JP6406329B2 - Gravure ink and printed matter - Google Patents

Description

  The present invention relates to a gravure ink and printed matter thereof.

  When various plastic base materials and paper base materials are used for packaging materials, printing using printing ink is usually performed for decoration or surface protection of the base material. The printed substrate is then subjected to a slitting process, and finally becomes a package for food packaging, cosmetic packaging, or any other application.

  In many cases, a gravure printing method is employed for printing on a film substrate or a paper substrate. The plate used for the gravure printing method is an intaglio plate with characters and patterns. Soak the ink in the plate to the extent that ink enters this cell, and rotate the plate while scraping off excess ink with a doctor blade. , Gravure ink is transferred to the base material and allowed to settle. Since this printing method can express fine shades, it is optimal for reproducing rich gradations such as photographs and is suitable for mass production because high-speed printing is possible. However, improvement of the working environment in printing has been promoted, and non-toluene solvent inks that do not use aromatic solvents such as toluene are the mainstream. On the other hand, with the diversification of packaging and advancement of packaging technology, food manufacturers and converters are demanding high quality and performance for printing inks.

  As characteristics required for gravure ink, in the field of surface printing on film base materials and paper, the performance of surface printing ink in which a printing layer is formed on the outer surface of the package, as well as printability, Adhesion to film / paper substrate, blocking resistance to prevent ink from being removed on the back of the film substrate when printed and wound up, blocking resistance between printed surfaces in printed materials, and table Various resistances are required, such as vinyl chloride blocking resistance between the soft vinyl chloride sheet used for cloth and printed materials, friction resistance to prevent the printed surface from being damaged, oil resistance to oils and fats, and heat resistance during bag making. ing.

  In recent years, the market for “anti-fogging films” having anti-fogging properties as food packaging films for vegetables and fruits has been expanding. These fresh foods are kept in refrigerated or cold state until they reach the consumer, and are transported and sold, but if there is a sudden temperature / humidity change in the process, the water contained in the food will evaporate, There is a problem that moisture is deposited as water droplets on the inner surface of the packaging film due to condensation or the like, resulting in “cloudiness” on the film surface, making it difficult to recognize the contents. In addition, fresh foods such as strawberries, bean sprouts and mushrooms also have a problem that the water adhering to the inner surface of the packaging film becomes water droplets, and the quality of the product is deteriorated by re-adhering to the foods. “Anti-fogging film” is a base material on which a surfactant is applied or kneaded, so it can suppress fogging, but the ink film may peel off when pressure is generated by contact with the ink film. In addition, blocking resistance between the antifogging film and the printed layer was also an important issue.

  Therefore, in Patent Document 1 and the like, a printing ink using a polyamide resin and a cellulose resin as a binder is disclosed. However, an ink mainly composed of a polyamide resin has a brittle ink film, and therefore the ink is rubbed with a guide roll of a printing press. Has been transferred and the appearance of the printed matter is impaired. Therefore, as disclosed in Patent Document 2, a polyurethane-based ink suitable for high-speed printing has been proposed. Furthermore, in a polyurethane-based gravure ink improved in high-speed printing and anti-blocking property, it is exemplified that a chelating agent and an amide wax component are used. (Patent Documents 3, 4, and 5). Patent Document 6 exemplifies gravure ink for paper having excellent dot reproducibility, adhesion and odor. However, a higher level of printing performance and physical properties are required, and no one has yet been invented that satisfies printability, blocking resistance to various substrates, oil resistance, and heat resistance.

JP-A-9-296143 JP 2012-012597 A JP 2013-127038 A Japanese Patent Laying-Open No. 2015-205993 JP, 2006-043600, A JP 2014-058653 A

  It is an object of the present invention to provide a gravure ink that has good printability and gloss of a printed layer, and further can satisfy both generality of the base material in blocking resistance and adhesiveness, heat resistance, and oil resistance. To do.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using the gravure ink described below, and have reached the present invention.
That is, this invention is gravure ink for printing on a paper base material or a plastic base material, Comprising: Binder resin (A), hydrocarbon wax (B), and an organic solvent, The following (1)-( It relates to an organic solvent-based gravure ink characterized by satisfying 3).
(1) The hardness (penetration) at 25 ° C. of the hydrocarbon wax (B) defined in Japanese Industrial Standard JIS K 2207 is 0.5 to 12, and the average particle diameter is 1 to 10 μm. is there.
(2) The hydrocarbon wax (B) is contained in 0.1 to 2.5% by mass in 100% by mass of the gravure ink.
(3) a binder resin (A), a vinyl chloride polyurethane resin (A1) - vinyl acetate copolymer resin, containing a mass ratio of 95 / 5-30 / 7 0.

The present invention also relates to the above organic solvent-based gravure ink for surface printing.

The present invention also provides the organic solvent-based gravure wherein the hydrocarbon wax (B) contains at least one selected from the group consisting of polyethylene wax (b1), polypropylene wax (b2) and Fischer-Tropsch wax (b3). It relates to ink.

Moreover, it is related with the said organic solvent gravure ink whose melting | fusing point of hydrocarbon wax (B) is 90-150 degreeC .

The present invention further contains a fatty acid amide (C) , the hydrocarbon wax (B) contains a polyethylene wax (b1),
The mass ratio (B) / (C) of the hydrocarbon wax (B) and the fatty acid amide (C) is in the range of 80/20 to 20/80, and the fatty acid amide (C ) And the polyethylene wax (B) are related to the organic solvent-based gravure ink which is 0.3 to 3% by mass .

The present invention also relates to the organic solvent-based gravure ink containing a fatty acid amide having an aliphatic hydrocarbon group having 10 to 25 carbon atoms.

Moreover, this invention relates to the said organic-solvent gravure ink which contains 0.5-2.0 mass% of titanium chelates in a gravure ink further as a chelate crosslinking agent.

Moreover, this invention relates to the printed matter printed with the said organic solvent type gravure ink.

  With the gravure ink of the present invention, the printability and the gloss of the printed layer are good, and further, the versatility of the base material in terms of blocking resistance and adhesiveness, heat resistance and oil resistance can both be achieved.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content is not limited.

One embodiment of the present invention is a gravure ink for printing on a paper substrate or a plastic substrate, which contains a binder resin (A) and a hydrocarbon wax (B), and includes the following (1) and (2) It is a gravure ink characterized by satisfying
(1) The hardness (penetration) at 25 ° C. of the hydrocarbon wax (B) at 25 ° C. defined by Japanese Industrial Standard JIS K 2207 is 0.5-12.
(2) The hydrocarbon wax (B) is contained in 0.1 to 2.5% by mass in 100% by mass of the gravure ink.

  The present inventors contain 0.1 to 2.5% by mass of hydrocarbon wax (B) having a hardness (penetration) according to JIS K 2207 of 0.5 to 12 in 100% by mass of gravure ink. As a result, it has been found that the printing suitability, the gloss of the printing surface, and the blocking resistance can both be achieved. The content of the hydrocarbon wax (B) is preferably 0.1 to 2.2% by mass in 100% by mass of the gravure ink. When the penetration of the hydrocarbon wax (B) is 0.5 or more, the friction resistance is good, and when it is 12 or less, the blocking resistance is drastically improved. The hardness (penetration) of the hydrocarbon wax (B) is preferably 0.5 to 10, more preferably 0.5 to 9.

  The ink film of gravure ink has moderate elasticity but lacks slipperiness, so blocking resistance and friction resistance have been problems. However, when the hydrocarbon wax (B) having the above characteristics is used in the gravure ink at a constant blending amount, the compatibility between the hydrocarbon wax (B) and the binder resin (A) is improved, and the elasticity of the ink film is increased. It can be assumed that the slipperiness is greatly improved, and the versatility of the base material in blocking resistance of the ink coating is improved.

  The gravure ink of the present invention is preferably used for surface printing. In this specification, surface printing and back printing are surface printing when printing is performed on a paper substrate and plastic substrate in the order of substrate / white / color and the printed pattern can be confirmed from the printed surface. The case where printing is performed in the order of base material / color / white and the printed pattern can be confirmed when viewed from the surface of the base material is referred to as back printing. Hereinafter, each material which comprises the gravure ink of this invention is demonstrated.

<Binder resin (A)>
The binder resin (A) is preferably a thermoplastic resin, and a resin capable of forming a printed coating film (film) after printing is appropriately selected. In the present specification, the thermoplastic resin means a resin that has the property of being softened by heating to be moldable and solidified by cooling.
When the binder resin (A) has a rubber elasticity preferably has a glass transition temperature (Tg) of less than -50 ° C. or higher 40 ° C., more storage modulus at 30 ° C. in a dynamic viscoelasticity measurement is 10 ⁷ to What is 10 ⁹ Pa is preferable. When binder resin (A) does not have rubber elasticity, what has a glass transition temperature of 40 to 200 degreeC is preferable. In any case, those that can be dissolved in an organic solvent are preferred.
In the present specification, the glass transition temperature of the binder resin (A) is a value measured by differential scanning calorimetry (DSC).

