JP2001002970A - Printing ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing ink composition capable of maintaining enough adhesion between ink layer and plastic film and also preventing laminate layer from whitening phenomenon due to permeation of the steam, even after, in particular, steam sterilization treatment of metalic cans processed from laminated metal plates. SOLUTION: This printing ink composition is such one as to use (A) carboxyl group-containing phenoxy resin comprising an esterified product from a phenoxy resin and a polybasic carboxylic acid anhydride or (B) a mixture of the above- mentioned carboxyl group-containing phenoxy resin with a phenoxy resin and/or a polyurethane resin, and pref. contain an organic compound having a blocked isocyanate group in the composition. The printing ink composition is suitable, in particular, for gravure printing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink composition, and more particularly, to imparting corrosion resistance and decorativeness to metal cans such as beverage cans containing beverages such as coffee and juice. The present invention relates to a printing ink composition useful for printing a polyester film for thermal lamination to be used.

[0002]

2. Description of the Related Art The outer surface of a metal can, such as a beverage can containing beverages such as coffee and juice, is generally coated and painted to impart corrosion resistance, decorativeness, etc., or to display the contents. Printed. Conventionally, when performing such coating and printing, a metal plate is coated with an undercoat (white coat), offset printing is performed thereon, and then the coated metal plate coated with a top coat (clear coat) is metallized. A method of processing into cans was used. However, in such a method, it is necessary to perform baking in each step to promote drying or curing of the paint or printing ink, which requires a great deal of time and energy.
Therefore, instead of the above method, a method of thermally laminating a plastic film previously printed by a gravure printing method on a metal plate with a thermosetting adhesive to produce a laminated metal plate has been put into practical use. There is an advantage that the number of processing steps is reduced as compared with the above-described method, thereby improving the productivity and reducing the cost. Further, as a plastic film for thermal lamination used for the above-described laminated metal plate, a polyester film is mainly used, and this polyester film is a material that has been widely used in the field of food packaging. The mainstream printing ink composition for gravure printing uses a mixture of a polyurethane resin and a vinyl chloride / vinyl acetate copolymer as a binder. However, when a metal can processed from a laminated metal plate printed with such a printing ink composition is subjected to a steam sterilization treatment (retort treatment), the ink layer and the polyester are deformed in a large deformation portion such as a neck portion. There are problems such as peeling between the film and the film, and whitening due to the transmission of water vapor in the laminate layer.

[0003]

An object of the present invention is to maintain sufficient adhesion between an ink layer and a plastic film even after steam sterilization of a metal can processed from a laminated metal plate. Another object of the present invention is to provide a printing ink composition capable of preventing a whitening phenomenon of a laminate layer due to permeation of water vapor.

[0004]

According to the present invention, first, as a binder, (a) a carboxyl group-containing phenoxy resin comprising an esterified product of a phenoxy resin and a polybasic carboxylic anhydride or (b) the carboxyl group A printing ink composition using a group-containing phenoxy resin and a mixture of a phenoxy resin and / or a polyurethane resin.

[0005] The present invention secondly, as a binder,
(A) a carboxyl group-containing phenoxy resin consisting of an esterified product of a phenoxy resin and a polybasic carboxylic anhydride, or (b) a mixture of the carboxyl group-containing phenoxy resin and a phenoxy resin and / or a polyurethane resin, And a printing ink composition comprising an organic compound having a blocked isocyanate group in the composition.

[0006] Thirdly, the present invention provides, as a binder,
(A) a carboxyl group-containing phenoxy resin consisting of an esterified product of a phenoxy resin and a polybasic carboxylic anhydride, or (b) a mixture of the carboxyl group-containing phenoxy resin and a phenoxy resin and / or a polyurethane resin, A printing ink composition for gravure printing comprising a printing ink composition, which optionally contains an organic compound having a blocked isocyanate group in the composition.

Hereinafter, the present invention will be described in detail. Binder The printing ink composition of the present invention comprises, as a binder, (a) a carboxyl group-containing phenoxy resin composed of an esterified product of a phenoxy resin and a polybasic carboxylic anhydride, or (b) the carboxyl group-containing phenoxy resin and a phenoxy resin. And / or a mixture with a polyurethane resin (hereinafter, (A) and (B) are collectively referred to as “carboxyl group-containing phenoxy binder”). The phenoxy resin used as a reaction raw material of the carboxyl group-containing phenoxy resin in the present invention is a thermoplastic resin having a hydroxyl group in a molecular chain obtained by reacting an equimolar or almost equimolar epichlorohydrin with a bisphenol compound. It is. The phenoxy resin can be used in combination with a carboxyl group-containing phenoxy resin as a binder component in the present invention.

The bisphenol compound used in the phenoxy resin includes, for example, bisphenol A [2,2
-Bis (4'-hydroxyphenyl) propane], bisphenol B [2,2-bis (4'-hydroxyphenyl) butane], bisphenol C [2,2-bis (3 '
-Methyl-4'-hydroxyphenyl) propane], bisphenol D [bis (4-hydroxyphenyl) methane], bisphenol E (4,4'-dihydroxybiphenyl), bisphenol F (3,3'-n-propyl-4) , 4'-dihydroxybiphenyl) and the like. Of these, bisphenol A and bisphenol F are particularly preferred. The bisphenol compounds may be used alone or in combination of two or more.

