folded so that the two substrate surfaces overlapped each other, and heat-sealed under the conditions below. The unsealed ends were then fixed to a small tensile tester, and the peel strength (heat-seal strength) was evaluated under the evaluation conditions below. (Heat sealing conditions) Equipment: Heat seal tester manufactured by Tester Sangyo Co., Ltd. Seal width: 10mm from the folded part Heater temperature: 160℃, sealing pressure: 2kg / cm 2 Sealing time: 1 sec (Evaluation conditions) Peeling mode: 90° peeling, pulling speed: 300 mm / min

[0085] [Synthesis Example 1-1] (Synthesis of polyester polyol A1) A round-bottom flask equipped with a stirrer, thermometer, water separator, and nitrogen gas inlet tube was charged with 26 parts neopentyl glycol (NPG), 26 parts 1,3-propanediol (1,3-PD), 8 parts adipic acid, 40 parts sebacic acid, and 0.002 parts tetrabutyl titanate. Esterification was carried out for 8 hours at 230°C under a nitrogen stream while removing the water produced by condensation. After confirming that the acid value of the polyester had reached 15 or less, the vacuum was gradually increased using a vacuum pump to terminate the reaction. This yielded polyester polyol (A1) with a number-average molecular weight of 2000, a hydroxyl value of 56.1 mgKOH / g, and an acid value of 0.3 mgKOH / g.

[0086] [Synthesis Examples 1-2 to 1-10] (Synthesis of polyester polyols A2 to A10) Polyester polyols A2 to A10 were obtained in the same manner as in Synthesis Example 1-1, except that the raw materials and charging ratios shown in Table 1 were used.

[0087] [Table 1]

[0088] [Synthesis Example 2-1] (Synthesis of polyurethane resin B1) A four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 23.1 parts of polyester polyol A1, 0.6 parts of isophorone diisocyanate (hereinafter also referred to as IPDI), 2.3 parts of tolylene diisocyanate (hereinafter also referred to as TDI), and 7.5 parts of ethyl acetate. The mixture was reacted at 120 ° C. for 6 hours under a nitrogen stream, and 7.5 parts of propyl acetate was added and cooled to obtain a solution of a terminal isocyanate prepolymer. The resulting solution of terminal isocyanate prepolymer was then gradually added at room temperature to a mixture of 1.6 parts of isophorone diamine (hereinafter also referred to as IPDA), 0.2 parts of n-dibutylamine (hereinafter also referred to as DBA), 34 parts of ethyl acetate, and 23 parts of isopropyl alcohol (hereinafter also referred to as IPA). The mixture was then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin B1 solution with a solids content of 28%, a weight average molecular weight of 65,000, and an amine value of 5 mgKOH / g.

[0089] [Synthesis Examples 2-2 to 2-16] (Synthesis of polyurethane resins B2 to B16) Polyurethane resins B2 to B16 were obtained in the same manner as in Synthesis Example 2-1, except that the raw materials and charging ratios shown in Tables 2-1 and 2 were used. MDI: Diphenylmethane diisocyanate

[0090] [Table 2-1]

[0091] [Table 2-2]

[0092] [Synthesis Example 3-1] (Synthesis of acidic compound C1) Under a nitrogen atmosphere, 104 parts of polyethylene glycol monomethyl ether (PEG) having a number average molecular weight of 400, 780 parts of polypropylene glycol monomethyl ether (PPG) having a number average molecular weight of 600, 10 parts of ε-caprolactone, and 1.8 parts of dibutyltin laurate were mixed. The reaction was continued at 160°C with heating and stirring until the solid content reached 98% or more, yielding a polyether-polyester monohydroxy block copolymer (number average molecular weight: 900). 900 parts of the polyether-polyester monohydroxy block copolymer was added with 84.5 parts of polyphosphoric acid containing 84% by mass of phosphorus pentoxide, and the mixture was reacted at 80°C for 5 hours while removing water, yielding an acidic compound C1 (solid content 100%, acid group type: phosphate group) with a number average molecular weight of 1,000. Got it.

[0093] [Synthesis Example 3-2] (Synthesis of acidic compound C2) Under a nitrogen atmosphere, 400 parts of polyethylene glycol monomethyl ether (PEG) having a number average molecular weight of 400, 7 parts of ε-caprolactone, and 1.8 parts of dibutyltin laurate are heated. The mixture was stirred and the reaction was continued at 160°C until the solid content reached 98% or more, yielding a polyether-polyester monohydroxy block copolymer (number average molecular weight: 810). Next, 84.5 parts of polyphosphoric acid containing 84% by mass of phosphorus pentoxide was added to 810 parts of the polyether-polyester monohydroxy block copolymer, and the mixture was reacted at 80°C for 5 hours while removing water, yielding an acidic compound C2 (solid content 100%, acid group type: phosphate group) having a number average molecular weight of 950.