  Further, the binder resin (A) preferably uses a resin having a glass transition temperature of −50 ° C. or higher and lower than 40 ° C. and a resin having a glass transition temperature of 40 ° C. or higher and 200 ° C. or lower. More preferably, a resin having a glass transition temperature of −50 ° C. to 0 ° C. and a resin having a glass transition temperature of 50 ° C. to 190 ° C. are used in combination.

  In this specification, rubber elasticity means that a polymer chain partially binds or aggregates to form a three-dimensional network structure, and behaves like a solid because the whole is connected. It shows the property that the elasticity appears remarkably because the partial chain can take various conformations without stopping.

  Examples of the binder resin (A) include, but are not limited to, polyurethane resin (A1), cellulose resin (A2), polyamide resin (A3), vinyl chloride-vinyl acetate copolymer resin, Vinyl chloride-acrylic copolymer resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, acrylic resin, styrene resin, dammar resin, styrene-maleic acid copolymer resin, polyester resin, alkyd resin , Polyvinyl chloride resin, rosin resin, rosin modified maleic resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, polyacetal resin, petroleum resin, and modified resins thereof. be able to. These resins can be used alone or in admixture of two or more.

Among the above, polyurethane resin (A1), cellulose resin (A2), polyamide resin (A3), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, Binder resin containing at least one selected from the group consisting of vinyl acetate resin, acrylic resin, styrene resin, styrene-maleic acid copolymer resin, dammar resin, rosin resin, rosin modified maleic acid resin, ketone resin and cyclized rubber ( A) is preferred.
Furthermore, a binder resin (A) containing at least one selected from the group consisting of a polyurethane resin (A1), a cellulose resin (A2), and a polyamide resin (A3) is preferable.

The binder resin (A) preferably contains at least two kinds of resins. Preferably, polyurethane resin (A1) / vinyl chloride-vinyl acetate copolymer resin, polyurethane resin (A1) / cellulose resin (A2), polyamide resin (A3) / cellulose resin (A2), acrylic resin / cellulose resin (A2) is a combination selected from the above, and in 100% by mass of the binder resin (A), it is preferable that the two resins contain 80 to 100% by mass in total, and more preferably 90 to 100% by mass.
Furthermore, polyurethane resin (A1) / vinyl chloride-vinyl acetate copolymer resin, polyurethane resin (A1) / cellulose resin (A2), polyamide resin (A3) / cellulose resin (A2), acrylic resin / cellulose resin ( A2) is preferably in a mass ratio of 95/5 to 30/70, respectively. More preferably, it is 90 / 10-50 / 50 by mass ratio. When this blending ratio and combination are used, the use of the hydrocarbon wax (B) described later significantly improves the friction resistance, blocking resistance, heat resistance and oil resistance.

  The binder resin (A) may have a linear structure, a branched structure, a crosslinked structure, or a graft structure. The molecular weight is preferably 5,000 to 100,000 in terms of weight average molecular weight. More preferably, it is 10,000-80,000.

<Polyurethane resin (A1)>
The polyurethane resin (A1) preferably has a weight average molecular weight of 10,000 to 100,000, a glass transition temperature of preferably −60 ° C. to 0 ° C., and further at 30 ° C. in dynamic viscoelasticity measurement. Those having a storage elastic modulus E ′ of 10 ⁷ to 10 ⁹ Pa are preferred. In addition, the glass transition temperature of a polyurethane resin (A1) is a DSC measurement value.

  The polyurethane resin (A1) preferably has an amine value and / or a hydroxyl value, and the amine value is preferably 1 to 20 mgKOH / g. Moreover, what has a hydroxyl group is especially preferable, and it is preferable that a hydroxyl value is 1-20 mgKOH / g.

  The polyurethane resin (A1) preferably contains a polyether polyol-derived structural unit, and the content thereof is preferably 5 to 80% by mass, more preferably 100% by mass of the solid content of the polyurethane resin (A1). It is 10-60 mass%, More preferably, it is 10-50 mass%.

  The polyurethane resin (A1) is not particularly limited and is appropriately produced by a known method. For example, a polyurethane resin composed of a polyol and a polyisocyanate, a polyurethane resin obtained by reacting a urethane prepolymer of a terminal isocyanate composed of a polyol and a polyisocyanate, and an amine chain extender are preferable.

  Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimer diol, and hydrogenated dimer diol. Of these, the use of polyether polyol, polyester polyol, and polycaprolactone polyol is preferred.

Examples of the polyether polyol include polymer or copolymer polyether polyols such as ethylene oxide, propylene oxide, and tetrahydrofuran. Among them, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are preferable, and the number average molecular weight is preferably 200 to 7,000. The number average molecular weight is calculated from the hydroxyl value with the terminal being a hydroxyl group, and is obtained from (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × Hydroxyl number / Hydroxyl value

  Examples of the polyester polyol include a condensate obtained by an esterification reaction of a dibasic acid and a diol. Dibasic acids include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1 4-cyclohexyl dicarboxylic acid, dimer acid, hydrogenated dimer acid and the like. Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octanediol. 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl- 1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer diol , Hydrogenated dimer diol, etc. It is below.

The diol is preferably a diol having a branched structure. The branched structure means a diol having an alkyl side chain in which at least one hydrogen atom of an alkylene group contained in the diol is substituted with an alkyl group, and includes propylene glycol, 1,3-butanediol, 2-methyl-1 , 3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4- Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, And 2,2,4-trimethyl-1,6-hexanediol and the like. These are particularly preferable because they improve printability, printing effect, and blocking resistance.
These polyester polyols can be used alone or in admixture of two or more. The dibasic acid is particularly preferably sebacic acid or adipic acid. Also, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups can be used in combination.

  The number average molecular weight of the polyester polyol is preferably 200 to 7,000. The number average molecular weight can be determined by the above (Formula 1). The acid value of the polyester polyol used in the present invention is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less.

  Further, the polyurethane resin (A1) preferably further has a low molecular diol and a structural unit composed of polyisocyanate. Since the content of the low molecular diol is the desired storage elastic modulus and glass transition temperature of the polyurethane resin (A1), there is no limit on the amount used, but the polyurethane resin (A1) has a solid content of 100% by mass, The amount is preferably 20.0 parts by mass, and more preferably 1.0 to 10.0% by mass. The low molecular diol preferably has a molecular weight of 50 to 800, and includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1 , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3, 5-trimethylpentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1- Monoglycerol ether, 2-monoglycerol ether Dimer diol, hydrogenated dimer diol.

  Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. Although not limited to the following, for example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate Cyanate, isophorone diisocyanate, dimaryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane Examples thereof include diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. These may be trimers to form an isocyanurate ring structure. These polyisocyanates can be used alone or in admixture of two or more. Of these, isocyanurate of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate is preferable.

  The amine chain extender is not limited to the following, but preferably has a molecular weight of 500 or less, and examples thereof include diamines and polyfunctional amines, such as ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine. In addition to diamine chain extenders such as isophorone diamine, dicyclohexylmethane-4,4′-diamine, p-phenylene diamine, 2-hydroxyethyl ethylene diamine, 2-hydroxyethyl propyl diamine, 2-hydroxyethyl propylene diamine, di- 2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2-hi B hydroxypropyl ethylenediamine hydroxyl can also be used diamine chain extender having like. These chain extenders can be used alone or in admixture of two or more. If necessary, a polyfunctional amine chain extender having three or more functions can also be used. Specifically, diethylenetriamine, iminobispropylamine: (IBPA, 3,3′-diaminodipropylamine), triethylenetetramine N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6-iminodihexylamine, 3,7-diazanonan-1,9-diamine, N, N′-bis (3- Aminopropyl) ethylenediamine. Of these, isophoronediamine, hexamethylenediamine, and iminobispropylamine are preferable.

  Moreover, a monovalent active hydrogen compound can also be used as a polymerization terminator for the purpose of terminating excess reaction. Such a compound is not particularly limited as long as it is a monoamine compound having a primary or secondary amino group, and examples thereof include dialkylamines such as di-n-butylamine and aminoalcohols such as 2-ethanolamine. . Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, particularly when it is desired to introduce a carboxyl group into the polyurethane resin. When using a polymerization terminator, the chain terminator and chain extender may be used together to carry out the chain extension reaction, and after the chain extension reaction has been performed to some extent with the chain extender, the end terminator is added alone. Thus, an end termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

  As a method for synthesizing the polyurethane resin (A1), it is preferable to react a polyol, a low molecular diol or the like with a polyisocyanate, and then react with an amine chain extender and, if necessary, a polymerization terminator to form a polyurethane resin. For example, a polyol and a polyisocyanate are reacted with an inert solvent for an isocyanate group as necessary, and further, if necessary, reacted at a temperature of 50 ° C. to 150 ° C. using a urethanization catalyst (urethanization reaction). And a prepolymer method in which a polyurethane resin is obtained by reacting this prepolymer with an amine chain extender, or a polymer polyol, a polyisocyanate, an amine chain extender and ( And a polymerization terminator) can be produced by a known method such as a one-shot method in which a polyurethane resin (A1) is obtained by reacting in one step. The amine chain extender can also be used in a urethanization reaction with polyisocyanate together with a polymer polyol.