[0009] The carboxyl group-containing phenoxy resin, which is the main component of the carboxyl group-containing phenoxy binder in the present invention, comprises an esterified product of the phenoxy resin and a polybasic carboxylic anhydride. The polybasic carboxylic acid anhydride may have one or more carboxylic acid anhydride groups in the molecule, and examples thereof include succinic anhydride, methylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, and anhydride. 2,3-dimethylsuccinic acid, trimethylsuccinic anhydride, tetramethylsuccinic anhydride, 1,2-butanedicarboxylic dianhydride, 1,2,3-propanetricarboxylic anhydride, 1,2,3,4- Aliphatic polycarboxylic anhydrides such as butanetetracarboxylic dianhydride, itaconic anhydride, citraconic anhydride, and maleic anhydride; Δ ¹ -tetrahydrophthalic anhydride, Δ ² -tetrahydrophthalic anhydride, Δ ³ − tetrahydrophthalic anhydride, delta ⁴ - tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic acid, 1,2,3,4-cyclopenta Alicyclic polycarboxylic anhydrides such as tetracarboxylic dianhydride and hexahydropyromellitic anhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,4,3 ', 4'- Biphenyltetracarboxylic dianhydride, 2,2-bis (3 ', 4'-dicarboxyphenyl) propane, 3,4,3', 4'-benzophenonetetracarboxylic dianhydride, 1,2-naphthalenedicarboxylic Examples thereof include aromatic polycarboxylic anhydrides such as acid anhydride, 1,8-naphthalene dicarboxylic anhydride, and chlorendic anhydride. Among these polybasic carboxylic anhydrides, succinic anhydride and the like are particularly preferred. The polybasic carboxylic anhydrides can be used alone or in combination of two or more.

In the present invention, "esterification of a phenoxy resin with a polybasic carboxylic acid anhydride" means that the hydroxyl group in the phenoxy resin and the acid anhydride group in the polybasic carboxylic acid anhydride are different. Reacts to form an ester group and to generate a free carboxyl group,
By this reaction, a carboxyl group can be introduced into the side chain of the phenoxy resin. Such an esterification reaction can be performed by a conventionally known method. In addition,
When the polybasic carboxylic anhydride involved in the esterification reaction has a free carboxyl group, the carboxyl group may also be involved in esterification with a hydroxyl group, but the esterification reaction is an equilibrium reaction, Since it takes a long time to reach, the reaction yield is low under normal reaction conditions and does not substantially hinder the present invention, but the reaction is carried out in the absence of an acidic catalyst (for example, in the absence of an acid catalyst or (In the presence of a basic catalyst such as sodium acetate and pyridine), the selectivity of the esterification reaction between the acid anhydride group and the hydroxyl group can be increased. The esterification rate in the carboxyl group-containing phenoxy resin (the rate at which the hydroxyl groups in the phenoxy resin as a reaction raw material are converted to ester groups) is preferably 0.01 to 100%.
, More preferably in the range of 0.05 to 90%, particularly preferably in the range of 0.1 to 80%. in this case,
If the esterification rate is 0.01% or less, the effect of improving the adhesion between the ink layer and the plastic film may be insufficient.

The weight average molecular weight of the carboxyl group-containing phenoxy resin in the present invention is preferably 10,000.
~ 100,000, more preferably 20,000.
The range is from 0 to 80,000. In this case, the weight average molecular weight of the carboxyl group-containing phenoxy resin is 10,000.
If it is less than 0, the strength of the obtained ink layer is reduced, or the adhesion to the plastic film is reduced, and the ink layer tends to peel off at the interface between the ink layer and the plastic film after the steam sterilization treatment. If it exceeds, the resulting ink composition tends to be viscous and the viscosity adjustment tends to be difficult, and it is difficult to industrially produce such a high molecular weight resin. In the present invention, the carboxyl group-containing phenoxy resin may be used alone or in combination of two or more. The carboxyl group-containing phenoxy resin is a resin having excellent thermal stability and processability, and a high affinity for various plastics and thermosetting adhesives.
By using a carboxyl group-containing phenoxy resin as a main component of the binder, a printing ink composition having excellent adhesion to a plastic film represented by a polyester film can be obtained.

The phenoxy resin optionally used in the present invention is a resin having excellent thermal stability and processability and a high affinity for various thermosetting adhesives. An excellent printing ink composition can be obtained by using together with a carboxyl group-containing phenoxy resin as a binder component in the above. The weight average molecular weight of the phenoxy resin in the present invention is preferably in the range of 10,000 to 100,000, and more preferably in the range of 20,000 to 80,000. In this case, the weight average molecular weight of the phenoxy resin is 10,000.
If it is less than 30, the solvent release from the ink layer is impaired, blocking is likely to occur, and the adhesion to the plastic film is reduced, and there is a possibility that peeling off at the interface between the ink layer and the plastic film after steam sterilization treatment. On the other hand, if it exceeds 100,000, the obtained ink composition may become viscous, making it difficult to adjust the viscosity, and it is difficult to industrially produce such a high molecular weight resin. is there. In the present invention, the phenoxy resins can be used alone or in combination of two or more.

In the present invention, the weight ratio ((a) :( b)) of the carboxyl group-containing phenoxy resin (a) to the phenoxy resin (b) is preferably from 20:80 to 10:
0: 0 range, more preferably 25:75 to 100:
0, particularly preferably in the range of 30:70 to 100: 0. In this case, if the weight ratio is less than 20:80,
Adhesion to the plastic film is reduced, and the film tends to peel off at the interface between the ink layer and the plastic film after the steam sterilization treatment.

