JP2017061683A - Printing ink, laminate, packaging container and manufacturing method of laminate, manufacturing method of packaging container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink less in odor, excellent in stability as ink and having good printability because of using a crosslinking agent without using acetylacetone or the like as a ligand.SOLUTION: A printing ink is obtained by blending metal alkoxide and hydroxy acid, wherein the metal alkoxide is metal alkoxide represented by the following formula (1), content of the metal alkoxide is 0.05 to 10 mass% in the printing ink, and content of the hydroxy acid is 0.05 to 10 mass% in the printing ink. In the formula (1), M is any metal atom selected from the Group 4 in the periodic table, and Rto Rrepresent each independently an alkyl group having 1 to 18 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a printing ink for forming a laminate that is applied to a substrate such as paper or plastic film and then laminated.

  Conventionally, printed materials for forms, printed materials for various books, printed materials for packaging such as carton paper, various printed materials for plastics, seals, printed materials for labels, printed materials for arts, printed materials for arts (printed products for art, printed beverages, canned foods, etc.) Various printing methods such as lithographic printing (normal lithographic printing using fountain solution and waterless lithographic printing without using fountain solution), letterpress printing, gravure printing, screen printing, etc. have been adopted to obtain various printed materials. In such printing, ink suitable for each printing method is used. In particular, packaging materials such as foods use packaging materials that use substrates such as various papers and plastic films from the viewpoints of designability, economy, content protection, transportability, etc. As printing inks, lithographic printing ink, gravure printing ink, screen printing ink and the like are known.

  Also, as a packaging material that uses printing ink, when it is used as a packaging container, it can be printed on the front surface or printed on the back surface, and then coated with an adhesive or anchor coat agent to dry laminate. Roughly divided into back-printing, in which resin or film is bonded by processing or extrusion lamination.

  As described above, since such packaging materials are very often used for the purpose of packaging foods, etc., each of the printing inks constituting the packaging materials is a product using materials excellent in environmental hygiene. The manufacturer is working. In particular, although there is an individual difference in odor, a printing ink having a low odor is desired.

  Usually, a printing ink contains a cross-linking agent in order to improve film physical properties or improve the adhesion of a resin or a film by the laminate. However, tetraacetylacetonate titanium, tetraacetylacetonate zirconium, and the like used as useful crosslinking agents coordinate acetylacetone within the structure, which causes odor.

  Patent Document 1 discloses a gravure printing ink for surface printing containing, as a chelate crosslinking agent, zirconium propionate, n-butyl phosphate ester, and one selected from the reaction product of tetraisopropoxytitanium and 2-ethylhexanoic acid. A composition is described, which does not use a metal complex having acetylacetone as a ligand as a crosslinking agent and does not contain an aromatic hydrocarbon-based organic solvent. Although it has excellent film properties such as adhesiveness to heat, heat resistance, oil resistance, and blocking resistance, there is no description or suggestion about odor. There is a tendency that the initial viscosity is increased, and accordingly, the amount of the diluted solvent at the time of printing is increased, and there is a possibility that the density of the printed matter is lowered and the film properties are lowered. It is also clear that there is an example (Example 7) in which the viscosity stability over time is not sufficiently ensured. Furthermore, although n-butyl phosphate ester is said to be useful as a crosslinking agent, it has a problem in terms of environmental hygiene because it has a phosphate structure.

  Patent Document 2 describes a solvent-based printing ink composition for extrusion lamination containing a reaction product of tetraisopropoxytitanium and 2-ethylhexanoic acid and / or zirconium propionate as a chelate crosslinking agent, A metal complex having acetylacetone as a ligand is not used as a cross-linking agent and does not contain an aromatic hydrocarbon organic solvent. It has excellent environmental hygiene, adhesion to plastic films, and excellent laminating properties in extrusion laminating. However, there is no description or suggestion about odor. In addition, it is said that the storage stability of the base ink is excellent, but it is the storage stability of the base ink with high pigment concentration and viscosity (the degree of increase in viscosity is unknown because the original viscosity is unknown). Therefore, there is no description or suggestion of storage stability at a viscosity suitable for printing. If the amount of the diluted solvent is not 70 parts with respect to 100 parts of the base ink, printing cannot be performed and the density may be insufficient. Further, in the extrusion laminating process, the number of steps for applying the anchor coating agent increases.

JP 2013-234238 A JP 2014-127543 A

  Accordingly, the present invention provides a printing ink that has a low odor, has a viscosity that can be adequately applied to printing, has excellent stability over time and re-dissolvability, and is excellent in laminating properties without using an anchor coating agent. The purpose is to do.

  The present inventors have found that the above object can be achieved by using a printing ink comprising a metal alkoxide crosslinking agent and a hydroxy acid, and have completed the present invention.

That is, the present invention
(1) A printing ink comprising a metal alkoxide and a hydroxy acid, wherein the metal alkoxide is a metal alkoxide represented by the following formula (1), and the content of the metal alkoxide is in the printing ink. The printing ink is characterized in that the content of the hydroxy acid is 0.05 to 10% by mass in the printing ink.

［式（１）中、Ｍは、周期表第４族の中から選ばれる何れかの金属原子、Ｒ^１〜Ｒ^４は、それぞれ独立に炭素数１〜１８個のアルキル基を示す。］

[In Formula (1), M is any metal atom selected from Group 4 of the periodic table, and R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 18 carbon atoms. ]

(2) The printing ink according to (1), wherein the metal atom of the metal alkoxide is titanium or zirconium,
(3) The printing according to (1) or (2), wherein the hydroxy acid is at least one selected from the group consisting of α-hydroxy acid, β-hydroxy acid and γ-hydroxy acid. ink,
(4) The hydroxy acid is a compound containing no aliphatic hydrocarbon group having 10 or more carbon atoms, two or more aryl groups, or a polycyclic aromatic hydrocarbon group. (3) the printing ink according to any one of
(5) The printing ink according to any one of (1) to (4), wherein the printing ink is used for an extruded laminate product that does not use an anchor coating agent.
(6) A laminate comprising a substrate and a printing ink layer made of printing ink provided on at least one of the substrates, wherein the printing ink is any one of (1) to (5) A laminate characterized by being a printing ink of
(7) A laminate comprising a substrate, a printing ink layer made of printing ink provided on at least one of the substrates, and a resin layer made of resin, wherein the printing ink is (1) to ( 5) The printing ink according to any one of the above, and a laminate having no anchor coat layer composed of an anchor coat agent between the printing ink layer and the resin layer,
(8) A packaging container produced using the laminate according to (6) or (7),
(9) It is a manufacturing method of the laminated body which consists of a printing process which forms a printing ink layer in at least one of a base material, Comprising: The said printing ink is printing ink in any one of (1)-(5) A method for producing a laminate,
(10) A method for producing a laminate comprising a printing step of forming a printing ink layer on at least one of a substrate and a coating step of forming a resin layer on the surface of the printing ink layer, wherein the printing ink is (1 ) To (5), the printing ink layer printing step, and an application step of forming an anchor coat layer by applying an anchor coating agent between the printing layer printing step and the resin layer coating step. A method for producing a laminate, characterized by not having
(11) A method for producing a packaging container comprising a molding step for molding a laminate, wherein the laminate is a laminate according to (6) or (7),
It is about.