[0094] [Synthesis Example 3-3] (Synthesis of acidic compound C3) Under a nitrogen atmosphere, 1150 parts of polypropylene glycol monomethyl ether (PPG) having a number average molecular weight of 1000, 8 parts of ε-caprolactone, and 1.8 parts of dibutyltin laurate were mixed. The mixture was heated and stirred at 160°C, and the reaction was continued until the solid content reached 98% or more, yielding a polyether-polyester monohydroxy block copolymer (number average molecular weight: 1150). Next, 84.5 parts of polyphosphoric acid containing 84% by mass of phosphorus pentoxide was added to 1150 parts of the polyether-polyester monohydroxy block copolymer, and the mixture was reacted at 80°C for 5 hours while removing water, yielding an acidic compound C3 (solid content 100%, acid group type: phosphate group) having a number average molecular weight of 1200.

[0095] [Synthesis Example 3-4] (Synthesis of acidic compound C4) Under a nitrogen atmosphere, 112 parts of polyethylene glycol monomethyl ether (PEG) having a number average molecular weight of 400, 840 parts of polypropylene glycol monomethyl ether (PPG) having a number average molecular weight of 600, 10 parts of ε-valerolactone, and 1.8 parts of dibutyltin laurate were mixed. The reaction was continued at 160°C with heating and stirring until the solid content reached 98% or more, yielding a polyether-polyester monohydroxy block copolymer (number average molecular weight: 1050). Next, 84.5 parts of polyphosphoric acid containing 84% by mass of phosphorus pentoxide was added to 950 parts of the polyether-polyester monohydroxy block copolymer, and the mixture was reacted at 80°C for 5 hours while removing water, yielding an acidic compound C4 (solid content 100%, acid group type: phosphate group) with a number average molecular weight of 1150.

[0096] [Synthesis Example 3-5] (Synthesis of acidic compound C5) Under a nitrogen atmosphere, 1280 parts of polyethylene glycol monomethyl ether (PEG) with a number average molecular weight of 800, 7 parts of ε-caprolactone, 4 parts of ε-valerolactone, and 1.8 parts of dibutyltin laurate were heated and stirred at 160°C, and the reaction was continued until the solids content reached 98% or more, yielding a polyether-polyester monohydroxy block copolymer (number average molecular weight: 1280). Next, 84.5 parts of polyphosphoric acid containing 84% by mass of phosphorus pentoxide was added to 1280 parts of the polyether-polyester monohydroxy block copolymer, and the reaction was continued at 80°C for 5 hours while removing water, yielding an acidic compound C5 with a number average molecular weight of 1350 (solids content: 100%, acid group type: phosphate group).

[0097] [Synthesis Example 3-6] (Synthesis of acidic compound C6) Under a nitrogen atmosphere, polyethylene glycol monomethyl ether (P 26 parts of PEG) and 7 parts of pyromellitic anhydride were heated and stirred at 160°C, and the reaction was continued until the solid content reached 98% or more, yielding a polyether monohydroxy compound (number average molecular weight: 850). Next, 84.5 parts of polyphosphoric acid containing 84% by mass of phosphorus pentoxide was added to 850 parts of the polyether monohydroxy compound, and the reaction was carried out at 80°C for 5 hours while removing water, yielding an acidic compound C6 (solid content 100%, acid group type: phosphate group) with a number average molecular weight of 950.

[0098] [Synthesis Example 3-7] (Synthesis of acidic compound C7) Under a nitrogen atmosphere, 410 parts of polyethylene glycol monomethyl ether (PEG) having a number average molecular weight of 2000 and 22 parts of pyromellitic anhydride were heated and stirred at 160°C, and the reaction was continued until the solid content reached 98% or more, thereby obtaining an acidic compound C7 having a number average molecular weight of 4000 (solid content 100%, acid group type: carboxy group).