In the present invention, it is preferable to use a polyurethane resin in combination with a carboxyl group-containing phenoxy resin or a mixture of the resin and the phenoxy resin as a binder component, thereby imparting flexibility to the ink layer. . The polyurethane resin,
It consists of a resin obtained by the reaction of a component mainly composed of an organic diisocyanate compound and an organic dihydroxy compound. Examples of the organic diisocyanate compound used in the polyurethane resin include, for example, fats such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, and the like. Aromatic diisocyanates; cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-
1,3-diisocyanate, cyclohexylene-1,4
-Diisocyanate, 1-methylcyclohexylene-
2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1,2-dimethylcyclohexylene-3,5-diisocyanate, 1,2-dimethylcyclohexylene-3,6-diisocyanate,
1,3-dimethylcyclohexylene-4,6-diisocyanate, 1,4-dimethylcyclohexylene-2,5
-Diisocyanate, 1,4-dimethylcyclohexylene-2,6-diisocyanate, 1-isocyanate-
3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane, cyclohexylene-1,3-bis (isocyanatomethyl), cyclohexylene-1,4
Alicyclic diisocyanates such as -bis (isocyanatomethyl), isophorone diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate;

Phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-xylylene-3,5-diisocyanate, o
-Xylylene-3,6-diisocyanate, m-xylylene-4,6-diisocyanate, p-xylylene-
2,5-diisocyanate, p-xylylene-2,6-
Diisocyanate, biphenylene-4,4'-diisocyanate, 3,3'-dimethoxybiphenylene-4,
4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-
4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate,
Aromatic diisocyanates such as 3'-dimethyldiphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate; a stoichiometric excess of these organic diisocyanates with a compound having two active hydrogens Both terminal isocyanate prepolymers obtained by the reaction can be exemplified. The organic diisocyanate compounds can be used alone or in combination of two or more.

The organic dihydroxy compound used for the polyurethane resin includes, for example, terephthalic acid,
Isophthalic acid, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, one or more dicarboxylic acids such as dodecadionic acid and ethylene glycol, 1,2-propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol,
Hydroxy-terminated polyesters obtained by reaction with one or more diol components such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, an ethylene oxide adduct of bisphenol A, and an ethylene oxide adduct of bisphenol F; Both-end hydroxypolyethers such as polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide copolymer; ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, Neopentyl glycol, 1,6-hexanediol, 3-methyl-
1,5-pentanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, bisphenol F
And diols such as ethylene oxide adducts. These organic dihydroxy compounds can be used alone or in combination of two or more.

As a method for producing a polyurethane resin, for example, an organic diisocyanate compound and an organic dihydroxy compound are reacted in a molar ratio of an excess of isocyanate group to synthesize a polyurethane prepolymer having an isocyanate group at least at one terminal of a molecular chain. It can be produced by a prepolymer method in which the chain is extended with a chain extender (eg, polyamine, polyhydric alcohol, etc.), a one-shot method in which an organic diisocyanate compound, an organic dihydroxy compound and a chain extender are reacted in a single step, or the like. it can. In these methods, a chain terminator (for example, monoamine,
Monohydric alcohol). In the above method and the above method, a solvent may or may not be used, but the former is preferable in order to obtain a uniform polyurethane resin, and in this case, the concentration of the obtained polyurethane resin solution is adjusted as necessary. After that, it is preferable to provide the printing ink composition. In the latter case, it is preferable to add a solvent after the reaction to dissolve the polyurethane resin, or to obtain a solid polyurethane resin once and then dissolve it in the solvent, and then provide the printing ink composition.
As the solvent used in these cases, for example, the same solvents as used in the preparation of the printing ink composition described below can be mentioned, and the solvent may be used alone or in combination of two or more. Can be used.

The functional groups present at the molecular chain terminals of the polyurethane resin differ depending on the molar ratio between the isocyanate groups and the hydroxyl groups in the raw materials for the reaction (the number of isocyanate groups / the number of hydroxyl groups). That is, when the molar ratio is less than 1, both ends of the molecular chain are mainly hydroxyl group resin, and when the molar ratio is 1, both ends of the molecular chain are mainly isocyanate group and hydroxyl group resin, When the molar ratio is more than 1 and less than 2, the resin mainly has isocyanate groups at both ends of the molecular chain. As the polyurethane resin in the present invention, a resin having a hydroxyl group at at least one terminal of a molecular chain is preferable in terms of excellent pigment dispersibility, excellent flexibility and adhesion.

The number average molecular weight of the polyurethane resin in the present invention is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 100,000, and particularly preferably in the range of 15,000 to 50,000. Range. In this case, if the number average molecular weight of the polyurethane resin is less than 5,000, solvent release from the ink layer is impaired, blocking is likely to occur, and adhesion to the plastic film is reduced. On the other hand, if it exceeds 200,000, the resulting ink composition tends to be viscous and the viscosity adjustment tends to be difficult. In the present invention, the polyurethane resins can be used alone or in combination of two or more.

The weight ratio of the polyurethane resin (c) to the total amount (a + b) of the carboxyl group-containing phenoxy resin (a) and the phenoxy resin (b) in the carboxyl group-containing phenoxy binder [(c): ((a) +
(B))] is preferably in the range of 0: 100 to 70:30, more preferably in the range of 5:95 to 50:50, and particularly preferably in the range of 10:90 to 30:70. In this case, if the weight ratio exceeds 70:30, the strength of the ink layer is reduced, and the ink layer and the plastic film tend to peel off after steam sterilization, and the pigment dispersibility is improved. In addition, the separation of the solvent from the ink layer is impaired, and blocking tends to occur.