  According to the present invention, since a cross-linking agent that does not use acetylacetone or the like as a ligand is used, there is little odor, excellent stability as an ink, good printability, and an anchor coating agent is used. A printing ink that can be laminated without any problems can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. The present embodiment is merely one form for carrying out the present invention, and the present invention is not limited by the present embodiment, and various modifications and embodiments are possible without departing from the gist of the present invention. Is possible.

  The printing ink of the present invention (hereinafter also simply referred to as “ink”) is preferably formed by blending a metal alkoxide and a hydroxy acid.

  The metal alkoxide is preferably a metal alkoxide represented by the following formula (1).

［式（１）中、Ｍは、周期表第４族の中から選ばれる何れかの金属原子、Ｒ^１〜Ｒ^４は、それぞれ独立に炭素数１〜１８個のアルキル基を示す。］

[In Formula (1), M is any metal atom selected from Group 4 of the periodic table, and R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 18 carbon atoms. ]

  In the metal alkoxide represented by the formula (1), titanium, zirconium and hafnium are preferable as the metal atom represented by M in the formula (1), and titanium or zirconium is particularly preferable.

In the metal alkoxide represented by the formula (1), R ^{1 to} R ⁴ in the formula (1) are each independently preferably an alkyl group having 1 to 18 carbon atoms, and each independently having 1 to 10 carbon atoms. An alkyl group is more preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable. These are particularly preferable in that high crosslinking reactivity can be obtained. When the number of carbon atoms exceeds 18, the reactivity becomes poor, which is not preferable.

  Examples of M that is titanium include tetramethoxide titanium, tetraethoxide titanium, tetra n-propoxide titanium, tetraisopropoxide titanium, tetra n-butoxide titanium, tetraisobutoxide titanium, diisopropoxide di-n-butoxide titanium. Di-tert-butoxydiisopropoxide titanium, tetra-sec-butoxide titanium, tetra-tert-butoxide titanium, tetra-2-ethylhexoside titanium, tetraoctyloxide titanium, tetraisooctyloxide titanium, tetrastearyl alkoxide titanium Etc. Examples of M as zirconium include tetramethoxide zirconium, tetraethoxide zirconium, tetra n-propoxide zirconium, tetraisopropoxide zirconium, tetra n-butoxide zirconium, tetraisobutoxide zirconium, diisopropoxide di- Examples include butoxide zirconium, di tert-butoxy diisopropoxide zirconium, tetra sec-butoxide zirconium, tetra tert-butoxide zirconium, tetra 2-ethylhexoside zirconium, tetraisooctyloxide zirconium, tetrastearyl alkoxide zirconium and the like. Among them, tetraethoxide titanium, tetra n-propoxide titanium, tetraisopropoxide titanium, tetra n-butoxide titanium, tetraisobutoxide titanium, tetra 2-ethylhexoside titanium, tetraoctyloxide titanium, tetraisooctyl Roxide titanium, tetra n-propoxide zirconium, tetraisopropoxide zirconium, tetra n-butoxide zirconium, tetraisobutoxide zirconium, tetra-2-ethylhexoside zirconium, tetraoctyloxide zirconium, tetraisooctyloxide zirconium More preferred. These can be used alone or in admixture of two or more.

  The content of the metal alkoxide is preferably 0.05 to 10% by mass in the ink, more preferably 0.1 to 5% by mass, and 0.5 to 3% by mass. Further preferred. If the amount is less than 0.05% by mass, the effect of improving the adhesiveness of the laminate is small because the number of crosslinking points is small. Become.

  The hydroxy acid is a compound having a carboxylic acid group and at least one hydroxyl group, an α-hydroxy acid having a hydroxyl group bonded to the α-position, a β-hydroxy acid having a hydroxyl group bonded to the β-position, and a γ-position. There are γ-hydroxy acids and the like to which a hydroxyl group is bonded, and preferably at least one selected from the group consisting of α-hydroxy acids, β-hydroxy acids, and γ-hydroxy acids. Moreover, it is preferable that there is one carboxylic acid group in the molecule. Such a hydroxy acid is considered that a hydroxyl group of a carboxylic acid group forms a complex with a metal atom of a metal alkoxide or coordinates. Among these, α-hydroxy acids are preferable because they are very stable because a metal atom is sandwiched between a hydroxyl group located at the α-position and a hydroxyl group of a carboxylic acid to form a five-membered ring complex.

  Examples of α-hydroxy acids include citric acid, DL-lactic acid, glyceric acid, isocitric acid, homocitric acid, 2-hydroxybutyric acid, 2-hydroxyisobutyric acid, DL-malic acid, tartaric acid, DL-mandelic acid, m- Hydroxymandelic acid, leucine acid, citramalic acid, tartronic acid, pantoic acid, α-phenyllactic acid, benzylidenelactic acid, glycolic acid, benzylic acid, benzylglycolic acid, quinic acid, 2-hydroxyvaleric acid, 2-hydroxyisovaleric acid, 2-hydroxycaproic acid, 2-hydroxyenanthic acid, 2-hydroxycaprylic acid, α-hydroxyisocaprylic acid, 2-hydroxypelargonic acid, 2-hydroxycapric acid, 2-ethyl-2-hydroxybutyric acid, 2-hydroxy- 2-methylbutyric acid, 2-ethyl-2-hydroxy-3-methylbuta Acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-2,3-dimethylbutanoic acid, 2-hydroxy-2,3,3-trimethylbutanoic acid, 2-hydroxy-3-methylvaleric acid, 2 -Hydroxy-2-ethylpentanoic acid, 2-hydroxy-2-methylpentanoic acid, 2-hydroxy-2,4-dimethylvaleric acid, 2-hydroxy-2-propylpentanoic acid, 2-hydroxy-4-oxopentanoic acid 2-hydroxy-4-methyl-3-oxopentanoic acid, α-hydroxyisocaproic acid, 2-hydroxy-2-methylhexanoic acid, 3-methyl-2-hydroxyhexanoic acid, 2-hydroxy-3-oxohexane Acid, 2-hydroxy-4-oxohexanoic acid, 2-hydroxy-5-oxohexanoic acid, 2-hydroxy-2-methylheptanoic acid 3-ethyl-2-hydroxyheptanoic acid, 2-hydroxy-2-methyloctanoic acid, 3-hydroxy-4-methoxymandelic acid, vanillylmandelic acid, 4-methoxymandelic acid, α-cyclohexylmandelic acid, 3-phenyl- D-lactic acid, 4-hydroxyphenyl lactic acid, β-naphthoxy lactic acid, 2- (2-naphthyl) -2-hydroxypropanoic acid, 2-hydroxy-2- (4-methylphenyl) propanoic acid, 2-hydroxy-3- (2-hydroxyphenyl) propanoic acid, 2-hydroxy-3- (4-hydroxyphenyl) propionic acid, 2-hydroxy-3- (2-methylphenoxy) propanoic acid, 2-hydroxy-3-phenylbutanoic acid, 2 -Hydroxy-4-phenylbutanoic acid, α-phenyl-α-hydroxybenzenepropanoic acid, 2- Dorokishi 4-phenyl pentanoic acid, 2-hydroxy-5-phenyl-pentanoic acid. Of these, citric acid, DL-lactic acid, glyceric acid, 2-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxyisovaleric acid, DL-malic acid, and DL-mandelic acid are more preferable.