  In the production of the prepolymer, the amount of polyol and polyisocyanate is the ratio of the number of moles of isocyanate groups of the polyisocyanate to the number of moles of hydroxyl groups in total of the polymer polyol. A range of 0 is preferable. More preferably, the NCO / OH ratio is 1.3 to 2.5.

  In addition, it is preferable in terms of reaction control to use an organic solvent for the synthesis of the prepolymer. The organic solvent that can be used is preferably an organic solvent that is inactive with an isocyanate group, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene. And the like; esters such as ethyl acetate and butyl acetate; and halogenated hydrocarbons such as chlorobenzene and perchlene. These may be used alone or in combination as a mixed solvent.

  Furthermore, a catalyst can also be used for the synthesis reaction of this prepolymer. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol compound.

  The above-obtained prepolymer having an isocyanate group at the terminal is reacted with diamine, triamine or the like as an amine chain extender at 10 to 60 ° C., and a high molecular weight polyurethane resin containing an active hydrogen group at the terminal (A1 ) Is obtained.

  The ratio of the total number of moles of amino groups of the amine chain extender to the number of moles of isocyanate groups in the prepolymer is 1.01 to 2.00, preferably 1.03 to 1.06. It is preferable to make it react.

<Cellulose-based resin (A2)>
Examples of the cellulose resin (A2) include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose, and the like. The alkyl group includes, for example, a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and the like, and an alkyl group may have a substituent. Among these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable. Particularly preferred is nitrocellulose. The molecular weight is preferably 5,000 to 1,000,000 in terms of weight average molecular weight, more preferably 10,000 to 200,000. Moreover, the thing whose glass transition temperature is 120 to 180 degreeC is preferable.

(Nitrocellulose)
Nitrocellulose is preferably obtained by reacting natural cellulose and nitric acid to obtain a nitrate ester in which three hydroxyl groups in the 6-membered ring of anhydrous glucopyranose groups in natural cellulose are substituted with nitrate groups, and average polymerization is performed. The degree is preferably in the range of 35 to 480, more preferably 50 to 200. When the average degree of polymerization is 50 or more, the strength of the ink film is improved, and the friction resistance and the rub resistance are preferable. Moreover, when the average degree of polymerization is 200 or less, solubility in a solvent, low-temperature stability of the ink, and compatibility with the combined resin are preferable. The nitrogen content is preferably 10.5 to 12.5% by mass.

<Polyamide resin (A3)>
The polyamide resin (A3) that can be used in the gravure ink of the present invention is not limited to the following, but includes thermoplastic polyamides that can be obtained by polycondensation of a polybasic acid and a polyvalent amine. In particular, a polyamide resin containing an acid component containing a polymerized fatty acid and / or dimer acid and a reaction product of an aliphatic and / or aromatic polyamine is preferable, and a resin partially containing a primary and secondary monoamine is more preferable. The polyamide resin (A3) preferably has a solubility in isopropanol of 30% by mass or more. When the solubility in alcohol is 30% by mass or more, the printability of the ink, the pigment dispersibility, the gloss, the color developability, and the low temperature stability are good.

The polybasic acid used as a raw material for the polyamide resin (A3) is not limited to the following, but adipic acid, sebacic acid, azelaic acid, phthalic anhydride, isophthalic acid, suberic acid, glutaric acid, fumaric acid. Examples include acid, pimelic acid, oxalic acid, malonic acid, succinic acid, maleic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid, trimellitic acid, dimer acid, hydrogenated dimer acid, and polymerized fatty acid. Acid, hydrogenated dimer acid and polymerized fatty acid are preferred. Here, the polymerized fatty acid is a dry or semi-dry fat or fatty acid, or one obtained by ester polymerization or transesterification thereof, and includes monobasic fatty acid, dimerized polymerized fatty acid, trimerized polymerized fatty acid and the like.
A monocarboxylic acid can be used in combination with the polybasic acid. Examples of the monocarboxylic acid used in combination include acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, and cyclohexanecarboxylic acid.

  Examples of polyvalent amines include polyamines, primary and secondary monoamines. Examples of the polyamine used in the polyamide resin (A3) include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, and methylaminopropylamine, and aliphatic polyamines such as diethylenetriamine and triethylenetetramine. Examples of polyamines include cyclohexylenediamine and isophoronediamine. Examples of araliphatic polyamines include xylylenediamine, and examples of aromatic polyamines include phenylenediamine and diaminodiphenylmethane. Furthermore, examples of primary and secondary monoamines include n-butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine and the like.

  A polyamide resin (A3) can be manufactured by the method similar to the synthesis | combining method of a normal polyamide resin (A3). The reaction temperature is 180 to 230 ° C., and it is preferably performed in an inert gas during the reaction. Since it is a dehydration reaction, it is preferable to use a fractional distillation facility. Further, the reaction may be performed under reduced pressure. Moreover, it is preferable that the equivalent ratio of the carboxyl group: amino group of a reaction component is 0.9: 1.0-1.0: 0.9.

  The polyamide resin (A3) preferably has a softening point of 100 to 140 ° C. and a weight average molecular weight of 2,000 to 70,000. When the softening point is 100 ° C. or higher, the ink film of the printed material has good surface tackiness and prevents blocking. When the softening point is 140 ° C. or lower, the ink film becomes soft and the adhesion to the substrate is improved. When the weight average molecular weight is 2,000 or more, the coating film strength of the ink becomes good, and the friction resistance, heat resistance, and high-speed printing suitability are improved. When the molecular weight is 70,000 or less, the viscosity of the ink can be lowered and the storage stability becomes good. In addition, a softening point represents the value measured by JISK2207 (ring ball method).

  The polyamide resin (A3) preferably has a structure derived from polymerized fatty acid and (hydrogenated) dimer acid. In the case of using a polymerized fatty acid, a monobasic fatty acid containing an unsaturated fatty acid or one obtained by ester polymerization thereof is preferable, and one obtained by polymerization of an unsaturated fatty acid having 16 to 22 carbon atoms or ester thereof. preferable. Polymerized fatty acids can be used alone or in combination at any ratio. Furthermore, from the viewpoints of adhesion to a plastic film, blocking resistance, oil resistance, and heat resistance, the polyamide resin (A3) preferably uses an alkanolamine as a primary or secondary monoamine component and has a hydroxyl group in the molecule.

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin is not particularly limited as long as vinyl chloride and vinyl acetate are copolymerized. The molecular weight is preferably 5,000 to 100,000 in terms of weight average molecular weight, and more preferably 20,000 to 70,000. In the solid content of 100% by mass of the vinyl chloride-vinyl acetate copolymer resin, the structure derived from the vinyl acetate monomer is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. In this case, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, blocking resistance and the like are improved.
Moreover, since the solubility to an organic solvent improves, what contains the hydroxyl group derived from a vinyl alcohol structure by saponification reaction, modification | denaturation reaction, or copolymerization is still more preferable, and it is preferable that it is 20-200 mgKOH / g as a hydroxyl value. The glass transition temperature is preferably 50 ° C to 90 ° C.

<Acrylic resin>
As the acrylic resin used for the gravure ink in the present invention, an acrylic resin obtained by polymerizing a monomer having an unsaturated double bond in a solvent using a polymerization initiator can be used. Examples of the monomer having an unsaturated double bond include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, alkyl ester compounds of (meth) acrylic acid such as lauryl (meth) acrylate, and at least one N-substituted methylol group such as N-methylol (meth) acrylamide. Containing (meth) acrylic acid amide derivatives, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate Relates, aminoalkyl esters of (meth) acrylic acid such as dipropylaminopropyl (meth) acrylate, mono- or diesters of (meth) acrylic acid such as glycols such as diethylene glycol and dipropylene glycol, styrene, α-methylstyrene, etc. Styrene derivatives, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl ester compounds of (meth) acrylic acid such as 3-hydroxypropyl (meth) acrylate, acrylic acid, methacrylic acid, malee Examples thereof include vinyl compounds having an acid group such as acid and itaconic acid. From the viewpoint of adhesion and heat resistance of the gravure ink of the present invention to a plastic film, an acrylic resin having a carboxyl group and / or a hydroxyl group is preferred. When the acrylic resin has a hydroxyl group, the monomer constituting the acrylic resin is (meth) Those containing a hydroxyalkyl ester compound of acrylic acid are preferred. The weight average molecular weight of the above acrylic resin is preferably in the range of 30,000 to 100,000. The acrylic resin preferably has a glass transition temperature (Tg) of 40 to 110 ° C.