In the present invention, a binder other than a phenoxy-based binder containing a carboxyl group (hereinafter referred to as a binder) is used.
"Other binders". ) Can also be used in combination. As other binders, for example, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, acrylic resin, styrene resin, acetal resin, ketone resin,
Examples include polyamide resins, alkyd resins, phenol resins, urea resins, melamine resins, petroleum resins, chlorinated rubbers, cyclized rubbers, cellulose derivatives, starch derivatives, rosin derivatives, shellac, and the like. These other binders can be used alone or in combination of two or more. The proportion of the other binder in the present invention is preferably 0 to 30% by weight, more preferably 0 to 15% by weight, based on the total amount of the carboxyl group-containing phenoxy binder and the other binder. In this case, when the usage ratio of the other binder exceeds 30% by weight, the adhesion between the ink layer and the plastic film and the effect of preventing the whitening phenomenon of the laminate layer after the steam sterilization treatment may be impaired.

Further, in the present invention, it is preferable that an organic compound having a blocked isocyanate group (hereinafter, simply referred to as "blocked isocyanate compound") is blended as a curing agent in the printing ink composition. By blending the blocked isocyanate compound, the adhesion between the ink layer and the plastic film can be further improved, and in particular, the adaptability to steam sterilization can be further increased.

The organic isocyanate compound used as a raw material of the blocked isocyanate compound is not particularly limited, and any known compounds can be used. Examples thereof include the organic diisocyanate compounds exemplified for the polyurethane resin. be able to. Examples of the organic diisocyanate compound as a raw material of the blocked isocyanate compound include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,2-dimethylcyclohexane-3,5-diisocyanate, and 1,2-dimethylcyclohexane-
3,6-diisocyanate, 1,3-dimethylcyclohexane-4,6-diisocyanate, 1,4-dimethylcyclohexane-2,5-diisocyanate, 1,4-
Dimethylcyclohexane-2,6-diisocyanate,
Preferred are isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate and the like.
Adducts of the organic diisocyanate compound with a polyhydric alcohol, a polyether having a hydroxyl group at one or both terminals, a low molecular weight polyester having a hydroxyl group at one or both terminals or an active hydrogen-containing compound such as water Alternatively, a cyclized polymer of the organic diisocyanate compound or the like can also be preferably used as the organic isocyanate compound used for producing the blocked isocyanate compound.

Examples of the blocking agent for blocking the isocyanate group in the organic isocyanate compound include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4
Phenols such as -xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol and 3,5-xylenol; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; methyl alcohol , Ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol,
i-butyl alcohol, sec-butyl alcohol, t
-Butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propyl glycol monomethyl ether, propyl glycol monoethyl Alcohols such as ether and benzyl alcohol; oximes such as formamidoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime and cyclohexane oxime; dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate And active methylene group-containing compounds such as acetylacetone and the like. It is possible. These blocking agents can be used alone or in combination of two or more.

When the blocked isocyanate compound is blended with the printing ink composition of the present invention, the content of the blocked isocyanate compound is based on the total amount of the composition.
Preferably 1 to 15% by weight, more preferably 1 to 10%
% By weight. In this case, if the content of the blocked isocyanate compound is less than 1% by weight, the effect of improving the adhesion between the ink layer and the plastic film, particularly the effect of improving the adaptability to steam sterilization treatment, tends to decrease.
If it exceeds 5% by weight, the ink layer becomes brittle, and the operability when processing a laminated metal plate or a metal can tends to decrease.

The printing ink composition of the present invention is prepared by mixing a carboxyl group-containing phenoxy-based binder with other conventional printing ink components containing a pigment and a solvent in a conventional manner. The pigment is appropriately selected according to a desired color tone, and is not particularly limited. Examples thereof include aluminum powder, titanium dioxide, zinc white, carbon black, isoindolinone yellow, benzimidazolone yellow, Examples include benzimidazolone orange, quinacridone red, phthalocyanine blue, phthalocyanine green, and the like. These pigments can be used alone or in combination of two or more.

Examples of the solvent include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2,4-dimethyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2-hexanone, and 3-hexanone. Hexanone, 2-methyl-3-hexanone, 5-methyl-2-
Hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-
3-heptanone, 2,6-dimethyl-4-heptanone,
2-octanone, 3-octanone, 2-nonanone, 3-
Nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, cyclohexanone, 2-acetylcyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone,
Ketone solvents such as cycloheptanone, 1-decalone and 2-decalone: aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and cumene;

1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2
-Trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, o -Halogenated hydrocarbon solvents such as dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, trichloromethylbenzene; dioxane, anisole, tetrahydrofuran, tetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol Over monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, ether solvents such as triethylene glycol monomethyl ether;

Ethyl acetate, n-propyl acetate, i-acetate
Propyl, n-butyl acetate, i-butyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monopropyl ether acetate,
Acetate solvents such as diethylene glycol monobutyl ether acetate; methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol;
sec-butyl alcohol, t-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n
Alcohol solvents such as -propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propyl glycol monomethyl ether, propyl glycol monoethyl ether, and benzyl alcohol; N-methyl-2-pyrrolidone, N- Acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N
-Methyl-3-pyrrolidone, N-acetyl-3-pyrrolidone, N-benzyl-3-pyrrolidone, formamide,
N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide,
Amide solvents such as N-dimethylacetamide and N-methylpropionamide; aprotic polar solvents such as dimethylsulfoxide; and the like.