  Examples of β-hydroxy acids include 3-hydroxybutyric acid, β-lactic acid, 3-hydroxyisobutyric acid, 2- (hydroxymethyl) butyric acid, tropic acid, nilic acid, salicylic acid, mevalonic acid, shikimic acid, 3-phenylsalicylic acid 3,5-dimethylsalicylic acid, 3,6-dimethylsalicylic acid, 4,5-dimethylsalicylic acid, 3-isopropylsalicylic acid, 3,5-dipropylsalicylic acid, 3-hydroxysalicylic acid, hydroxypivalic acid, dimethylolpropionic acid, 3 -Hydroxy-2,2-bis (hydroxymethyl) propionic acid, 2- (hydroxymethyl) -3-hydroxypropionic acid, 3-hydroxyvaleric acid, 3-hydroxyisovaleric acid, 3-hydroxycaproic acid, 3-hydroxy Enanthic acid, 3-hydroxycaprylic acid, 3-hydroxypelral Gonic acid, 3-hydroxycapric acid, 3-hydroxy-3-methylvaleric acid, 2-methyl-3-hydroxypentanoic acid, 3-hydroxy-4-methylpentanoic acid, 3-hydroxy-2,4-dimethylpentanoic acid 2-propyl-3-hydroxypentanoic acid, 3-hydroxy-4-oxopentanoic acid, 3-hydroxy-3-methyl-2-oxopentanoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-4 -Methylhexanoic acid, 3-hydroxy-5-methylhexanoic acid, 3-hydroxy-5-oxohexanoic acid, 3-hydroxy-3-methylheptanoic acid, 3-hydroxy-3-allylheptanoic acid, 2-butyl-3 -Hydroxyoctanoic acid, 3-hydroxy-4-phenylbutyric acid, 3-hydroxy-3-phenylpropionic acid, 3-hydride Xy-3,3-diphenylpropionic acid, 3-hydroxy-3- (2-naphthyl) propionic acid, 3-hydroxy-5-phenylvaleric acid, 3-hydroxy-3-methyl-2-phenylpentanoic acid, 3- Hydroxy-5- (4-hydroxyphenyl) pentanoic acid, 3-hydroxy-2- (4-biphenylyl) pentanoic acid, 3-hydroxy-4-methyl-2- (4-biphenylyl) pentanoic acid, 3-hydroxy-6 -Phenylhexanoic acid and the like. Of these, 3-hydroxybutyric acid, β-lactic acid, 3-hydroxyisobutyric acid, and tropic acid are more preferable.

  Examples of γ-hydroxy acids include succinic acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 4-hydroxyisovaleric acid, 4-hydroxycaproic acid, 4-hydroxyenanthic acid, 4-hydroxycaprylic acid, 4- Hydroxypelargonic acid, 4-hydroxycapric acid, m-salicylic acid, 4-hydroxy-2-hydroxymethylbutyric acid, 4-hydroxy-4-phenylbutyric acid, 2-propyl-4-hydroxyvaleric acid, 4-hydroxy-4-methyl Pentanoic acid, 3-methyl-4-hydroxyoctanoic acid, 2-phenyl-4-hydroxyoctanoic acid and the like are preferable. Of these, succinic acid and 4-hydroxybutyric acid are more preferable.

  These can be used alone or in admixture of two or more. In particular, a compound that does not contain any of an aliphatic hydrocarbon group having 10 or more carbon atoms, two or more aryl groups, or a polycyclic aromatic hydrocarbon group is more preferable. By using such a hydroxy acid, an increase in viscosity can be suppressed and stability over time can be obtained.

  The content of the hydroxy acid is preferably 0.05 to 10% by mass, more preferably 0.3 to 5% by mass, and 0.5 to 3% by mass in the ink. Further preferred. If it is less than 0.05% by mass, the effect of suppressing the reaction during storage is small, and if it is more than 10% by mass, it is difficult to dissolve in ink.

  Moreover, it is preferable to contain alcohol. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol and the like. Of these, methanol, ethanol, n-propanol, and isopropanol are more preferable. These can be used alone or in admixture of two or more. By including the alcohol, gelation (abrupt increase in viscosity) due to the reaction between the resin and the metal alkoxide can be suppressed.

  The alcohol is preferably 1 to 40% by mass in the ink, more preferably 3 to 30% by mass, and still more preferably 5 to 25% by mass. If the amount is less than 1% by mass, the reaction between the resin and the metal alkoxide cannot be suppressed, which may cause a sudden increase in viscosity. If the amount exceeds 40% by mass, depending on the resin in the ink, poor dissolution may occur. There is a fear.

  Moreover, it is preferable to contain glycol ether. Examples include aliphatic glycol ethers, aromatic glycol ethers, and ester glycol ethers. Examples of aliphatic glycol ethers include ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, Ethylene glycol mono-tert-butyl ether, ethylene glycol tert-butyl ethyl ether, ethylene glycol tert-butyl methyl ether, ethylene glycol mono 2-ethylbutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol dimethyl ether , Ethylene glycol di Chill ether, ethylene glycol dibutyl ether, ethylene glycol diisobutyl ether, ethylene glycol di sec-butyl ether, ethylene glycol di tert-butyl ether, ethylene glycol diglycidyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monopropyl ether , Diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol dimethyl ether, diethylene glycol tert-butyl methyl ether, triethylene glycol monomethyl ether, triethylene glycol Noethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monoisobutyl ether, triethylene glycol mono-sec-butyl ether, triethylene glycol mono-tert-butyl ether, triethylene glycol Ethylene oxide modified glycol ethers such as ethylene glycol glycidyl methyl ether and tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, dipropylene Glico Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monohexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monopropyl ether, triisopropylene glycol monomethyl ether And propylene oxide-modified glycol ethers such as tetrapropylene glycol monomethyl ether. Examples of aromatic glycol ethers include ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono-o-tolyl ether, ethylene glycol mono-m-tolyl ether, ethylene glycol mono-p-tolyl ether, ethylene Examples include glycol dibenzyl ether, diethylene glycol monophenyl ether, diethylene glycol diphenyl ether, and propylene glycol monophenyl ether. Examples of ester glycol ethers include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, etc. Is mentioned. Of these, propylene glycol monomethyl ether is more preferable.