The glass transition temperatures of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin can be measured by DSC, but can also be estimated by the FOX equation shown below.
<FOX expression> 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
[In the FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tgi (K), the mass fraction of each monomer is Wi, and (W1 + W2 + ... + Wi +... Wn = 1). ]

  In 100% by mass of the gravure ink of the present invention, the binder resin (A) is preferably contained in a solid content of 3.0 to 25.0% by mass. Moreover, it is still more preferable that it is contained at 4.5-20.0 mass%.

<Hydrocarbon wax (B)>
The hydrocarbon wax (B) used in the present invention is not limited to the following, but is a polyethylene wax (b1), a polypropylene wax (b2), a Fischer-Tropsch wax (b3), a paraffin wax, a microwax. Stalin wax etc. are mentioned. Among these, hydrocarbon wax (B) containing at least one selected from the group consisting of polyethylene wax (b1), polypropylene wax (b2) and Fischer-Tropsch wax (b3) is preferable, and polyethylene wax (b1), Fischer At least one selected from the group consisting of Tropsch wax (b3) is more preferable.

When the hardness (penetration) of the hydrocarbon wax (B) is in the range of 0.5 to 12, the compatibility with the binder resin (A) is good, and the slip resistance of the ink film is imparted. Friction, scratch resistance and blocking resistance are improved. Furthermore, the plate fogging property in gravure printing is also improved. The hydrocarbon wax (B) preferably has a density of 900 to 990 kg / m ³ at 23 ° C. as defined in JIS K7112 (Method B). More preferably, it is 925-990 kg / m < ³ >. Moreover, it is preferable that melting | fusing point in DSC measurement is 90-150 degreeC, and, as for hydrocarbon-type wax (B), More preferably, it is 100-125 degreeC. The melting point of the hydrocarbon wax (B) represents the melting point of the peak top (minimum value) of the endothermic peak in the DSCDSC temperature rise curve.
Moreover, since the gloss of a gravure ink printing surface and the printing effect in overprinting improve, it is preferable that an average particle diameter is 1-10 micrometers. Furthermore, 2-8 micrometers is preferable. In addition, the average particle diameter in hydrocarbon wax (B) represents the value of D50 in the measurement by the laser diffraction / light scattering method. Furthermore, the hydrocarbon wax (B) preferably has a melt viscosity at 140 ° C. measured in accordance with JIS K 6862 of 20 to 8000 mPa · s.

<Polyethylene wax (b1)>
The polyethylene wax (b1) is classified into ethylene polymerization type polyethylene and thermal decomposition type low density polyethylene. Ethylene-polymerized polyethylene is further divided into high-density polymerized polyethylene, low-density polymerized polyethylene, polyethylene oxide, acid-modified polyethylene, and special monomer-modified polyethylene. Either type can be used or used in combination. May be. The acid-modified polyethylene is preferably copolymerized with an acidic monomer such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride during the polymerization of ethylene, and the special monomer-modified polyethylene is an acrylic ester or styrene during the polymerization of ethylene. Those obtained by copolymerization of monomers, vinyl acetate and the like are preferred.
Among these, polyethylene wax (b1) containing at least one selected from the group consisting of high-density polymerized polyethylene, low-density polymerized polyethylene, oxidized polyethylene, acid-modified polyethylene, and special monomer-modified polyethylene is preferable. The polyethylene wax (b1) has a molecular weight of 2000 to 8000 as determined by the viscosity method, and a number average molecular weight of 500 to 6000 is particularly preferable. In the polyethylene wax (b1), the number average molecular weight is a value obtained from GPC measurement.

The polyethylene wax (b1) preferably has a density of 925 to 990 kg / m ³ at 23 ° C. as defined in JIS K7112 (Method B). Moreover, it is preferable that the melt viscosity in 140 degreeC measured based on JISK6862 is 50-8000 mPa * s. Moreover, the polyethylene wax (b1) may have an acid value. When it has an acid value, it is preferable that an acid value is 0.5-70 mgKOH / g. The polyethylene wax (b1) preferably has a melting point in DSC measurement of 90 to 150 ° C, more preferably 100 to 120 ° C.

<Polypropylene wax (b2)>
The polypropylene wax (b2) has a molecular weight of 5,000 to 30,000 as determined by the viscosity method, and preferably has a number average molecular weight of 1,000 to 40,000. The polypropylene wax (b2) preferably has a density at 23 ° C. defined in JIS K7112 (Method B) of 900 to 990 kg / m ³ , more preferably 925 to 990 kg / m ³ . The melt viscosity at 180 ° C. measured according to JIS K 6862 is preferably 50 to 2000 mPa · s. Moreover, the polypropylene wax (b2) may have an acid value. When it has an acid value, it is preferably 0.5 to 70 mgKOH / g. The polypropylene wax (b2) preferably has a melting point in DSC measurement of 90 to 150 ° C, more preferably 100 to 120 ° C.

<Fischer-Tropsch wax (b3)>
The Fischer-Tropsch wax (b3) is a wax produced from carbon monoxide and hydrogen as raw materials by the Fischer-Tropsch manufacturing method, and has a substantially saturated, straight-chain molecular structure. Due to its straight chain structure, it has a high melting point, low viscosity and is hard. The Fischer-Tropsch wax (b3) hardly deteriorates even when exposed to heat for a long time, and exhibits extremely high thermal stability.

The Fischer-Tropsch wax (b3) preferably has a number average molecular weight of 400 to 2,000. The Fischer-Tropsch wax (b3) preferably has a density of 925 to 990 kg / m ³ at 23 ° C. as defined in JIS K7112 (Method B). Moreover, it is preferable that the melt viscosity in 140 degreeC measured based on JISK6862 is 1-200 mPa * s. The Fischer-Tropsch wax (b3) may have an acid value. When it has an acid value, it is preferably 0.5 to 50 mgKOH / g. Further, the Fischer-Tropsch wax (b3) preferably has a melting point of 90 to 130 ° C., more preferably 100 to 120 ° C. in DSC measurement.

  The method for adding the hydrocarbon wax (B) to the gravure ink is not particularly limited, and the hydrocarbon wax (B) may be mixed and dispersed together with the pigment and the binder resin (A) in the pigment dispersion step of the ink. Then, a hydrocarbon wax (B) dispersed in advance with an organic solvent may be added to and included in the gravure ink. The dispersion method is not particularly limited, and a disper, roller mill, ball mill, pebble mill, attritor, sand mill, or the like can be used.

<Fatty acid amide (C)>
The gravure ink of the present invention preferably contains a fatty acid amide (C) in addition to the hydrocarbon wax (B). By using both in combination, the physical properties of the film such as the versatility of the base material in blocking resistance are dramatically improved. The fatty acid amide (C) used preferably has an aliphatic hydrocarbon group having 10 to 25 carbon atoms and an amide group. The fatty acid amide (C) is dissolved or dispersed in the gravure ink, but after printing, it is oriented on the surface of the printed film to develop slipperiness and improve the blocking resistance against the overlapping substrate with the printing roll. it is conceivable that.

The C10-25 aliphatic hydrocarbon group refers to a saturated or unsaturated aliphatic hydrocarbon group having a linear, branched, or cyclic structure, and includes an alkyl group, an alkenyl group, an alkenediyl group, and a cycloalkyl group. Etc. Of these, a saturated or unsaturated aliphatic hydrocarbon group having a linear structure is preferable.
Examples of the fatty acid amide (C) include monoamide (C1), substituted amide (C2), bisamide (C3), methylolamide (C4), ester amide (C5) and the like. It is preferably at least one selected from the group consisting of (C2) and bisamide (C3). The content of the fatty acid amide (C) is preferably 0.01 to 3% by mass and more preferably 0.1 to 2% by mass in 100% by mass of the gravure ink.

<Monoamide (C1)>
Monoamide (C1) is represented by the following general formula (1).
General formula (1)
R ¹ -CONH ₂
(In the formula, R ¹ represents an aliphatic hydrocarbon group having 10 to 25 carbon atoms.)
Examples of the monoamide (C1) include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide and the like.

<Substituted amide (C2)>
The substituted amide (C2) is represented by the following general formula (2).
General formula (2)
R ² -CONH-R ³
(In the formula, R ² and R ³ represent an aliphatic hydrocarbon group having 10 to 25 carbon atoms, and may be the same or different.)
Examples of the substituted amide (C2) include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.

<Bisamide (C3)>
Bisamide (C3) is represented by the following general formula (3) or general formula (4).
General formula (3)
R ⁴ —CONH—R ⁵ —HNCO—R ⁶
General formula (4)
^{R 7 -NHCO-R 8 -CONH-} R 9
(Wherein R ⁴ , R ⁶ , R ⁷ , and R ⁹ represent an aliphatic hydrocarbon group having 10 to 25 carbon atoms, which may be the same or different, and R ⁵ and R ⁸ are an alkylene group or Represents an arylene group.)
Examples of the bisamide (C3) include methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, and hexamethylene bis stearic acid amide. Acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-distearyl adipic acid amide, N, N Examples include '-distearyl sebacic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide, and the like.