These solvents can be used alone or as a mixture of two or more kinds.
Ketone solvents, aromatic hydrocarbon solvents, and mixtures thereof are preferred, and methyl ethyl ketone, toluene, and mixtures thereof are particularly preferred. Furthermore, examples of the compounding components other than those described above include extenders, plasticizers, softeners, pressure-sensitive adhesives, thickeners, waxes, coupling agents, and dispersants.

The printing ink composition of the present invention is used, for example, for imparting corrosion resistance and decorativeness to metal cans such as beverage cans containing beverages such as coffee and juice, and for displaying contents. It can be used very suitably for gravure printing of polyester films for thermal lamination, gravure printing of other plastic films for thermal lamination used for the same purpose, and for various materials in other uses and fields. It can also be used widely for other types of printing of various materials, including gravure printing and polyester films. When gravure printing, for example, a polyester film with the printing ink composition of the present invention, a monochromatic gravure printing machine,
Known printing machines such as a multicolor gravure printing machine and a drum type printing machine can be employed.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Here, preferred embodiments of the printing ink composition of the present invention are more specifically exemplified as follows. The carboxyl group-containing phenoxy resin has a weight average molecular weight in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 80,000, and an esterification ratio in the range of 0.01 to 100%. Preferably in the range of 0.05 to 90%, particularly preferably 0.1 to 90%.
80%, the weight average molecular weight of the phenoxy resin is in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 80,000, and the number average molecular weight of the polyurethane resin is 5,000 to 200,00
0, more preferably 10,000-100,0.
00, particularly preferably 15,000 to 50,000.
A printing ink composition that is in the range of 0. The weight ratio ((a) :( b)) between the carboxyl group-containing phenoxy resin (a) and the phenoxy resin (b) is 2
0:80 to 100: 0, more preferably 25:
75 to 100: 0, particularly preferably 30:70 to
The weight ratio of the polyurethane resin (c) to the total amount of the carboxyl group-containing phenoxy resin (a) and the phenoxy resin (b) ((a) + (b)) ((c) :( (A) + (b))] is 0: 100
~ 70: 30, more preferably 5: 95 ~ 5.
0:50 range, particularly preferably 10:90 to 30: 7.
The printing ink composition as described above, which is in the range of 0. The above-mentioned or the printing ink composition, wherein the blocked isocyanate compound is contained in the composition in an amount of 1 to 15% by weight, more preferably 1 to 10% by weight, based on the total amount of the composition. The carboxyl group-containing phenoxy resin is an ester of bisphenol A type phenoxy resin and polybasic carboxylic anhydride and / or an ester of bisphenol F type phenoxy resin and polybasic carboxylic anhydride, and the phenoxy resin is bisphenol The printing ink composition according to any one of the above-mentioned items, which is an A-type phenoxy resin and / or a bisphenol F-type phenoxy resin. The printing ink composition according to any one of the above items, wherein the printing ink composition is a printing ink composition for gravure printing.

[0033]

The embodiments of the present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these embodiments. “Parts” and “%” in Examples and Comparative Examples are based on weight. The evaluation in Examples and Comparative Examples was performed as follows. Retort resistance test A laminated steel sheet was placed in an autoclave, and (α) 1.
4 atm and 125 ° C or (β) 2 atm and 135
After exposure to water vapor at 30 ° C for 30 minutes each, the adhesion and whitening state of the laminate layer were visually observed. If no abnormality was observed, it was good (良好). The evaluation was made as normal (△) when possible, and as poor (×) when abnormalities exceeding practical levels were observed. Drawing Test Laminated steel sheet is drawn to a diameter of 25 mm x a height of 8 mm at room temperature using a deep drawing Erichsen molding machine, and then placed in an autoclave and subjected to the above (α) or (β).
Under the conditions described above, each neck was exposed to water vapor for 30 minutes, and the appearance of the neck portion was visually observed. If no abnormality was recognized, it was good (○). Δ), a case where an abnormality exceeding the practical level was observed was evaluated as defective (x). Press test Laminated steel sheet was pressed using a press forming machine to a diameter of 50 mm.
× After press working to a height of 5 mm at room temperature, put into an autoclave, exposed to steam for 30 minutes each under the conditions of the above (α) or (β), and visually observed the appearance of the neck part. The case where no abnormality was observed was evaluated as good (○), the case where some abnormality was observed but was practicable was evaluated as normal (△), and the case where an abnormality exceeding the practical level was observed was evaluated as poor (×). .

Example 1 A printing ink composition A having the following composition was prepared by a conventional method. Printing ink composition A phthalocyanine blue 10 parts Carboxyl group-containing phenoxy resin (Note 1) 15 parts (weight average molecular weight = 40,000, solid content 30%) Phenoxy resin 9 parts (weight average molecular weight = 40,000, trade name Pheno) Tote PX-283, manufactured by Toto Kasei Co., Ltd. Polyurethane resin (Note 2) 15 parts (number average molecular weight = 30,000, solid content 30%) Methyl ethyl ketone 26 parts Toluene 25 parts 100 parts (Note 1) , Manufactured according to the following <Reference Production Example 1>. (Note 2) This resin was produced according to the following <Reference Production Example 2>. Next, gravure printing was performed on the polyester film using the printing ink composition A, and then a thermosetting adhesive was applied at a solid content of 2 g / m ² on the printing surface of the film.
Thereafter, the film was thermocompression-bonded to a chromium-treated steel sheet using a heat roll at 190 ° C. and baked at 220 ± 5 ° C. to obtain a laminated steel sheet. Table 1 shows the evaluation results of the laminated steel sheet. In the printing test, the printing ink composition A showed an abnormality when the water vapor exposure condition was (β) in the press test. However, in the remaining tests, there was no abnormality or mild, and the printing ink composition A had good properties as a whole. .