  The glycol ether is preferably 0.1 to 20% by mass in the ink, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass. If the amount is less than 0.1% by mass, the effect of suppressing the drying property of the ink is small, and troubles are likely to occur at the time of production or printing due to the dry solid matter of the ink. Printing defects such as show-through and blocking may occur, and dissolution failure may occur depending on the resin in the ink.

  The resin used in the ink of the present invention can be selected according to the purpose, application, etc., and preferably contains at least one such as a thermoplastic resin or a curable resin. More specifically, a thermoplastic resin containing a hydroxy group in the molecule is more preferable.

The thermoplastic resin containing a hydroxy group in the molecule is a cellulose derivative such as nitrocellulose, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, a urethane resin containing a hydroxy group, a rosin-modified phenol resin, or the like. Is preferred. As for the molecular weight and the degree of substitution of the cellulose derivative, those in the range used in ordinary paints and inks can be used without any problem, but those having a hydroxy group in the molecule and having a degree of substitution of about 30 to 85%. preferable. In the case of gravure ink, nitrocellulose is particularly preferable from the viewpoint of heat resistance. Nitrocellulose is a nitro group-substituted cellulose resin in which a part of hydroxyl groups of a cellulose skeleton is nitrated. Although general nitrocellulose can be used without any problem, an average of 1.3 to 2.7 nitro groups is substituted per glucose unit constituting the cellulose skeleton. It is more preferable that it is 1.9-2.3.
Generally, a thermoplastic resin containing a hydroxyl group in the molecule is highly reactive, so it reacts with the metal alkoxide during drying and starts to gel rapidly, so the (initial) viscosity rises or gels rapidly. Even if there is no ink, the re-solubility becomes worse due to quick drying, and the dried ink may accumulate on the plate or doctor blade during printing, resulting in foreign matter, or the gravure plate may become clogged and blurred. However, by adding the hydroxy acid of the present invention, gelation is suppressed and re-solubility is improved.

  In particular, the combined use of the cellulose derivative and the urethane resin is preferable in terms of adhesion to the substrate of gravure ink, blocking resistance, oil resistance, and heat resistance. The mixing ratio of the cellulose derivative and the urethane resin is preferably cellulose derivative: urethane resin = 100: 0 to 60:40, more preferably cellulose derivative: urethane resin = 95: 5 to 65:35, cellulose It is more preferable that it is derivative | guide_body: urethane resin = 85: 15-70: 30. By being in this range, the laminate on the ink film, particularly the extrusion laminate adhesion is excellent.

  A curable resin (thermosetting, photocuring, electron beam curable, etc.) is also preferable. Curing resins include polyester (meth) acrylate resin, epoxy (meth) acrylate resin, urethane (meth) acrylate resin, polyether (meth) acrylate resin, diallyl phthalate resin, phenol resin, melamine resin, epoxy resin, urea resin , Unsaturated polyester resin, silicon resin, urethane resin and the like.

  Further, other thermoplastic resins may be included. Other thermoplastic resins may be used as long as good adhesiveness can be obtained. For example, shellacs, rosins, chlorinated rubber, cyclized rubber, vinyl chloride, vinylidene chloride, polyamide resin, vinyl chloride-vinyl acetate. Copolymer, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, acrylic resin, ethylene-vinyl alcohol resin, styrene maleic acid resin, casein And thermoplastic resins such as alkyd resins, which may be used alone or in combination of two or more. Properties such as those in which these resins are dissolved in a solvent, those in which they are dissolved in water, or emulsion types in which they are dispersed in water, such as acrylic emulsions, urethane emulsions, polyvinyl alcohol resins, ethylene-vinyl alcohol emulsions, and polypropylene emulsions. Is mentioned.

  The content of the resin as a whole is preferably 1 to 70% by mass in terms of solid content in the ink, more preferably 2 to 65% by mass, and still more preferably 3 to 60% by mass. When the amount is less than 1% by mass, sufficient adhesion cannot be obtained. When the amount is more than 70% by mass, the solid content is too high, the viscosity becomes high, and the coating is difficult.

  Furthermore, other solvents may be included, and any other solvent may be used as long as it dissolves or disperses the resin in the solvent. Those usually used in the gravure ink are of an organic solvent type or an aqueous type, and examples thereof include an organic solvent and / or water. Those usually used in the offset ink are of an organic solvent type or an oil type, and include petroleum solvents and vegetable oils. Those usually used in the photocurable ink are monomers or oligomers, and examples thereof include (meth) acrylic acid alkyl esters, phenoxyalkyl esters, alicyclic alkyl esters, and alkoxyalkyl esters.

  Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, methanol, ethanol, isopropyl alcohol (IPA), and normal propyl alcohol. , Alcohol solvents such as 1-butanol, 2-butanol, isobutanol, tert-butanol, esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate Solvents, acetone, methyl ethyl ketone (MEK), ketone solvents such as methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol ether solvents such as ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and esterified products thereof. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Such as chromatography monoethyl ether acetate. In order to suppress odor, it is preferable not to contain an aromatic hydrocarbon solvent or a ketone solvent.

  Petroleum solvents include aroma-free solvents, normal paraffin solvents, isoparaffin solvents, machine oil, cylinder oil, and vegetable oils such as soybean oil, linseed oil, rapeseed oil, coconut oil, olive oil, and tung oil. Processed ones, fatty acid esters derived from these vegetable oils, vinylidene olefins and the like can be mentioned.