<Methylolamide (C4)>
Methylolamide (C4) is represented by the following general formula (5).
General formula (5)
R ¹⁰ -CONHCH ₂ OH
(In the formula, R ¹⁰ represents an aliphatic hydrocarbon group having 10 to 25 carbon atoms.)
Examples of methylol amide (C4) include methylol palmitic acid amide, methylol stearic acid amide, methylol behenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, and methylol erucic acid amide.

<Esteramide (C5)>
The ester amide (C5) is represented by the following general formula (6).
General formula (6)
R ¹¹ —CONH—R ¹² —OCO—R ¹³
(In the formula, R ¹¹ and R ¹³ each represent an aliphatic hydrocarbon group having 10 to 25 carbon atoms, which may be the same or different, and R ¹² represents an alkylene group or an arylene group.)
Examples of the ester amide (C5) include stearamide ethyl stearate, oleylamide ethyl oleate, and the like.
The arylene group is preferably at least one selected from a phenylene group, a toluylene group, and an m-xylylene group.

  The melting point of the fatty acid amide (C) is preferably 50 ° C to 150 ° C. Applicable as monoamide (C1). For example, lauric acid amide (melting point 87 ° C.), palmitic acid amide (melting point 100 ° C.), stearic acid amide (melting point 101 ° C.), behenic acid amide (melting point 110 ° C.), hydroxystearic acid amide (melting point 107 ° C.), oleic acid Examples include amide (melting point: 75 ° C.) and erucic acid amide (melting point: 81 ° C.). Examples of the substituted amide (C2) include N-oleyl palmitic acid amide (melting point 68 ° C.), N-stearyl stearic acid amide (melting point 95 ° C.), N-stearyl oleic acid amide (melting point 67 ° C.), and N-oleyl stearin. And acid amide (melting point: 74 ° C.), N-stearyl erucamide (melting point: 69 ° C.), and the like. Examples of the bisamide (C3) include methylene bis stearic acid amide (melting point 142 ° C.), ethylene bis stearic acid amide (melting point 145 ° C.), ethylene bishydroxy stearic acid amide (melting point 145 ° C.), ethylene bisbehenic acid amide (melting point 142 ° C), hexamethylenebisstearic acid amide (melting point 140 ° C), hexamethylenebisbehenic acid amide (melting point 142 ° C), hexamethylene hydroxystearic acid amide (melting point 135 ° C), ethylene bisoleic acid amide (melting point 119 ° C), Ethylenebiserucamide (melting point 120 ° C.), hexamethylenebisoleic acid amide (melting point 110 ° C.), N, N′-distearyladipic acid amide (melting point 141 ° C.), N, N′-distearyl sebacic acid amide ( Melting point 136 ° C.), N, N′-diolet Ruajipin acid amide (melting point 118 ℃), N, N'- dioleyl sebacic acid amide (melting point 113 ° C.), and the like. Examples of methylolamide (C4) include methylol stearamide (melting point: 110 ° C.). Examples of the ester amide (C5) include stearamide ethyl stearate (melting point: 82 ° C.). Among these, those having a molecular weight of 200 to 800 are preferable. More preferably, it is 250-700.

  Moreover, as a fatty acid which comprises fatty acid amide (C), a C10-22 saturated fatty acid and / or a C16-25 unsaturated fatty acid are preferable, a C12-18 saturated fatty acid and / or carbon number is preferable. More preferably, it contains 18 to 22 unsaturated fatty acids. Saturated fatty acids are preferably lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, and unsaturated fatty acids are preferably oleic acid and erucic acid. Particularly preferred is a fatty acid amide (C) comprising at least one fatty acid selected from the group consisting of lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, oleic acid and erucic acid.

  The gravure ink of the present invention preferably further contains polyethylene wax (b1) and / or Fischer-Tropsch wax (b3) and fatty acid amide (C). The use ratio of the fatty acid amide (C) is preferably a fatty acid amide (C): hydrocarbon wax (B) = 10: 90 to 90:10 by mass ratio. More preferably, it is fatty acid amide (C): polyethylene wax (B) = 20: 80 to 80:20. Moreover, it is preferable to contain 0.3-3 mass% of the sum total of fatty acid amide (C) and polyethylene wax (E) in 100 mass% of gravure inks of this invention.

<Pigment>
In the gravure ink of this invention, it is preferable to contain a pigment, and it is preferable to contain 0.2-38 mass% in 100 mass% of gravure inks. The pigment can be any of organic pigments, inorganic pigments and extender pigments, but inorganic pigments containing titanium oxide, and extender pigments include silica, barium sulfate, kaolin, clay, calcium carbonate, carbonate Magnesium and the like are preferable. As the organic pigment, it is preferable to use an organic compound or an organic metal complex. Organic pigments are not limited to the following examples, but soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, ansanthrone, dianthraquinonyl, anthrapyrimidine, perylene , Perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, carbon black, etc. Is mentioned. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance Long blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, and the like.

  Specific examples of preferable organic pigments are shown below by color index. At least one or two or more selected from the group consisting of the following black pigments, indigo pigments, green pigments, red pigments, purple pigments, yellow pigments, orange pigments and brown pigments are preferred. Furthermore, at least one or more selected from the group consisting of black pigments, indigo pigments, red pigments, and yellow pigments are preferred. In particular, the use of indigo pigments and red pigments is particularly preferred.

<Black pigment>
Specifically, C.I. I. Among the black pigments of CI Pigment Black 1 to 34, a black pigment that is an organic compound or an organometallic complex is preferable. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7, C.I. I. Pigment black 9, C.I. I. Pigment black 20 and the like.

<Indigo pigment>
Specifically, C.I. I. Among the indigo pigments of CI Pigment Blue 1 to 80, indigo pigments that are organic compounds or organometallic complexes are preferable. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 5, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 22, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 25, C.I. I. Pigment blue 26, C.I. I. Pigment blue 60, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62, C.I. I. Pigment blue 63, C.I. I. Pigment blue 64, C.I. I. Pigment blue 75, C.I. I. Pigment blue 79, C.I. I. And CI Pigment Blue 80.

<Green pigment>
Specifically, C.I. I. Among the green pigments of CI Pigment Green 1 to 50, a green pigment that is an organic compound or an organometallic complex is preferable. I. Pigment green 1, C.I. I. Pigment green 4, C.I. I. Pigment green 7, C.I. I. Pigment green 8, C.I. I. Pigment green 10, C.I. I. And CI Pigment Green 36.

<Red pigment>
Specifically, C.I. I. Of the red pigments of CI Pigment Red 1 to 279, red pigments that are organic compounds or organometallic complexes are preferable. I. Pigment Red 1 to C.I. I. Pigment red 12, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 20, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 38, C.I. I. Pigment red 41, C.I. I. Pigment red 43, C.I. I. Pigment red 46, C.I. I. Pigment red 48, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 48: 6, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 53: 2, C.I. I. Pigment red 53: 3, C.I. I. Pigment red 54, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 68, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 89, C.I. I. Pigment red 95, C.I. I. Pigment red 112, C.I. I. Pigment red 114, C.I. I. Pigment red 119, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 136, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 147, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 164, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 169, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 181, C.I. I. Pigment red 182, C.I. I. Pigment red 183, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 192, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 200, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 210, C.I. I. Pigment red 211, C.I. I. Pigment red 213, C.I. I. Pigment red 214, C.I. I. Pigment red 216, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 237, C.I. I. Pigment red 238, C.I. I. Pigment red 239, C.I. I. Pigment red 240, C.I. I. Pigment red 242, C.I. I. Pigment red 245, C.I. I. Pigment red 247, C.I. I. Pigment red 248, C.I. I. Pigment red 251, C.I. I. Pigment red 253, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 256, C.I. I. Pigment red 257, C.I. I. Pigment red 258, C.I. I. Pigment red 260, C.I. I. Pigment red 262, C.I. I. Pigment red 263, C.I. I. Pigment red 264, C.I. I. Pigment red 266, C.I. I. Pigment red 268, C.I. I. Pigment red 269, C.I. I. Pigment red 270, C.I. I. Pigment red 271, C.I. I. Pigment red 272, C.I. I. Pigment red 279, and the like.

<Purple pigment>
Specifically, C.I. I. Among the purple pigments of CI Pigment Violet 1 to 50, a purple pigment that is an organic compound or an organometallic complex is preferable. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 5: 1, C.I. I. Pigment violet 13, C.I. I. Pigment violet 19 (γ type, β type), C.I. I. Pigment violet 23, C.I. I. Pigment violet 25, C.I. I. Pigment violet 27, C.I. I. Pigment violet 29, C.I. I. Pigment violet 31, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 37, C.I. I. Pigment violet 38, C.I. I. Pigment violet 42, C.I. I. Pigment violet 50, and the like.

<Yellow pigment>
Specifically, C.I. I. Of the yellow pigments of CI Pigment Yellow 1 to 219, yellow pigments that are organic compounds or organometallic complexes are preferable. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, pigment yellow 17, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 42, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 120, pigment yellow 125, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 137, C.I. I. Pigment, yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185 and C.I. I. And CI Pigment Yellow 213.

