JP7346795B1 - Laminating printing ink composition for back printing - Google Patents

Abstract

[Problem] Laminate printing for back printing that has excellent printability such as ink storage stability, adhesive wettability, blocking resistance, abrasion resistance, doctor cutability, guide roll removal, etc., and excellent retort resistance of printed materials. An ink composition is provided.
[Solution] A pigment, a polyurethane resin having an amino group and a hydroxyl group as a binder resin, an organic solvent, and a penetration degree at 25° C. specified by JIS K 2207 of 4.0 to 14.0, and an average particle size. A laminating printing ink composition for back printing, containing 0.05 to 5.0% by mass of a hydrocarbon wax having a diameter of 3.0 to 10.0 μm based on the total solid content of the laminating printing ink composition for back printing. .
[Selection diagram] None

Description

The present invention relates to a laminating printing ink composition for back printing, mainly for printing on films for packaging materials and the like.

BACKGROUND OF THE INVENTION Packaging materials using various plastic films are used for foods, confectionery, household goods, pet food, etc. from the viewpoints of design, economy, protection of contents, transportability, etc. Furthermore, many packaging materials are subjected to gravure printing or flexographic printing with the intention of imparting designs and messages that appeal to consumers.
In order to obtain these packaging materials, we use unprinted printing that is printed on the surface of the base film of the packaging material, or apply adhesives or anchors as necessary to the printed surface that is printed on the surface of the base film of the packaging material. A printing agent is applied and the film is printed for lamination.

In printing for laminating a film, after sequentially printing a color ink composition and a white ink composition on various films such as polyester, nylon, aluminum foil, foil, etc., on the printed layer of the white ink composition, Polyethylene films, polypropylene films, etc. for the purpose of heat sealing are laminated by dry lamination using an adhesive or extrusion lamination using an anchor coating agent.
The laminate printing ink composition for back printing used in back printing includes a polypropylene glycol-containing polyurethane resin and a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group as binder resins, and essential components to improve adhesion. A laminating printing ink composition for back printing containing carbon dioxide has been proposed (see, for example, Patent Document 1).

In recent years, there has been a growing demand for the cosmetic appearance of printed matter and the physical properties of the coating after printing, such as adhesive wettability, blocking resistance, abrasion resistance, doctor cutting, guide toll removal, etc. during printing. The physical properties of the coating film after printing, such as the suitability for laminating printed matter, are also becoming required.
When conventional laminating printing ink compositions for back printing are used, the ink adhered to the guide rolls is not removed sufficiently and the ink adhered to the guide rolls is re-transferred to the printing surface, causing stains. There has not been a laminate printing ink composition for back printing that satisfies all of the problems such as the occurrence of streaks, insufficient wettability of the adhesive, and reduced retort resistance.

Japanese Patent Application Publication No. 2005-298618

The present invention provides a laminate for back printing that has excellent printability such as ink storage stability, adhesive wettability, blocking resistance, abrasion resistance, doctor cutability, guide toll removal, etc., and excellent retort resistance of printed materials. An object of the present invention is to provide a printing ink composition.

The present inventors have discovered that the above-mentioned problems can be solved by creating the following laminating printing ink composition for back printing, and have arrived at the following invention.
1. Pigment, polyurethane resin having amino groups and hydroxyl groups as binder resin, organic solvent, penetration degree at 25°C specified by JIS K 2207 is 4.0 to 14.0, and average particle size is 3.0 to 10. A laminating printing ink composition for back printing, containing 0.05 to 5.0% by mass of a hydrocarbon wax having a diameter of 0.0 μm based on the total solid content of the laminating printing ink composition for back printing.
2. 2. The laminating printing ink composition for back printing according to 1, wherein the hydrocarbon wax is a polyethylene wax.
3. The laminate printing ink composition for back printing according to 1 or 2, wherein the polyurethane resin has an amine value of 1.0 to 13.0 mgKOH/g and a hydroxyl value of 0.5 to 12.0 mgKOH/g.
4. Any one of 1 to 3, wherein the polyurethane resin has at least one of a primary amino group or a secondary amino group at the end, and has a hydroxyl group at the end of the molecule and at a site other than the end of the molecule. The laminating printing ink composition for back printing as described.
5. 5. The laminating printing ink composition for back printing according to any one of 1 to 4, which contains a vinyl chloride/vinyl acetate copolymer resin having a hydroxyl group and/or a vinyl chloride/acrylic copolymer resin having a hydroxyl group.
6. 6. The laminate printing ink composition for back printing according to any one of 1 to 5, wherein the organic solvent is a mixed solvent containing an ester-based organic solvent and an alcohol-based organic solvent.
7. 7. The laminate printing ink composition for back printing according to any one of 1 to 6, further containing water.

According to the present invention, back printing has excellent printability such as ink storage stability, adhesive wettability, blocking resistance, abrasion resistance, doctor cutability, guide toll removal, etc., and excellent retort resistance of printed matter. A laminating printing ink composition can be provided. It should be noted that surface printing ink compositions require effects other than many of these effects since they are not laminated onto their printing layer.

The present invention is a laminate printing ink composition for back printing which contains a pigment, a polyurethane resin having an amino group and a hydroxyl group as a binder resin, and an organic solvent, and furthermore, the composition has a needle penetration temperature of 25° C. as defined in JIS K 2207. A hydrocarbon wax having a hardness of 4.0 to 14.0 and an average particle diameter of 3 to 10 μm is added to the total solid content of the laminating printing ink composition for back printing at 0.05 to 5.0 μm. This is a laminate printing ink composition for back printing containing 0% by mass.
Hereinafter, the laminating printing ink composition for back printing of the present invention will be specifically explained.