  Monomers or oligomers include phenoxyethyl acrylate, cyclohexyl (meth) acrylate, ethoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, butylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated glycerin triacrylate, ditrimethylolpropane tetra ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentahexa (meth) acrylate, trimethylolpropane 3EO modified tri (meth) acrylate, bisphenol A4EO modified Di (meth) acrylate, bisphenol A10EO modified di (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, trimethylolpropane 9EO modified tri (meth) acrylate, trimethylolpropane 3PO modified tri (meth) acrylate, pentaerythritol EO modified tetra (meth) acrylate, epoxidized soybean oil (meth) acrylate, polyester (Meth) acrylates such as (meth) acrylate, vinyl-2-chloroethyl ether, vinyl-normal butyl ether, 1,4-cyclohexanedimethanol divinyl ether, vinyl glycidyl ether, bis (4- (vinyloxymethyl) cyclohexylmethyl ) Glutarate, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl Ether, adipic acid divinyl ester, tris (4-vinyloxy) butyl trimellrate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butyl isophthalate, ethylene glycol divinyl ether, 1,4-butane Diol divinyl ether, nonanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylol propane divinyl ether, trimethylol propane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythrine Vinyl ethers such as lithol divinyl ether, pentaerythritol trivinyl ether, cyclohexanedimethanol divinyl ether, ethylene oxide modified trimethylolpropane divinyl ether, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3- (phenoxymethyl) oxetane 3,3-diethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, di ((3 -Oxetanes such as ethyl-3-oxetanyl) methyl) ether and pentaerythritol tetrakis ((3-ethyl-3-oxetanyl) methyl) ether, 1,4-butanediol diglycidyl ether, 1,2-epoxy 4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4′-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether , Triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol -A-diglycidyl ether, bisphenol-S-diglycidyl ether, pentaerythritol tetraglycidyl ether, resorcinol diglycidyl ether, phthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobisphenol -A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, hydrogenated bisphenol-A-diglycidyl ether, tris- (2,3-epoxypropyl) isocyanurate, 1- {2,3 -Di (propionyloxy)}-3,5-bis (2,3-epoxypropyl) -1,3,5-triazine-2,4,6. (1H, 3H, H) -trione, 1,3-bis {2,3-di (propionyloxy)}-5- (2,3-epoxypropyl) -1,3,5-triazine-2,4,6. (1H, 3H, 5H) -trione, monoallyl diglycidyl isocyanurate, diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, tri Methylolpropane polyglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, adipine Diglycidyl ether, o-phthalic acid diglycidyl ether, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, 4,4′-bis (2 , 3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyl Oxirane, 2- (3,4-epoxycyclohexyl) -3 ′, 4′-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy-bis (3,4-epoxycyclohexylmethane) 4 ', 5'-epoxy- 2′-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), bis- (3,4-epoxycyclohexylmethyl) adipate, bis ( Epoxys such as 2,3-epoxycyclopentyl) ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 2- (3,4-epoxycyclohexyl) -3 ′, 4′-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy-bis (3,4-epoxycyclohexylmethane), 4 ′, 5′-epoxy-2′- Methylcyclohexylmethyl-4,5 Fats such as epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), bis- (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether Examples thereof include cyclic epoxies.

  The content of the alcohol, glycol ether and other solvents as a whole is preferably 10 to 95% by mass in the ink, and more preferably 20 to 85% by mass. If the amount is less than 10% by mass, sufficient printability cannot be obtained. If the amount is more than 95% by mass, the solid content decreases and the density decreases.

  If necessary, a curing agent can be added to the ink of the present invention. For example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexyl diisocyanate and their trimethylolpropane Polyisocyanate curing agents such as modified products such as trimers, isocyanurates, burettes, and allophanates can be used, and these can be used alone or in combination of two or more.

  If necessary, a photopolymerization initiator can be added to the ink of the present invention. For example, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4 -(4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4,4′-bis ( Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, phenylglyoxylic acid methyl ester, 2,2-dimethoxy-1,2-diphenylethane-1 -One, oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxy Mixture of ethoxy] ethyl ester and oxyphenylacetic acid, 2- [2-hydroxyethoxy] ethyl ester, 2,4-diethylthioxanthone, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 2-ethylhexyl acid, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, 2-methyl-1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 4-phenylbenzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propane -1-one, 4-benzoyl-4′-methyldiphenyl sulfide, bis (η5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, 1,2-octanedione, 1- [4- (phenylthio) )-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl (2 -Hydroxy-2-propyl) ketone, benzophenone, trimethylbenzophenone, methylbenzophenone, isopropylthioxanthone, o-benzoylbenzoate 4-phenylbenzophenone, 4-, 4′-dichlorobenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl- 4-methoxybenzophenone, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, Michler's ketone, trimethylbenzophenone, methylbenzophenone mixture, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, L- Chloroform-4-propoxythioxanthone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, L-phenyl-2-hydroxy-2-methylpropano 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer Photo radical generators such as boron tetrafluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium salt, tetrafluoride Tri-4-methylphenylsulfonium salt of antimony fluoride, diphenyliodonium salt of tetrakis (pentafluorophenyl) boron, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, etc. of A photo-acid generator is mentioned, These can be used 1 type or in combination of 2 or more types.

  Furthermore, a sensitizer can also be added as needed. For example, amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy) and the like can be mentioned. These can be used alone or in combination of two or more.

  Furthermore, the ink of the present invention preferably contains a pigment. Examples of the pigment include organic pigments, inorganic pigments, various fluorescent pigments, metal powder pigments, extender pigments, and the like, such as phthalocyanine-based, insoluble azo-based, condensed azo-based, dioxazine-based, anthraquinone-based, quinacridone-based, perylene-based, and perinone. Organic pigments such as thioindigo, titanium oxide, dial, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, pearl, aluminum, carbon black, etc. And is not particularly limited. These pigments may be used alone or in combination of two or more.

  Moreover, it is preferable that the ink of the present invention is used for an extruded laminate product that does not use an anchor coat agent. Originally, the anchor coating agent has been used for the purpose of improving adhesion and laminating suitability during extrusion laminating, but the anchor coating agent itself has been pointed out to be harmful or changed to a less harmful anchor coating agent. However, although there was a problem that the laminate strength as an extruded laminate product was lowered, the ink of the present invention has sufficient adhesion to the printing ink layer surface and laminate strength without using an anchor coating agent. An extrusion laminate processed product that can be secured can be produced, and an application step of applying an anchor coating agent to form an anchor coat layer is not required.

  It is preferable that the laminated body of this invention is equipped with a base material and the printing ink layer which consists of printing ink provided in at least one of this base material.

  The printing ink layer is preferably provided by a silk screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, or a knife jet coater method. Of these, the gravure printing method, flexographic printing method or silk screen printing method is preferably used because of its high quality and high productivity, and the gravure printing method is more preferable, especially the gravure printing method using a multicolor gravure printing machine. Is more preferable.

  It is preferable to obtain a printing ink layer by providing the ink of this invention so that a film thickness may be set to 0.01-10 micrometers in at least one of a base material. When the film thickness is smaller than 0.01 μm, it is difficult to obtain a sufficient concentration, and when the film thickness is larger than 10 μm, it is difficult to provide a printing ink layer and blocking occurs.

  The base material preferably includes at least one selected from paper, aluminum foil, a plastic film or sheet and a laminate having heat-sealing properties thereof. The base material may be laminated by a method using a thermoplastic resin or the like by dry lamination, non-solvent lamination or extrusion lamination, a method of bonding through an adhesive, or the like, or a combination of these appropriately It may be. Moreover, the laminated body which provided heat sealability can also be used as a base material. Examples of methods for imparting heat-sealability include known sealant film bonding, resin coating by extrusion lamination, heat-sealable resin processing by heat-sealant or hot-melt coating or co-extrusion, and the like. A layer to which heat sealability is imparted by a method is also referred to as a heat seal layer. Although there will be no restriction | limiting in particular if the thickness of a base material is in the range which does not have trouble in printability, winding-up property, etc., 5-300 micrometers is preferable and 6-250 micrometers is more preferable.