<Orange pigment>
Specifically, C.I. I. Of the orange pigments of CI Pigment Orange 1 to 81, an orange pigment that is an organic compound or an organometallic complex is preferable. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 16, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 37, C.I. I. Pigment o orange 38, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment range 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, or C.I. I. And CI Pigment Orange 74.

<Brown pigment>
C. I. Pigment brown 23, C.I. I. Pigment brown 25, or C.I. I. And CI Pigment Brown 26.

  Of the above, preferably C.I. I. Pigment red 57: 1, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 146, C.I. I. Pigment red 242, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 14, C.I. I. Pigment orange 38, C.I. I. Pigment orange 13, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 139, C.I. I. Pigment red 185, C.I. I. Pigment red 122, C.I. I. Pigment red 178, C.I. I. Pigment red 149, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment orange 34, C.I. I. Pigment orange 64, C.I. I. Pigment black 7 and the like, and it is preferable to use at least one selected from these groups or two or more.

  More specifically, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 146, C.I. I. Pigment red 242, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 14, C.I. I. Pigment orange 38, C.I. I. Pigment orange 13, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 139, C.I. I. Pigment red 185, C.I. I. Pigment red 122, C.I. I. Pigment red 178, C.I. I. Pigment red 149, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment orange 34, C.I. I. Pigment orange 64, C.I. I. Pigment black 7 or the like is preferably used.

  The color of the gravure ink of the present invention may be selected from ink compositions of other hues as required (a total of five colors of yellow, red, indigo and black as basic colors, red (orange), grass (green ), Purple 3 colors, transparent yellow, peony, vermilion, brown, pearl).

  On the other hand, examples of the inorganic pigment include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. Of the inorganic pigments, the use of titanium oxide is particularly preferred. Titanium oxide has a white color and is preferable from the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance. From the viewpoint of printing performance, the titanium oxide is preferably subjected to silica and / or alumina treatment.

  Examples of inorganic pigments other than white include, for example, aluminum particles, mica (mica), bronze powder, chrome vermillion, chrome lead, cadmium yellow, cadmium red, ultramarine, bitumen, bengara, yellow iron oxide, iron black, titanium oxide, Zinc oxide and the like can be mentioned, and aluminum is in the form of powder or paste, but it is preferably used in the form of paste from the viewpoint of handleability and safety, and may be either a leafing type or a non-leafing type.

  The pigment is an amount sufficient to ensure the density and coloring power of the gravure ink, that is, 1 to 50% by mass relative to the total mass of the ink composition, and 10 to 90% by mass in the solid content mass ratio in the ink composition. It is preferable that it is contained in the ratio. These pigments can be used alone or in combination of two or more.

<Organic solvent>
The gravure ink of the present invention preferably contains an organic solvent as a liquid medium. Although not limited to the following, organic solvents used include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, Known organic solvents such as isobutyl acetate, ester organic solvents, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol and n-butanol, and glycol ether solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether They can be used and may be used in combination. Among these, an organic solvent not containing an aromatic organic solvent such as toluene and xylene (non-toluene organic solvent) is more preferable. More preferably, an organic solvent comprising an ester organic solvent or an alcohol organic solvent is preferable. In this case, the glycol ether organic solvent may be contained in an amount of 6% by mass or less in 100% by mass of the ink. In addition, although the gravure ink of this invention may contain water as a liquid medium, the content is 0.1-5 mass% in 100 mass% of liquid media.

<Additives>
The gravure ink of the present invention can appropriately contain conventionally known ones as additives, and in the production of ink compositions, additives such as pigment derivatives, dispersants, wetting agents, adhesion aids, leveling as necessary. Agents, antifoaming agents, antistatic agents, viscosity modifiers, chelate crosslinking agents, trapping agents, antiblocking agents, wax components other than those mentioned above, isocyanate curing agents, silane coupling agents, and the like can be used.

(Chelate crosslinking agent)
It is preferable to use a chelate crosslinking agent in the gravure ink of the present invention. As the chelate crosslinking agent, titanium chelate, zirconium chelate, or the like can be used as the metal chelate crosslinking agent. Titanium chelates such as tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate, tetrastearyl titanate, etc., triethanolamine titanate, titanium acetyl acetate toner, titanium Examples thereof include titanium chelates such as tetraacetylacetonate, tetraisopropoxytitanium, titanium ethylacetoacetate, titanium lactate, octylene glycol titanate, n-butyl phosphate titanium, and propanedioxitanium bis (ethylacetylacetate). Examples of the zirconium chelate include zirconium propionate and zirconium acetyl acetate. Among chelate crosslinking agents, a chelate crosslinking agent that does not generate acetylacetone after the crosslinking reaction is preferable from an environmental viewpoint.
The chelate crosslinking agent content in the gravure ink is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 2.0% by mass. When the content is 0.1% by mass or more, the heat resistance, oil resistance, and vinyl chloride blocking resistance are improved. When the content is 5.0% by mass or less, the stability over time of the ink is improved. By using these chelate crosslinking agents, the adhesiveness to a plastic substrate or a surface-coated paper substrate is enhanced, and the friction resistance of the formed ink film is improved.

  In order to disperse the pigment stably, a dispersant can be used in combination. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. The dispersant is preferably contained in the ink in an amount of 0.1 to 10.0% by mass with respect to 100% by mass of the total mass of the ink from the viewpoint of the storage stability of the ink. Furthermore, it is more preferable that it is contained in the range of 0.1 to 3.0% by mass.

<Manufacture of gravure ink>
The gravure ink of the present invention can be produced by dissolving and / or dispersing a binder resin (A), a hydrocarbon wax (B) and the like in a liquid medium. Although not limited to the following, for example, a pigment, a polyurethane resin (A1), a vinyl chloride-vinyl acetate copolymer resin, a polyethylene wax (b1) and, if necessary, a dispersant are mixed and dispersed in an organic solvent. A gravure ink can be produced by producing a pigment dispersion, and further blending the obtained pigment dispersion with a polyurethane resin (A1) and, if necessary, other resins and additives. The particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used. In the case where bubbles or unexpectedly large particles are included in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

  The viscosity of the gravure ink is preferably in a viscosity range of 40 to 500 cps at 25 ° C. with a B-type viscometer in order to correspond to high-speed printing (50 to 300 m / min) in the gravure printing method. More preferably, it is 50-400 cps. This viscosity range corresponds to a viscosity at Zahn Cup # 4 of about 9 to 50 seconds. The viscosity of the gravure ink can be adjusted by appropriately selecting the type and amount of raw materials used, for example, the amount of pigment, binder resin (A), organic solvent and the like. The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the organic pigment in the ink.

<Printed matter>
After printing on the base material using the gravure ink of the present invention, a volatile component is removed to form a printed layer, thereby obtaining a printed matter. The printing method is a gravure printing method, for example, diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing, alone or mixed and supplied to each printing unit and applied. Then, it can be obtained by fixing the film by drying in an oven.

<Plastic base material>
The plastic substrate that can be used in the printed material of the present invention is preferably a film substrate, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene, AS resin, ABS resin and the like. Examples thereof include film base materials such as polystyrene resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, and cellophane, and film base materials made of these composite materials. A metal or metal oxide such as silica, alumina, or aluminum may be deposited on the plastic substrate, and the deposition surface may be coated with a paint such as polyvinyl alcohol. In general, the surface of a substrate to be printed is often subjected to a surface treatment such as a corona treatment. Further, for these plastic substrates, it is also possible to use a film obtained by processing a plastic film in advance such as coating and kneading of an antifogging agent, surface coating of a matting agent, and kneading.

  Antifogging agents are preferably surfactants, for example, ionic surfactants such as polyhydric alcohol fatty acid esters such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, and ethylene oxide adducts. One or more agents are used.

<Paper base material>
Furthermore, you may use a paper base material for printed matter preparation of this invention. The paper substrate is ordinary paper or cardboard, and the film thickness is not particularly specified. For example, 0.2 to 1.0 mm, 20 to 150 g / m ² can be used, and the printing surface is corona. It may be processed. The paper substrate may be vapor-deposited with a metal such as aluminum for the purpose of imparting design properties, and surface coating with acrylic resin, urethane resin, polyester resin, polyolefin resin or other resins. It may be given, and surface treatments, such as corona treatment, may be given further. Examples include coated paper and art paper.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. Parts and% represent parts by mass and mass%, respectively, unless otherwise noted.