Reference Production Example 1 In a flask equipped with a stirrer and a thermometer, 280 parts of methyl ethyl ketone and phenoxy resin (trade name: Phenotote PX-283) 12
After 0 parts were charged and dissolved by heating, water in the system was removed by azeotropic distillation. Then, in the flask,
After adding 1.1 parts of succinic anhydride and reacting at 85 ° C. for 3 hours, methyl ethyl ketone was added to obtain a carboxyl group-containing phenoxy resin solution having a solid content of 30%. This carboxyl group-containing phenoxy resin solution has a viscosity of 450
cps / 25 ° C., and the carboxyl group-containing phenoxy resin had a weight average molecular weight of 40,000 and an esterification rate of 2.6%.

Reference Production Example 2 In a flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, a flask having an average molecular weight of 2,000 obtained by the reaction of adipic acid and 3-methyl-1,5-pentanediol. Polyester diol 1,0
After charging 00 parts and 200 parts of isophorone diisocyanate and reacting at 120 ° C. for 6 hours under a nitrogen stream,
300 parts of methyl ethyl ketone was added to obtain 1,500 parts of a homogeneous solution of the polyurethane prepolymer. Then, 65.2 parts of isophoronediamine, 5.1 parts of di-n-butylamine, 1,676 parts of methyl ethyl ketone and i-
A mixture of 988 parts of propyl alcohol was added to the polyurethane prepolymer solution and reacted at 50 ° C. for 3 hours to obtain a polyurethane resin solution having a solid content of 30%.
This polyurethane resin solution has a viscosity of 1,800 cps.
/ 25 ° C., and the number average molecular weight of the polyurethane resin was 30,000.

Example 2 To 100 parts of the printing ink composition A obtained in Example 1, 6 parts of a blocked isocyanate compound (Note 3) (trade name Desmodur TPLS2957, manufactured by Sumitomo Chemical Co., Ltd.) was mixed. A printing ink composition B was prepared. (Note 3) This compound is a compound obtained by blocking the isocyanate group of the cyclized trimer of hexamethylene diisocyanate with ε-caprolactam. Next, a laminated steel sheet was obtained in the same manner as in Example 1 using the printing ink composition B. Table 1 shows the evaluation results of the laminated steel sheet.

Example 3 A printing ink composition C having the following composition was prepared by a conventional method. Printing ink composition C Titanium dioxide 30 parts Carboxyl group-containing phenoxy resin (see note 1) 15 parts Phenoxy resin (trade name: Phenotote PX-283) 9 parts Polyurethane resin (see note 2) 15 parts Methyl ethyl ketone 16 parts Toluene 15 parts 100 Using printing ink composition C, in the same manner as in Example 1,
A laminated steel plate was obtained. Table 1 shows the evaluation results of the laminated steel sheet. In the printing test, the printing ink composition C showed abnormalities when the water vapor exposure condition was (β) in the press test, but there were no abnormalities or slight in the remaining tests, and the overall properties were good. .

Example 4 A block isocyanate compound (trade name Desmodur TP) was added to 100 parts of the printing ink composition C obtained in Example 3.
LS2957) was mixed with 6 parts to prepare a printing ink composition D. Using Printing Ink Composition D, a laminated steel sheet was obtained in the same manner as in Example 1.

Comparative Example 1 A printing ink composition E having the following composition was prepared by a conventional method. Printing Ink Composition E Phthalocyanine Blue 10 parts Vinyl chloride / vinyl acetate resin 5 parts (trade name: Vinylite VAGH, manufactured by Union Carbide Corporation (UCC)) Polyurethane resin (manufactured by Reference Production Example) 30 parts Methyl ethyl ketone 30 Part Toluene 25 parts 100 parts Using printing ink composition E, in the same manner as in Example 1,
A laminated steel plate was obtained. Table 1 shows the evaluation results of the laminated steel sheet.

Comparative Example 2 A block isocyanate compound (trade name Desmodur TP) was added to 100 parts of the printing ink composition E obtained in Comparative Example 1.
LS2957) was mixed with 6 parts to prepare a printing ink composition F. A laminated steel sheet was obtained in the same manner as in Example 1 using the printing ink composition F. Table 1 shows the evaluation results of the laminated steel sheet.

Comparative Example 3 A printing ink composition G having the following composition was prepared by a conventional method. Printing ink composition G Titanium dioxide 30 parts Vinyl chloride / vinyl acetate resin (trade name: Vinylite VAGH) 5 parts Polyurethane resin (manufactured by Reference Production Example) 30 parts Methyl ethyl ketone 20 parts Toluene 15 parts 100 parts Printing ink composition Using G, as in Example 1,
A laminated steel plate was obtained. Table 1 shows the evaluation results of the laminated steel sheet.

Comparative Example 4 A block isocyanate compound (trade name Desmodur TP) was added to 100 parts of the printing ink composition G obtained in Comparative Example 3.
LS2957) was mixed with 6 parts to prepare a printing ink composition H. Using Printing Ink Composition H, a laminated steel sheet was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the laminated steel sheet.