  Moreover, the laminated body of this invention can also be set as an adhesive tape by forming an adhesive layer and an adhesive layer on the base material of the other surface in which the printing ink layer was formed, and also forming a mold release layer. Any adhesive layer or adhesive layer may be used as long as it is in close contact with the base material layer and the release layer, such as a rubber adhesive material and an acrylic resin adhesive material, and the release layer can be easily peeled off. The release layer may be a polyethylene film, a polyester film, or paper (release paper).

  The laminate of the present invention comprises a base material, a printing ink layer made of printing ink provided on at least one of the base materials, and a resin layer made of resin, and includes the printing ink layer and the resin layer. It is preferable not to have an anchor coat layer made of an anchor coat agent in between. More specifically, a printing ink layer can be obtained by dry laminating, non-solvent laminating, wet laminating or heat laminating a resin-containing adhesive, extruding laminating resin, or laminating via an adhesive. Apply resin directly on top. In particular, an extrusion laminate obtained by melting a resin is more preferable. Further, two or more layers of resins may be stacked and extrusion laminated. In this case, the resin used may be the same type or a different type of resin. In this way, it is most preferable to apply the resin directly on the printing ink layer by extrusion lamination. Extrusion laminating processing is possible because sufficient adhesion and lamination strength with the printing ink layer can be secured without having an anchor coat layer. Can be used for goods. However, you may have an anchor coat layer which consists of an anchor coat agent on a printing ink layer, and it does not exclude providing a resin layer on this anchor coat layer by extrusion lamination.

  The resin used for the extrusion laminate is polyethylene resin, polypropylene resin, mixed resin of polyethylene and polypropylene, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid copolymer resin, ethylene- (meth) acrylic acid methyl copolymer. Resin, ethyl ethylene- (meth) acrylate copolymer resin, ethylene-vinyl alcohol copolymer resin, polyamide resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyester acrylate resin, epoxy acrylate resin, Urethane acrylate resin, polyether acrylate resin, diallyl phthalate resin, nitrocellulose resin, polyurethane resin, polyester resin, acrylic resin, chlorinated polyolefin resin, vinyl chloride-vinegar Vinyl copolymer preferably contains at least one rosin-based resin. Moreover, the same kind of resin as the base material or a different kind of resin may be used.

  The film thickness by lamination is not particularly limited, but the film thickness by extrusion lamination is preferably 1 to 100 μm from the viewpoints of coatability, cost, and productivity. The film thickness of the film or sheet laminate is preferably 2 to 200 μm.

  It is preferable that the manufacturing method of the laminated body of this invention consists of a printing process which forms a printing ink layer in at least one of the said base materials.

  The printing process for forming the printing ink layer is applied to at least one surface of the substrate by a known printing process or a process such as coating, spraying, or dipping to form a printing ink layer. Examples of the printing process include printing processes such as a silk screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, and a knife jet coater method. Of these, the gravure printing method, flexographic printing method or silk screen printing method is preferably used because of high quality and high productivity, and the gravure printing method is more preferable, especially the gravure printing method using a multicolor gravure printing machine. More preferably. More specifically, a printing ink layer may be formed by a gravure printing method after creating a laminated substrate by the above-described lamination method, but gravure printing is performed on one side of the base material layer that serves as a base. After forming the printing ink layer by the method, another substrate may be formed on the other side different from this by the laminating method described above. Moreover, you may provide the said printing ink layer on both surfaces of a base material.

  Furthermore, the method for producing a laminate of the present invention preferably comprises a printing step for forming a printing ink layer on at least one of the substrates, and a coating step for forming a resin layer on the surface of the printing ink layer. More preferably, there is no application step of forming an anchor coat layer by applying an anchor coat agent between the layer printing step and the resin layer application step. This eliminates the need for an application step of applying the anchor coat agent to form the anchor coat layer.

  The laminate of the present invention is for packaging, food preservation, agriculture, civil engineering, fishery, automotive interior and exterior use, marine use, daily necessities, building material interior and exterior use, housing equipment use, medical / medical equipment use, and pharmaceutical use. It can be used for household appliances, furniture, stationery and office supplies, sales promotion, commercial, electrical and electronics industries, and industrial materials.

The packaging container of the present invention is preferably prepared using the laminate.
Especially, it can use preferably as a packaging container of various forms for food packaging. There are two types of packaging containers: two-way seal, three-side seal, four-side seal, pillow seal, standing pouch, envelope attachment, gusset, fusing seal, tube, caramel packaging, overhold, fin seal, steamed packaging, twist, rocket, tetra Any of well-known forms used for food packaging applications such as packs, gable tops, bricks, shibori, cups, trays, bottles, bricks, containers, boxes, cases, weights, covers, lids, caps and labels may be used.

Such a packaging container is required to have functions such as designability, economy, content protection, and transportability, and when printing is performed on the above-described various substrates or when the printing surface becomes the inner surface (back printing). In order to protect the printing surface, it is preferable to perform laminating so as not to directly touch the contents or when the printing surface becomes the outer surface (surface printing).
In particular, it is preferable to use the printing ink of the present invention for a packaging container whose contents are food, because odor is suppressed.

  It is preferable that the manufacturing method of the packaging container of this invention consists of a formation process which shape | molds the said laminated body.

  The molding process may be any food packaging container that is preferably used. Two-side seal, three-side seal, four-side seal, pillow seal, standing pouch, envelope sticker, gusset, fusing seal, tube, caramel packaging, overhold , Fin seal, bun packaging, twist, rocket, tetrapack, gable top, brick, shibori, cup, tray, bottle, brick, container, box, case, watch weight, cover, lid, cap, label, etc. Any of the well-known container forming steps used may be used.

  The printing ink can be produced by a known method by uniformly dissolving or dispersing a pigment, resin, metal alkoxide, hydroxy acid, various additives, and the like in a solvent. Dissolver or disperser is various agitators or dispersers such as dissolver, roll mill, ball mill, bead mill, sand mill, attritor, paint shaker, agitator, Henschel mixer, colloid mill, pearl mill, ultrasonic homogenizer, wet jet mill, kneader, homomixer, etc. You can use the machine. These devices may be used alone or in combination of two or more. When bubbles or coarse particles are contained in the printing ink, it is preferable to remove them using a known filter or centrifuge in order to reduce the printability and the quality of the printed matter.