[0099] [Example 1] (Ink S1 manufacturing) 30 parts of titanium dioxide pigment (Teika Corporation JR806, rutile-type titanium dioxide surface-treated with silica and alumina, oil absorption 21 g / 100 g), 10 parts of polyurethane resin B1 solution, Vinyl chloride-acrylic copolymer resin solution (VINNOL manufactured by Wacker Chemie) E15 / 40A (vinyl chloride component:acrylic component = 84:16, solid content 24% solution) 6 parts, mixed solvent (ethyl acetate / IPA = 75 / 25 (mass ratio)) 16 parts, stirred and mixed, and then milled in a sand mill, and then mixed with 20 parts of polyurethane resin B1 solution, 17 parts of mixed solvent (ethyl acetate / isopropyl alcohol = 75 / 25 (mass ratio)), 0.1 parts of acidic compound (C1) containing block copolymer, 0.2 parts of fatty acid amide (palmitic acid amide), chlorinated polypropylene 0.3 parts of a resin solution (Nippon Paper Industries 370M solids content 50% solution) was mixed and a white mark was printed. Printing ink S1 was obtained (Tables 3-1 to 3 show the totals of each component).

[0100] [Examples 2 to 28] (Manufacturing inks S2 to S28) Inks S2 to S28 were obtained in the same manner as in Example 1, except that the raw materials and charging ratios shown in Tables 3-1 and 3-2 were used. Phthalocyanine: LIONOLBLUEFG-73 manufactured by Toyo Color Co., Ltd. Nitrocellulose solution: Nitrocellulose solution with a nitrogen content of 11% by mass (solid content 30%, solvent: isopropyl alcohol)

[0101] [Comparative Examples 1 to 6] (Ink SS1 to SS6 manufacturing) Inks SS1 to SS6 were obtained in the same manner as in Example 1, except that the raw materials and charging ratios shown in Table 3-3 were used.

[0102] [Creating printed materials using ink S1] The viscosity of Ink S1 was adjusted by dilution with a mixed solvent (ethyl acetate / IPA = 75 / 25 (mass ratio)) so that the viscosity in Zahn cup #3 (manufactured by Rigo Co., Ltd.) was 15 seconds (at 25°C). Using a gravure proofing machine equipped with a 30 μm deep gravure plate, the ink was printed on the corona-treated side of a single-sided corona-treated polypropylene (OPP) film (Pylen P2161 manufactured by Toyobo Co., Ltd.), and dried at 40 to 50°C to obtain a print using Ink S1.

[0103] [Production of printed matter using inks S2 to S28 and inks SS1 to SS6] Prints were obtained using inks S2 to S28 and inks SS1 to SS6, respectively, in the same manner as in the example of the print using ink S1, except that inks S2 to S28 and inks SS1 to SS6 were used.

[0104] [Preparation of laminate using ink S1] On the printed layer of the print using the ink S1, an adhesive (TM-2 An adhesive solution (non-volatile content 30%) was prepared by mixing 15 parts of PET film (50HV), 1 part of a hardener (CAT-RT86L-60 manufactured by Toyo-Morton Co., Ltd.), and ethyl acetate. The adhesive layer was formed by coating and drying the solution. An unstretched polypropylene (CPP) film (thickness 60 μm, surface corona The laminate was then heated at 40°C for 4 days and then coated with ink S1. A laminate was produced.

[0105] [Preparation of laminates using inks S2 to S28 and inks SS1 to SS6] Except for using the printed matter using inks S2 to S28 and inks SS1 to SS6, the inks S2 to S28 and inks SS1 to SS6 were used in the same manner as the laminate using ink S1. Each of the laminates was prepared using the above materials.

[0106] [evaluation] The above inks S1 to S28 (Examples) and SS1 to SS6 (Comparative Examples), and the laminates using each of them, were evaluated for lamination strength, heat seal strength, plate fogging, plate clogging, and storage stability by the methods described below. The results are shown in Tables 3-1 to 3-3.

[0107] [Laminate strength] The laminate was cut into a piece 150 mm long and 15 mm wide, and the laminate strength in the 90° direction was measured using a tensile tester. (Evaluation criteria) 5: 1.5N / 15mm or more (excellent) 4: 1.0N / 15mm or more, less than 1.5N / 15mm (good) 3: 0.8N / 15mm or more, less than 1.0N / 15mm (acceptable) 2: 0.5N / 15mm or more, less than 0.8N / 15mm (unacceptable) 1: Less than 0.5N / 15mm (poor) The practical level is 3 to 5.