[0044]

[Table 1]

[0045]

The plastic film for thermal lamination printed on a plastic film typified by a polyester film using the printing ink composition of the present invention, when thermally laminated on a metal can such as a beverage can, has an ink layer and a plastic film. Adhesiveness, and the adhesiveness between the ink layer and the thermosetting adhesive layer are both excellent, even after steam sterilization, without causing separation between these layers,
In addition, there is no occurrence of whitening of the laminate layer due to permeation of water vapor. Therefore, the printing ink composition of the present invention has particularly excellent properties as a gravure printing ink composition for a polyester film for thermal lamination, and gravure printing and other types of printing of various other materials. It is also useful.

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[Procedure amendment]

[Submission date] April 26, 2000 (200.4.2
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink composition, and more particularly, to imparting corrosion resistance and decorativeness to metal cans such as beverage cans containing beverages such as coffee and juice. Used plastic film for thermal lamination such as polyester film for thermal lamination
The present invention relates to a printing ink composition used for printing on a printing ink.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0003

[Correction method] Change

[Correction contents]

[0003]

An object of the present invention is to maintain sufficient adhesion between an ink layer and a plastic film even after steam sterilization of a metal can processed from a laminated metal plate. Thermal lamination that can prevent the whitening phenomenon of the laminate layer due to water vapor transmission
An object of the present invention is to provide a printing ink composition used for printing a plastic film for printing .

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004]

According to the present invention, first, as a binder, (a) a carboxyl group-containing phenoxy resin comprising an esterified product of a phenoxy resin and a polybasic carboxylic anhydride or (b) the carboxyl group A mixture of a phenoxy resin having a group and a phenoxy resin and / or a polyurethane resin.
Used for printing plastic film for thermal lamination
Printing ink composition that consists.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

[0005] The present invention secondly, as a binder,
(A) a carboxyl group-containing phenoxy resin consisting of an esterified product of a phenoxy resin and a polybasic carboxylic anhydride, or (b) a mixture of the carboxyl group-containing phenoxy resin and a phenoxy resin and / or a polyurethane resin, And printing a plastic film for heat lamination , characterized in that the composition contains an organic compound having a blocked isocyanate group in the composition.
A printing ink composition used for

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006] Thirdly, the present invention provides, as a binder,
(A) a carboxyl group-containing phenoxy resin consisting of an esterified product of a phenoxy resin and a polybasic carboxylic anhydride, or (b) a mixture of the carboxyl group-containing phenoxy resin and a phenoxy resin and / or a polyurethane resin, For gravure printing comprising a printing ink composition, characterized in that the composition optionally contains an organic compound having a blocked isocyanate group, for printing a plastic film for thermal lamination.
Printing ink composition used .

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

Hereinafter, the present invention will be described in detail. Binder of the plastic film for thermal lamination in the present invention
Printing ink compositions used for printing (hereinafter simply referred to as
Ming printing ink composition ". ) Is, as a binder, (a) a carboxyl group-containing phenoxy resin composed of an esterified product of a phenoxy resin and a polybasic carboxylic anhydride, or (b) a carboxyl group-containing phenoxy resin and a phenoxy resin and / or a polyurethane resin. A mixture (hereinafter, (a) and (b) are collectively referred to as a “carboxyl group-containing phenoxy binder”) is used. The phenoxy resin as a reaction raw material of the carboxyl group-containing phenoxy resin in the present invention is a thermoplastic resin having a hydroxyl group in a molecular chain obtained by reacting an equimolar or almost equimolar epichlorohydrin with a bisphenol compound. is there. The phenoxy resin can be used in combination with a carboxyl group-containing phenoxy resin as a binder component in the present invention.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

In the present invention, it is preferable to use a polyurethane resin in combination with a carboxyl group-containing phenoxy resin or a mixture of the resin and the phenoxy resin as a binder component, thereby imparting flexibility to the ink layer. . The polyurethane resin,
It consists of a resin obtained by the reaction of a component mainly composed of an organic diisocyanate compound and an organic dihydroxy compound. Examples of the organic diisocyanate compound used in the polyurethane resin include, for example, fats such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, and the like. Aromatic diisocyanates; cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-
1,3-diisocyanate, cyclohexylene-1,4
-Diisocyanate, 1-methylcyclohexylene-
2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1,2-dimethylcyclohexylene-3,5-diisocyanate, 1,2-dimethylcyclohexylene-3,6-diisocyanate,
1,3-dimethylcyclohexylene-4,6-diisocyanate, 1,4-dimethylcyclohexylene-2,5
-Diisocyanate, 1,4-dimethylcyclohexylene-2,6-diisocyanate, 1-isocyanate-
3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane, cyclohexylene-1,3-bis (isocyanatomethyl), cyclohexylene-1,4
- bis (isocyanatomethyl), isophorone diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, alicyclic Jiisoshia Ne over preparative such as dicyclohexylmethane-4,4'-diisocyanate;

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

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Phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-xylylene-3,5-diisocyanate, o
-Xylylene-3,6-diisocyanate, m-xylylene-4,6-diisocyanate, p-xylylene-
2,5-diisocyanate, p-xylylene-2,6-
Diisocyanate, biphenylene-4,4'-diisocyanate, 3,3'-dimethoxybiphenylene-4,
4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-
4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate,
3'-dimethyl diphenylmethane-4,4'-diisocyanate, aromatic Jiisoshia Ne over preparative such as naphthylene-1,5-diisocyanate; compounds having two stoichiometric excess active hydrogen of the organic diisocyanates and And the isocyanate prepolymers at both ends obtained by the above reaction. The organic diisocyanate compounds can be used alone or in combination of two or more.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