(Hydroxyl value)
It calculated | required according to JISK0070.
(Acid value)
It calculated | required according to JISK0070.
(Amine number)
The amine value was determined according to the following method according to JISK0070 in terms of mg of potassium hydroxide in the same amount as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of resin.
0.5-2 g of the sample was precisely weighed (sample solid content: Sg). To a precisely weighed sample, 50 mL of a mixed solution of methanol / methyl ethyl ketone = 60/40 (mass ratio) was added and dissolved. Bromophenol blue was added as an indicator to the obtained solution, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine titer was determined by the following (formula 2) using the titration amount (AmL) at this time.
(Formula 2) Amine number = (A × f × 0.2 × 56.108) / S [mgKOH / g]

(Weight average molecular weight)
The weight average molecular weight was determined as a converted molecular weight using polystyrene as a standard substance by measuring a molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation). The measurement conditions are shown below.
Column: The following columns were used in series.
Guard column H _XL -H made by Tosoh Corporation
TSKgelG5000H _XL made by Tosoh Corporation
Tosoh Corporation TSKgelG4000H _XL
TSKgelG3000H _XL manufactured by Tosoh Corporation
TSKgel G2000H _XL made by Tosoh Corporation
Detector: RI (differential refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min

(Synthesis example 1) [Polyurethane resin PU1]
200 parts of polypropylene glycol (hereinafter “PPG700”) having a number average molecular weight of 700, 127 parts of isophorone diisocyanate (hereinafter “IPDI”), and 81.8 parts of ethyl acetate were reacted at 80 ° C. for 4 hours under a nitrogen stream, to obtain a terminal isocyanate. A resin solution of urethane prepolymer was obtained. Next, 49.5 parts of isophoronediamine (hereinafter “IPDA”), 3 parts of 2-ethanolamine (hereinafter “2EtAm”), mixed solvent of ethyl acetate / isopropanol (hereinafter “IPA”) = 50/50 (mass ratio) 803. To the mixture of 9 parts, the obtained resin solution of the terminal isocyanate urethane prepolymer was gradually added at 40 ° C., and then reacted at 80 ° C. for 1 hour, solid content 30%, amine value 9.5 mgKOH / g A polyurethane resin solution PU1 having a hydroxyl value of 7.3 mg KOH / g and a weight average molecular weight of 40000 was obtained.

(Synthesis example 2) [Polyurethane resin PU2]
150 parts of a polyester polyol (hereinafter referred to as “PMPA”) having a number average molecular weight of 2000 obtained by the reaction of adipic acid and 3-methyl-1,5-pentanediol, 50 parts of PPG 700, 103.4 parts of IPDI, and 75. Eight parts were reacted at 80 ° C. for 4 hours under a nitrogen stream to obtain a resin solution of a terminal isocyanate urethane prepolymer. Next, IPDA 43.6 parts, 2 EtAm 1.0 part, ethyl acetate / IPA = 50/50 (mass ratio) mixed solvent 736.2 parts mixed with the above terminal isocyanate urethane prepolymer resin solution at 40 ° C. The polyurethane resin solution PU2 having a solid content of 30%, an amine value of 8.2 mgKOH / g, a hydroxyl value of 2.4 mgKOH / g, and a weight average molecular weight of 42,000 was obtained by gradually adding and then reacting at 80 ° C. for 1 hour.

With respect to the hydrocarbon wax (B) described in Table 1, each characteristic value was measured according to the following.
The hardness (penetration) was measured at 25 ° C. according to JIS K2207.
The density was measured at 23 ° C. according to JIS K7112 (Method B).
The melting point was determined by DSC (differential scanning calorimetry measurement). The measuring machine used was DSC8231 manufactured by Rigaku Corporation, and the measurement temperature range was 25 to 180 ° C, the heating rate was 10 ° C / min, and the peak top (minimum value) of the endothermic peak in the DSC curve was taken as the melting point.
The glass transition temperature (Tg) was determined by DSC (differential scanning calorimetry measurement). In addition, the measuring machine uses DSC8231 made by Rigaku Co., Ltd., measuring temperature range -50 to 250 ° C, temperature rising rate 10 ° C / min, the midpoint between endothermic start temperature and end temperature based on glass transition in DSC curve is glass The transition temperature was used.
The average particle size is measured by laser diffraction / scattering method with a 10% solid content dispersion of hydrocarbon wax (B) mixed with ethyl acetate / isopropanol = 50/50 (mass ratio). The value of D50 was taken as the average particle size. Note that D50 represents the median diameter in the volume-based cumulative distribution. The measuring machine used was Microtrack MT3000II manufactured by Microtrack Bell.
In addition, Table 2 shows the fatty acid amide (C) used for preparing the gravure ink of the present invention.

(Example 1) [Preparation of gravure ink S1]
As binder resin (A), 31 parts of polyurethane resin solution PU1 (solid content 30%), vinyl chloride vinyl acetate copolymer resin (Solvine TAO: manufactured by Nissin Chemical Industry Co., Ltd., vinyl chloride / vinyl acetate / vinyl alcohol = 91/2) / 7 (mass ratio) copolymer resin, solid content 30% ethyl acetate solution)) 14 parts, hydrocarbon wax (B) polyethylene wax (Honeywell A-C400A) 0.8 parts, indigo pigment C. I. 11 parts of Pigment Blue 15: 3 and 43.2 parts of a solution of n-propyl acetate / IPA = 70/30 (mass ratio) were mixed and dispersed with an Eiger mill for 30 minutes to obtain gravure ink S1.

(Examples 2 to 44) [Creation of gravure inks S2 to S44]
Gravure inks S2 to S44 were obtained in the same manner as in Example 1 except that the raw materials and the blends described in Table 3-1 and Table 3-2 were changed. Abbreviations in the table represent the following. In the table, a numerical value without a unit represents a part, and a blank represents that it is not blended.
Versamide 750: BASF softening point 116 ° C. Terminal amino group-containing polyamide resin (solid content 30% isopropanol solution)
DLX5-8: Nitrocellulose produced by ICI Novel enterprises, nitrogen content 12.0% (solid content 30% isopropanol solution)
Dianal BR-107: Mitsubishi Rayon Co., Ltd. acrylic resin 30% ethyl acetate / isopropyl alcohol solution, weight average molecular weight 60000, glass transition temperature 50 ° C., acid value 3.5 mgKOH / g.
In this specification, examples other than Examples 1 to 18 are reference examples.

(Example 45) <Printing of gravure ink>
The gravure inks S22 and S1 obtained above were mixed with a mixed solvent of MEK: n-propyl acetate (hereinafter “NPAC”): IPA = 40: 40: 20 (mass ratio) with a viscosity of 16 seconds (25 ° C., Diluted to be Zahn Cup No. 3), S22 was equipped with a corroded 175 line solid plate (plate depth 25 μm), and S1 (indigo) was a Helio 175 line gradation plate (plate-type compressed gradation 100% to 3%) Using a gravure printing machine, surface printing was performed on the treated surfaces of the following base materials in the order of base material / S29 / S1 at a printing speed of 80 m / min, and printed materials J1 (OPP), K1 (anti-fogging), L1 (paper) Substrate) was obtained.
<Base material>
OPP: Biaxially stretched polypropylene (OPP) film subjected to single-sided corona discharge treatment (FOR Thickness 25 μm, manufactured by Futamura Chemical Co., Ltd.)
-Anti-fogging: Double-side anti-fog treatment OPP film (AF-662, 25 μm thickness, manufactured by Futamura Chemical Co., Ltd.)
・ Paper substrate: Coated paper (Product name: Ryuo Coat Paper 65g / m ^2, manufactured by Daio Paper Co., Ltd.)

(Examples 46 to 88)
About gravure ink S2-S44 described in Table 3-1 and Table 3-2, it prints by the printing structure of Table 5-1 and Table 5-2, and printed matter J2-J44 (OPP), K2- K44 (anti-fogging) and L2 to L44 (paper base material) were obtained.

(Comparative Examples 1 to 12) [Preparation of gravure inks T1 to T12]
Gravure inks T1 to T12 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 4 were used. In the table, a numerical value without a unit represents a part, and a blank represents that it is not blended.

(Comparative Examples 13-24)
For the gravure inks T1 to T12 described in Table 4, surface printing is performed in the same manner as in Example 45 with the printing configuration described in Table 6, and printed materials JJ1 to JJ12 (OPP), KK1 to KK12 (antifogging) ), LL1 to LL12 (paper substrate) were obtained. In Table 6, “the printing state is bad and not evaluated” means that the aggregation and precipitation of the components in the gravure ink were remarkable, and thus the evaluation was impossible.

<Evaluation>
Gravure inks S1 to S44 (Examples), T1 to T12 (Comparative Examples), and printed materials J1 to J44 (OPP), K1 to K44 (antifogging), L1 to L44 (paper base material), printed materials JJ1 to JJ12 (OPP) ), KK1 to KK12 (antifogging), and LL1 to LL12 (paper base material), the following evaluation was performed.