[0108] [Heat seal strength] The laminate was heat-sealed at 160°C with the polyethylene film side facing inwards, and cut into a length of 150 mm and a width of 15 mm, and the heat-seal strength in the 90° direction was measured using a tensile tester. (Evaluation criteria) 5:40N / 15mm or more (excellent) 4: 30N / 15mm or more, less than 40N / 15mm (good) 3: 20N / 15mm or more, less than 30N / 15mm (acceptable) 2: 10N / 15mm or more, less than 20N / 15mm (unacceptable) 1: Less than 10N / 15mm (poor) The practical level is 3 to 5.

[0109] [Plate fogging] The above inks S1 to S28 (Examples) and SS1 to SS6 (Comparative Examples) were diluted with a mixed solvent (ethyl acetate / IPA = 75 / 25 (mass ratio)) so that the viscosity in a Zahn cup #3 (manufactured by Rigo Co., Ltd.) was 15 seconds (at 25°C). The diluted inks were printed on a gravure printing press at a printing speed of 200 m / min and after 60 minutes of idle printing, the state of the plate surface was visually judged. 5: No overlapping at all (Excellent) 4: There is slight plate fogging at the edges of the image (good) 3: There is slight printing fogging on the edges of the image and inside the image (acceptable). 2: There is slight plate fogging at the edges of the image, inside the image area, and in the non-image area (unacceptable) 1: Significant overprinting is observed throughout the entire plate (poor) The practical level is 3 to 5.

[0110] [Plate clogging] Using the above inks S1 to S28 (Examples) and SS1 to SS6 (Comparative Examples), 100 m of each ink was printed on OPP film at a speed of 30 m / 20 min using a gravure plate with a depth of 35 μm on a gravure printing tester (TS-1 type printing machine; manufactured by Azumaya Iron Works). After that, excess ink adhering to the gravure plate was lightly washed off with the above mixed solvent, and the state of clogging of the cell was evaluated. 5: Less than 10% ink remains in the cell 4: Remaining ink in the cell is 10% or more but less than 30% 3: Remaining ink in the cell is 30% or more but less than 50% 2: Remaining ink in the cell is 50% or more but less than 70% 1: More than 70% of the ink remains in the cell The practical level is 3 to 5.

[0111] [Storage stability] The state of pigment sediment was evaluated as a measure of the storage stability of the ink. Specifically, the inks S1 to S28 (Examples) and SS1 to SS6 (Comparative Examples) were stored in sealed 70 cc containers (round bottom, bottom diameter 3 cm) at 40°C for two weeks, and the state of sediment was visually evaluated. 5: No sediment at all 4: A soft precipitate appears at the bottom, but disappears after shaking five times. 3: A soft precipitate appears at the bottom, but disappears after 10 shakes. 2: After shaking 10 times, the remaining precipitate is less than 5 mm in height from the bottom. 1: After shaking 10 times, the remaining precipitate is 5 mm or more in height from the bottom. The practical level is 3 to 5.

[0112] [Table 3-1]

[0113] [Table 3-2]

[0114] [Table 3-3]

Claims

1. A pigment, a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulose-based resin, and an acid and a photogravure or flexographic ink comprising: The acidic compound is a block copolymer having a structure derived from polyether and / or polyester. Gravure or flexographic inks containing polymers.

2. 2. The gravure or flexographic ink of claim 1, wherein the pigment comprises titanium oxide.

3. 3. The gravure or flexographic ink according to claim 1, wherein the polyurethane resin contains a structure derived from a dibasic acid, and the dibasic acid contains sebacic acid.

4. 4. The gravure or flexographic ink according to claim 3, wherein the content of sebacic acid is 50% by mass or more based on the total mass of the dibasic acid.

5. 3. The gravure or flexographic ink according to claim 1, wherein the polyurethane resin contains a structure derived from a polyisocyanate, and the polyisocyanate comprises an aromatic polyisocyanate and an aliphatic polyisocyanate.

6. The content of aromatic polyisocyanate is 50% by mass or more of the total mass of polyisocyanate.

6. The gravure or flexographic ink according to claim 5,

7. 3. The gravure or flexographic ink according to claim 1, further comprising a fatty acid amide.

8. 3. The gravure or flexographic ink according to claim 1, further comprising a chlorinated polypropylene resin.

9. 3. A gravure or flexographic ink according to claim 1, wherein the acidic compound has a phosphoric acid group.

10. 3. A gravure or flexographic ink according to claim 1 or 2, wherein the block copolymer comprises a lactone-derived structure.

11. A printed matter having a printing layer made of the gravure or flexographic ink according to claim 1 or 2 on a substrate 1.

12. A print comprising at least a substrate 1 and the gravure or flexographic ink according to claim 1 or 2. A laminate having a printing layer, and a substrate 2 in this order.

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