The printing ink composition of the present invention is used, for example, for imparting corrosion resistance and decorativeness to metal cans such as beverage cans containing beverages such as coffee and juice, and for displaying contents. In addition to being very suitable for gravure printing of polyester films for thermal lamination, gravure printing of other plastic films for thermal lamination used for the same purpose, and even other modes of various materials including polyester films It can be widely used for printing. When gravure printing is performed on, for example, a polyester film using the printing ink composition of the present invention, a known printing machine such as a single-color gravure printing machine, a multicolor gravure printing machine, or a drum-type printing machine can be employed.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Here, preferred embodiments of the printing ink composition of the present invention are more specifically exemplified as follows. The carboxyl group-containing phenoxy resin has a weight average molecular weight in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 80,000, and an esterification ratio in the range of 0.01 to 100%. Preferably in the range of 0.05 to 90%, particularly preferably 0.1 to 90%.
80%, the weight average molecular weight of the phenoxy resin is in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 80,000, and the number average molecular weight of the polyurethane resin is 5,000 to 200,00
0, more preferably 10,000-100,0.
00, particularly preferably 15,000 to 50,000.
0 of the plastic film for thermal lamination
Printing ink composition used for printing. The weight ratio ((a) :( b)) between the carboxyl group-containing phenoxy resin (a) and the phenoxy resin (b) is 2
0:80 to 100: 0, more preferably 25:
75 to 100: 0, particularly preferably 30:70 to
The weight ratio of the polyurethane resin (c) to the total amount of the carboxyl group-containing phenoxy resin (a) and the phenoxy resin (b) ((a) + (b)) ((c) :( (A) + (b))] is 0: 100
~ 70: 30, more preferably 5: 95 ~ 5.
0:50 range, particularly preferably 10:90 to 30: 7.
0 for the plastic for thermal lamination described above .
A printing ink composition used for printing a film . For printing a plastic film for heat lamination as described above or above, wherein the composition contains a blocked isocyanate compound in an amount of 1 to 15% by weight, more preferably 1 to 10% by weight, based on the total amount of the composition. Use
Use is the printing ink composition. The carboxyl group-containing phenoxy resin comprises an ester of a bisphenol A type phenoxy resin and a polybasic carboxylic anhydride and / or an ester of a bisphenol F type phenoxy resin and a polybasic carboxylic anhydride, and the phenoxy resin is bisphenol The thermal laminate according to any one of the above-mentioned items, which is an A-type phenoxy resin and / or a bisphenol F-type phenoxy resin.
Printing ink composition used for printing plastic films for printing . The heat laminate according to any one of the above-mentioned, wherein the printing ink composition is a printing ink composition for gravure printing.
Printing ink composition used for printing plastic films for printing .

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0045

[Correction method] Change

[Correction contents]

[0045]

The plastic film for thermal lamination printed on a plastic film typified by a polyester film using the printing ink composition of the present invention, when thermally laminated on a metal can such as a beverage can, has an ink layer and a plastic film. Adhesiveness, and the adhesiveness between the ink layer and the thermosetting adhesive layer are both excellent, even after steam sterilization, without causing separation between these layers,
In addition, there is no occurrence of whitening of the laminate layer due to permeation of water vapor. Therefore, the printing ink composition of the present invention has extremely excellent properties particularly as a gravure printing ink composition for a polyester film for heat lamination, and various other plastics for heat lamination.
It is also useful for gravure and other types of printing of film .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CH08W CH08X CK02X ER006 ES006 FD090 FD200 4J005 AA24 BD02 4J039 AE04 AE07 AF07 BC32 CA07 EA43 EA48 FA02 GA03

Claims (8)

[Claims] 1. As a binder, (a) a carboxyl group-containing phenoxy resin comprising an esterified product of a phenoxy resin and a polybasic carboxylic anhydride, or (b) the carboxyl group-containing phenoxy resin and a phenoxy resin and / or a polyurethane resin. A printing ink composition, characterized by using a mixture thereof. 2. A phenoxy resin having a carboxyl group,
The printing ink composition according to claim 1, wherein the weight average molecular weight is in the range of 10,000 to 100,000, and the esterification ratio is in the range of 0.01 to 100%. 3. A phenoxy resin having a weight average molecular weight of 1
The printing ink composition according to claim 1, wherein the printing ink composition has a range of from 000 to 100,000. 4. The polyurethane resin having a number average molecular weight of 5,
The printing ink composition according to any one of claims 1 to 3, which is in a range of 000 to 200,000. 5. The printing ink composition according to claim 1, wherein the weight ratio between the carboxyl group-containing phenoxy resin and the phenoxy resin is in the range of 20:80 to 100: 0. 6. The printing ink according to claim 1, wherein the weight ratio of the polyurethane resin to the total amount of the carboxyl group-containing phenoxy resin and the phenoxy resin is in the range of 0: 100 to 70: 30% by weight. Composition. 7. The printing ink composition according to claim 1, wherein the composition contains an organic compound having a blocked isocyanate group. 8. The printing ink composition according to claim 1, wherein the printing ink composition is a printing ink composition for gravure printing.