The viscosity of the printing ink is not particularly limited as long as it does not interfere with printing. Considering the production suitability and handling of printing inks used in gravure printing and flexographic printing, it is preferably 10 to 1,000 mPa · s at 25 ° C. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone plate viscometer. The measurement conditions are appropriately set according to the viscosity of the printing ink. For example, using a cone plate viscometer TV-22 (manufactured by Toki Sangyo Co., Ltd.) equipped with a standard cone rotor (1 ° 34 ′ × R24), a viscosity of 60 mPa · s or less has a shear rate of 192 sec ^−1. The viscosity of greater than 60 mPa · s at a rotational speed of 50 rpm and less than or equal to 150 mPa · s is a shear rate of 77 sec ⁻¹ , and the viscosity of greater than 150 mPa · s at a rotational speed of 20 rpm is a shear rate of 9.6 sec ⁻¹ and a rotational speed of 2 It can be measured at 5 rpm. Moreover, in the printing ink used by offset printing, it is preferable that it is 5-50 Pa.s at 25 degreeC. In this case, it can be measured using a commercially available viscometer such as an L-type viscometer, an LA-type viscometer or a cone plate viscometer.

  Printing ink used in gravure printing and flexographic printing can be applied as it is, but depending on the coating conditions and coating effect, with Zahn Cup # 3 (manufactured by Chugai Co., Ltd.) It can be used by adjusting to a desired viscosity by dilution. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C.

  The dilution solvent may be any one as long as it can be used by adjusting the viscosity of the printing ink, and examples thereof include organic solvents and water, and commercially available ones can also be used. Commercially available products include WA735 (alcohol solvent), TA52 (alcohol solvent), PU515 (non-toluene solvent), SL9155 (non-toluene solvent), CN104 (non-toluene solvent), AC372 (non-toluene solvent) , PP575 (toluene-containing solvent) (all of which are manufactured by Tokyo Ink Co., Ltd.).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these. In addition, the part in an Example and a comparative example represents a mass part, and% represents the mass%.

[Preparation of printing ink]
Ink 1 (Example 1)
10 parts of a urethane resin solution (solid content 25%) and 50 parts of a nitrocellulose resin solution (solid content 25%, substitution degree 2.1), 6 parts of carbon black (# 95, manufactured by Mitsubishi Chemical Corporation), 12 parts of ethyl acetate and 8 parts of n-propyl acetate were charged and kneaded with a paint shaker to prepare a mill base. 1.5 parts of malic acid was dissolved in a mixture of 3 parts of n-propyl alcohol, 4 parts of isopropyl alcohol, 3 parts of methanol, and 2 parts of propylene glycol monomethyl ether, and 0.5 parts of tetraisopropoxide titanium was added. Mixing was performed to prepare a mixed solution. This mixed solution was added to the mill base and mixed to produce the printing ink of Example 1. Similarly, according to the composition of Table 1 and Table 2, printing inks of Examples 2 to 15 were produced.

  Similarly, according to the composition of Table 3 and Table 4, printing inks of Comparative Examples 1 to 13 were produced.

  Similarly, according to the composition of Table 5 and Table 6, printing inks of Examples 16 to 24 were produced.

  The inks of Examples 1 to 24 and Comparative Examples 1 to 13 were evaluated for initial viscosity, stability over time, laminate adhesion, re-solubility, and odor, and are shown in Table 7. In Table 7, “−” indicates that the ink was not evaluated for stability over time due to solidification (the test piece could not be created) or gelated (solidified) over time, so the test piece was prepared. That was not possible.

<Initial viscosity>
About each obtained ink, the viscosity (initial viscosity) was measured using cone plate type viscometer TV-22 (made by Toki Sangyo Co., Ltd.) equipped with a standard cone rotor (1 ° 34 ′ × R24).
The viscosity of 60 mPa · s or less is greater than 60 mPa · s at a shear rate of 192 sec-1 and a rotation speed of 50 rpm, and the viscosity of 150 mPa · s or less is greater than 150 mPa · s at a shear rate of 77 sec-1 and a rotation speed of 20 rpm. Was measured at a shear rate of 9.6 sec −1 and a rotational speed of 2.5 rpm.
If the initial viscosity is extremely high, the printability cannot be satisfied unless diluted with a large amount of organic solvent. Increasing the dilution rate causes a decrease in the printed film thickness, resulting in insufficient density of the printed material and a decrease in physical properties of the coating film.
The initial viscosity is 4: ◎: less than 80 mPa · s, ○: 80 mPa · s or more, less than 100 mPa · s (practical withstandability), Δ: 100 mPa · s or more, less than 120 mPa · s, ×: 120 mPa · s or more Rated by stage.

<Stability over time>
Each ink was put into a 45 degreeC thermostat, left still for 3 days, and the viscosity change rate was calculated | required by the following formula about the initial viscosity and the viscosity after 3 days.
(Viscosity change rate) = (viscosity after 3 days) / (initial viscosity)
If the rate of change in viscosity is large, the dilution rate during printing must be increased, resulting in a decrease in the printed film thickness, resulting in insufficient density of the printed material and a decrease in the physical properties of the coating film.
Viscosity change rate: ◎: less than 1.05, ◯: 1.05 or more, less than 1.1 (can be practically used), Δ: 1.1 or more, less than 1.2, x: 1.2 or more The evaluation was made in four stages: measurement was impossible due to solidification.

<Laminate adhesion>
Each ink was applied to Maricoat (Coat White Ball, manufactured by Hokuetsu Kishu Paper Co., Ltd.) using a bar coater # 8 to obtain a printed matter. Using an extrusion laminating machine on the ink coating surface of the printed material after 1 day, low-density polyethylene (Sumikasen L718-H, manufactured by Sumitomo Chemical Co., Ltd.) melted at 320 ° C. is applied to a thickness of 20 μm and laminated. I got a thing. Further, the laminate after one day of extrusion lamination was cut into a 15 mm wide test piece, and a T-type peel test was performed at a speed of 50 mm / min using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.). Went. The laminate adhesion was judged as superior or inferior by the presence or absence of material destruction.
Those having particularly excellent laminate adhesion do not cause peeling between the low-density polyethylene and the ink coating film, resulting in material destruction. For those with poor laminate adhesion, peeling progresses between the low-density polyethylene and the ink coating.
Laminate adhesion was evaluated in two stages: ◯: material destruction, x: peeling.

<Resolubility>
Each ink was applied to an aluminum foil (Sunfoil, manufactured by Toyo Aluminum Co., Ltd.) using a bar coater # 8 to obtain a printed matter. The printed matter after one day has been cut into 5 cm × 5 cm test pieces, and the test pieces are impregnated for 30 seconds in a container filled with a mixed solvent of 25/25/50 in a mixing ratio of ethyl acetate / n-propyl acetate / isopropyl alcohol. I let you. Then, the test piece was taken out and the area ratio in which the ink coating film surface of the printed material was dissolved was observed. The larger the dissolved area ratio, the better the re-solubility and the more difficult the plate clogging occurs during printing. The smaller the area ratio, the lower the re-solubility, and the more likely the plate clogging occurs during printing, causing blurring.
The re-solubility was evaluated in four stages: ◎: 70% or more, ◯: less than 70%, 60% or more, Δ: less than 60%, 50% or more (can be practically used), and x: less than 50%.