<Plate castability>
Plate fogging evaluation was performed on the gravure inks S1 to S44 (Examples) and T1 to T12 (Comparative Examples). The dilution solvent is MEK: NPAC: IPA = 40: 40: 20, the viscosity is 16 seconds (25 ° C.) with Zahn cup # 3, and the area of the plate cover part after 60 minutes of idling of the plate in the printing press is Visual evaluation and evaluation were performed.
○: Plate cover area is 0 to 5% (good)
○ △ ・ ・ ・ plate cover area is 6-10% (practical)
Δ ··· The plate covering area is 11 to 30% (somewhat poor).
Δ × The plate cover area is 31 to 50% (defect).
× ··· The plate cover area is 50% or more (very bad)
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Trapability>
The printed materials J1 to J44, JJ1 to JJ12, L1 to L44, and LL1 to LL12 were evaluated for trapping properties using a KEYENCE microscope (VHX-5000). The evaluation was performed on the gradation pattern portion.
○: Printing unevenness occurs when the plate depth is less than 70% (good)
○ △ ... Printing unevenness occurs when the plate depth is 70% or more and less than 80%.
Δ: Printing unevenness occurs when the plate depth is 80% or more and less than 90% (slightly poor)
Δ ×: Printing unevenness occurs when the plate depth is 90% to less than 100% (defect).
× ···· become red ink all network points of overlap, has not spread wet at all (very poor)
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Glossy>
With respect to 100% gradation of printed materials J1 to J44 (OPP) and JJ1 to JJ12 (OPP), the gloss was evaluated by a gloss value of 60 ° of a BYK-Gardner Micro-TRI-gross meter and visually.
○ ・ ・ ・ ・ ・ Gloss value of 50 or more (good)
○ △ ・ ・ ・ ・ Gloss value of 20 or more and less than 50 (practical)
△ ・ ・ ・ ・ ・ Slightly matte (slightly defective)
△ × ・ ・ ・ ・ Strong matte feeling (defect)
× ··· No gloss (very bad)
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Abrasion resistance>
With respect to the printed materials J1 to J44 (OPP) and JJ1 to JJ12 (OPP), the coating strength was measured using a Gakushin type friction fastness tester manufactured by Tester Sangyo Co., Ltd., and evaluated according to the following evaluation criteria. The measurement conditions were a test piece width of 20 mm, a load of 200 g, 30 reciprocations, and No. 3 for Kanakin.
○ …… No ink film is removed (good)
○ △ ・ ・ ・ The area where the ink coating is taken is less than 10% (practical)
Δ: The area where the ink film is removed is 10% or more and less than 30% (slightly poor)
△ × ・ ・ ・ ・ The area where the ink film is taken is 30% or more and less than 50% (defect)
× ・ ・ ・ ・ ・ taken over the entire surface (very bad)
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Blocking resistance>
Printed materials J1 to J44 (OPP), K1 to K44 (antifogging), L1 to L44 (paper base material), JJ1 to JJ12 (OPP), KK1 to KK12 (antifogging), LL1 to LL12 (paper base material) The blocking resistance was evaluated under the following conditions.
(Sample and pressure)
OPP printed surface / PVC sheet 0.5kg / cm ²
Printed surface of OPP printed matter / non-corona treated surface of OPP substrate 0.5 kg / cm ²
Anti-fog OPP film printed matter / treated surface of anti-fog OPP film 5.0 kg / cm ²
Paper base print / paper base uncoated surface 5.0 kg / cm ²
(Standing conditions) 40 ° C.-80% RH 14 hours (Evaluation method) The printed surface and various substrates are peeled off, and the degree of ink film removal (peeling) from the printed surface is visually determined.
In addition, in the above, it represents below the vinyl chloride sheet.
PVC sheet: Soft PVC sheet Hagitec Co., Ltd. Model number 2556-607-02 Thickness 0.2mm
Judgment criteria ○ The ink film on the printed surface does not peel at all, and the peel resistance is low (good)
○ △ ・ ・ ・ The peeled area of the ink film is 1% or more and less than 5%, and the peel resistance is small (practical)
Δ: The ink film peeled area is 5% or more and less than 20% (slightly poor)
Δ × ··· Ink film peeling area of 20% or more and less than 50% (defect)
× ・ ・ ・ ・ ・ Ink film peels 50% or more (very bad)
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Adhesiveness>
About printed matter J1-J44 (Example) and JJ1-JJ12 (comparative example), after leaving at 25 degreeC for 1 day, respectively, the adhesive tape (cellophane tape by Nichiban Co., Ltd.) of width 12mm was stuck on the printing surface, and this was rapidly The appearance of the printed surface when peeled was visually determined. The criteria for determination were as follows.
○ …… The ink film on the printing surface does not peel at all (good)
○ △ ・ ・ ・ The peeled area of the ink film is 1% or more and less than 5% (practical)
Δ: The ink film peeled area is 5% or more and less than 20% (slightly poor)
Δ × ··· Ink film peeling area of 20% or more and less than 50% (defect)
× …… The ink film is peeled off by 50% or more (very bad)
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Heat resistance>
About printed matter J1-J44 (Example) and JJ1-JJ12 (comparative example), each cut into the size of 2 cm x 10 cm, and the aluminum foil (thickness 30 micrometers) cut into the same size and the printed surface of a printed matter were piled up It was. Using a heat sealer manufactured by Sentinel, the aluminum foil was pressed at 120 ° C. for 1 second at a pressure of 2 × 9.8 N / cm ² , and the degree of peeling of the ink film when the aluminum foil was peeled was visually determined. The criteria for determination were as follows.
○ ・ ・ ・ ・ ・ The ink on the printing surface does not peel off at all (good)
○ △ ・ ・ ・ The peeled area of the ink film is 1% or more and less than 5% (practical)
Δ: The ink film peeled area is 5% or more and less than 20% (slightly poor)
Δ × ··· Ink film peeling area of 20% or more and less than 50% (defect)
× …… The ink film is peeled off by 50% or more (very bad)
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Oil resistance>
About printed matter J1-J44 (Example) and JJ1-JJ12 (comparative example), it cuts into a size of 2 cm x 20 cm, respectively, and commercially available margarine (trade name: manufactured by Neosoft Snow Brand Milk Products Co., Ltd.) melted on the printed surface. After coating on the entire surface and allowing to stand at 25 ° C. for 6 hours, the degree of ink peeling was visually determined with a Gakushoku-type friction fastness tester manufactured by Tester Sangyo Co., Ltd. The conditions were a load of 200 g, 10 reciprocations, and No. 3 Kanaki. The criteria for determination were as follows.
○ ・ ・ ・ ・ ・ The ink on the printing surface does not peel off at all (good)
○ △ ・ ・ ・ The peeled area of the ink film is 1% or more and less than 5% (practical)
Δ: The ink film peeled area is 5% or more and less than 20% (slightly poor)
Δ × ··· Ink film peeling area of 20% or more and less than 50% (defect)
× ················ 50% or more of ink film is removed
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

  From the evaluation results, by using the gravure ink of the present invention, the printability and the gloss of the printed layer are good, and further, the substrate versatility in terms of blocking resistance and adhesiveness, heat resistance, and oil resistance are compatible. I was able to. Furthermore, in the present invention, it was confirmed that the printing suitability (trapping property) in overprinting was greatly improved.

Claims (8)

A gravure ink for printing on a paper or plastic substrate, which contains a binder resin (A), a hydrocarbon wax (B) and an organic solvent, and satisfies the following (1) to (3) Features organic solvent-based gravure ink.
(1) The hardness (penetration) at 25 ° C. of the hydrocarbon wax (B) defined in Japanese Industrial Standard JIS K 2207 is 0.5 to 12, and the average particle diameter is 1 to 10 μm. is there.
(2) The hydrocarbon wax (B) is contained in 0.1 to 2.5% by mass in 100% by mass of the gravure ink.
(3) a binder resin (A), a vinyl chloride polyurethane resin (A1) - vinyl acetate copolymer resin, containing a mass ratio of 95 / 5-30 / 7 0.   The organic solvent-based gravure ink according to claim 1, which is for surface printing.   The hydrocarbon wax (B) contains at least one selected from the group consisting of polyethylene wax (b1), polypropylene wax (b2) and Fischer-Tropsch wax (b3). The organic solvent-based gravure ink described.   The organic solvent-based gravure ink according to any one of claims 1 to 3, wherein the hydrocarbon wax (B) has a melting point of 90 to 150 ° C. Furthermore, it contains a fatty acid amide (C) , the hydrocarbon wax (B) contains a polyethylene wax (b1),
The mass ratio (B) / (C) of the hydrocarbon wax (B) and the fatty acid amide (C) is in the range of 80/20 to 20/80, and the fatty acid amide (C ) And the polyethylene wax (B) is 0.3 to 3% by mass, and the organic solvent-based gravure ink according to any one of claims 1 to 4.   The organic solvent gravure ink according to claim 5, wherein the fatty acid amide (C) contains a fatty acid amide having an aliphatic hydrocarbon group having 10 to 25 carbon atoms. Furthermore, 0.5-2.0 mass% of titanium chelate is contained in gravure ink as a chelate crosslinking agent, The organic solvent type gravure ink in any one of Claims 1-6 characterized by the above-mentioned.
Claim 1-7 printing product of printing by the organic solvent-based gravure ink according to any one.