<Odor>
Each ink was applied to Maricoat (Coat White Ball, manufactured by Hokuetsu Kishu Paper Co., Ltd.) using a bar coater # 8 to obtain a printed matter. For the printed matter, take the average of 5 people, smelling the smell, taking 3 as the one that hardly feels smell, 1 that feels weak smell, and 0 that feels strong smell. Judged by.
The odor was evaluated in three stages: ○: average value of 2 or more, Δ: average value of less than 2, 1.5 or more (can be practically used), and x: average value of less than 1.5.

<Odor (Odor measurement)>
As a result of the evaluation in <Odor>, the printed matter that was judged as “x” was cut into 4 cm × 2.5 cm test pieces after 1 day, placed in a vial, and preheated at 100 ° C. for 30 minutes. Then, the head space was analyzed by a gas chromatograph mass spectrometer (HS-20, manufactured by Shimadzu Corporation), and the presence or absence of a peak of odor substance was confirmed.

According to Table 7, it is clear that the inks of Examples 1 to 24 are excellent in terms of initial viscosity, stability over time, laminate adhesion, re-solubility, and odor. It is clear that the inks of Comparative Examples 1 to 13 are inferior in initial viscosity, stability over time, laminate adhesion, re-solubility, and odor.
Specifically, Comparative Example 1 (2-ethylhexanoic acid), which is an example of a carboxylic acid that is not a hydroxy acid, has good initial viscosity, stability over time, and laminate adhesion, but is poor in re-solubility and has odor. (A 2-ethylhexanoic acid peak was confirmed by odor measurement). Comparative Example 2 similar to Cited Document 2 (Example 6), which uses zirconium tetrakispropionate as a crosslinking agent and does not use a hydroxy acid, is excellent in initial viscosity, stability over time, and adhesion to a laminate. Is not used, the re-solubility is inferior and there is also an odor (the peak of propionic acid was confirmed by the odor measurement). Comparative Example 3 similar to Cited Document 2 (Example 8) using tetraisopropoxide titanium as a cross-linking agent and using 2-ethylhexanoic acid which is not a hydroxy acid has an initial viscosity, stability over time, and laminate adhesion. Although the re-solubility is good, there is odor (the peak of 2-ethylhexanoic acid was confirmed by odor measurement). Comparative Example 4 similar to Cited Document 1 (Example 14) using n-butyl phosphate titanium as a cross-linking agent and not using a hydroxy acid has good adhesion to the laminate and good resolubility, but has an initial viscosity. High, stability over time, and odor (the peak of n-butyl phosphate was confirmed by odor measurement). In Comparative Examples 5 to 7, which are examples in which no hydroxy acid is used, the ink has solidified. Similarly, Comparative Example 8, which is an example in which no hydroxy acid is used, did not solidify, but had a high initial viscosity and gelled with time. Comparative Example 9 which does not use a crosslinking agent and is only a hydroxy acid has good re-solubility and no odor, but is inferior in initial viscosity, stability over time, and laminate adhesion. In Comparative Example 10 in which neither a crosslinking agent nor a hydroxy acid is used, the initial viscosity, stability over time, and re-solubility are good and there is no odor, but the laminate adhesion is poor. Comparative Example 11, which is a conventional example using tetraacetylacetonate titanium as a cross-linking agent, has good initial viscosity, stability over time, laminate adhesion, and redissolvability, but has odor (the peak of acetylacetone by odor measurement). Was confirmed). In Comparative Example 12 in which the crosslinking agent was excessively added, the initial viscosity was high, the temporal stability was inferior, and gelation occurred. Comparative Example 13 with excessive addition of hydroxy acid has no odor, but has high initial viscosity, poor temporal stability, and poor laminate adhesion and re-dissolvability.

  According to the printing ink of the present invention, it can be easily printed on paper and film, has good printability, and even when laminated on the printing surface, the odor can be suppressed. Useful for packaging applications. In addition, it can be used to display information for customers such as campaigns, how to eat foods, how to use goods, etc., because it can be used to provide packaging design, etc. by using printing ink. Can do. Furthermore, since it can be applied by various printing methods, it is not limited to food packaging applications, but is used for food preservation applications, agricultural applications, civil engineering applications, fishery applications, automotive interior / exterior applications, marine applications, daily necessities applications, building material interior / exterior applications, housing facilities. Equipment, medical / medical equipment use, pharmaceutical use, home appliance use, furniture use, stationery / office supplies use, sales promotion use, commercial use, electrical and electronics industry use, industrial material use, etc. It can be widely applied to packaging containers using the label, sheet and the like.

Claims (11)

A printing ink comprising a metal alkoxide and a hydroxy acid,
The metal alkoxide is a metal alkoxide represented by the following formula (1), and the content of the metal alkoxide is 0.05 to 10% by mass in the printing ink,
Content of the said hydroxy acid is 0.05-10 mass% in the said printing ink, Printing ink characterized by the above-mentioned.

[In Formula (1), M is any metal atom selected from Group 4 of the periodic table, and R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 18 carbon atoms. ]   The printing ink according to claim 1, wherein the metal atom of the metal alkoxide is titanium or zirconium.   The printing ink according to claim 1 or 2, wherein the hydroxy acid is at least one selected from the group consisting of α-hydroxy acid, β-hydroxy acid, and γ-hydroxy acid.   4. The compound according to claim 1, wherein the hydroxy acid is a compound containing neither an aliphatic hydrocarbon group having 10 or more carbon atoms, an aryl group having 2 or more carbon atoms, or a polycyclic aromatic hydrocarbon group. Printing ink according to crab.   The printing ink according to any one of claims 1 to 4, wherein the printing ink is used for an extrusion-laminated product that does not use an anchor coating agent. A laminate comprising a substrate and a printing ink layer made of printing ink provided on at least one of the substrates,
The said printing ink is the printing ink in any one of Claims 1-5, The laminated body characterized by the above-mentioned. A laminate comprising a substrate, a printing ink layer made of printing ink provided on at least one of the substrates, and a resin layer made of resin,
The printing ink according to any one of claims 1 to 5, wherein the printing ink has no anchor coat layer made of an anchor coating agent between the printing ink layer and the resin layer. body.   A packaging container produced using the laminate according to claim 6 or 7. A method for producing a laminate comprising a printing step of forming a printing ink layer on at least one of a substrate,
The said printing ink is the printing ink in any one of Claims 1-5, The manufacturing method of the laminated body characterized by the above-mentioned. A printing step of forming a printing ink layer on at least one of the substrates;
An application step of forming a resin layer on the surface of the printing ink layer, and a manufacturing method of a laminate comprising:
The printing ink is the printing ink according to any one of claims 1 to 5, and an anchor coat agent is applied between a printing process of the printing ink layer and a coating process of the resin layer to form an anchor coat layer. The manufacturing method of the laminated body characterized by not having the application | coating process to do. A method for manufacturing a packaging container comprising a molding process for molding a laminate,
The method for manufacturing a packaging container, wherein the laminate is a laminate according to claim 6 or 7.