<Pigment>
Pigments used in the laminate printing ink composition for back printing of the present invention include inorganic color pigments, organic color pigments, extender pigments, etc. that have been conventionally used in gravure inks. Examples of inorganic color pigments include titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, deep blue, ultramarine blue, carbon black, and graphite. Examples of organic coloring pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. Examples of extender pigments include calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
The content of these pigments in the printing ink composition is usually about 1 to 50% by mass.

<Polyurethane resin>
As the polyurethane resin, a polyurethane resin having an amino group and a hydroxyl group can be used.
Among polyurethane resins having amino groups and hydroxyl groups, polyurethane resins having one or more types selected from primary amino groups, secondary amino groups, and tertiary amino groups at the end of the molecule are preferred; More preferred is a polyurethane resin having one or more selected from primary amino groups and secondary amino groups, and containing hydroxyl groups at the terminals and at sites other than the terminals.

Since the polyurethane resin has specific functional groups such as the above-mentioned amino group and hydroxyl group, the printing ink composition for back printing has excellent storage stability, printability, adhesiveness, and lamination suitability.
The amine value of the polyurethane resin is preferably 1.0 mgKOH/g or more, more preferably 1.5 mgKOH/g or more. Further, it is preferably 13.0 mgKOH/g or less, more preferably 11.0 mgKOH/g or less, and even more preferably 10.0 mgKOH/g or less. In addition, in order to exhibit even better adhesion, the hydroxyl value is preferably 0.5 mgKOH/g or more, more preferably 1.0 mgKOH/g or more, and even more preferably 3.0 mgKOH/g or more. Further, it is preferably 12.0 mgKOH/g or less, more preferably 11.0 mgKOH/g or less, and even more preferably 10.0 mgKOH/g or less.
If the amine value is less than 1.0 mgKOH/g, the adhesiveness of the printing ink composition for films of the present invention to the film may be reduced, and furthermore, the suitability for lamination may be reduced. When the amine value exceeds 13.0 mgKOH/g, blocking resistance may decrease.
If the hydroxyl value is less than 0.5 mgKOH/g, resolubility and adhesiveness may decrease. When the hydroxyl value exceeds 12.0 mgKOH/g, blocking resistance tends to decrease.

In the present invention, the above-mentioned amine value means the amine value per 1 g of solid content, and is determined by potentiometric titration method (for example, COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATION) using a 0.1N hydrochloric acid aqueous solution. K-900), Hiranuma Sangyo Co., Ltd.) and converted to the equivalent amount of potassium hydroxide.
In the present invention, the hydroxyl value can be determined by applying the method specified in JIS K1557-1:2007. That is, after dissolving the polyurethane resin sample in a pyridine solution containing an acetylating reagent (e.g., acetic anhydride) to acetylate the hydroxyl groups, the excess acetylating reagent is hydrolyzed with water, and the resulting acetic acid is The amount is determined by titration with potassium hydroxide. At this time, since the carboxyl groups contained in the polyurethane resin are also titrated with potassium hydroxide, the hydroxyl value (mgKOH/g) is calculated by subtracting the acid value of the polyurethane resin from the above titration result.

The polyurethane resin will be explained in detail.
As the polyurethane resin, a polyurethane polyurea resin and/or a polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound is preferable. A polyurethane resin other than a polyurethane polyurea resin may or may not be used together with such a polyurethane polyurea resin.
A polyurethane polyurea resin is obtained by chain-extending and/or terminal-terminating a urethane prepolymer obtained from an organic diisocyanate component and a polymeric diol component.
The polyurethane polyurea resin obtained using the ketiminated compound can be used as a chain extender and/or a reaction terminator. A polyurethane polyurea resin obtained by reacting a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound with a urethane prepolymer in an organic solvent; b. A polyurethane polyurea resin obtained by adding a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound in an organic solvent to a urethane prepolymer, stirring the mixture, adding water, and then performing chain extension and reaction termination. This is what I did. By using a polyurethane polyurea resin obtained using a ketiminated compound, the amine odor of a lanate printing ink composition for back printing obtained is reduced and the stability over time is excellent.
The polyurethane polyurea resin may contain biomass polyurethane polyurea resin in consideration of the environment.

<Polyurethane polyurea resin>
The polyurethane polyurea resin is a polyurethane polyurea resin having a hydroxyl group and at least one type selected from a primary amino group and a secondary amino group at the end of the molecule. As these polyurethane polyurea resins, polyurethane resins obtained by synthesizing a urethane prepolymer by reacting an organic diisocyanate compound and a polymeric diol compound and reacting this with the following chain extender and reaction terminator are preferably used. Can be used.
(Synthesis of urethane prepolymer)
Each of the above urethane prepolymers is obtained by reacting the following organic diisocyanate compound with a polymeric diol compound.

(Organic diisocyanate compound)
Examples of the organic diisocyanate compounds include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, and dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI); Examples include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and araliphatic diisocyanate compounds such as α,α,α',α'-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in combination of two or more. Among these, alicyclic diisocyanate compounds, aliphatic diisocyanate compounds, and araliphatic diisocyanate compounds are more preferred.
In addition, as other organic diisocyanate compounds, aromatic compounds such as 1,3- and/or 1,4-phenylene diisocyanate, 4,4-diisocyanatobiphenyl, 3,3-dimethyl-4,4-diisocyanatobiphenyl, etc. Diisocyanate compounds, alicyclic diisocyanate compounds such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), aliphatic diisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate Compounds and araliphatic diisocyanate compounds such as m- and/or p-xylylene diisocyanate (XDI) can also be utilized. When other organic diisocyanate compounds are used in combination, they can be used together so that the number of isocyanate groups in the other organic diisocyanate compounds is 50% or less with respect to the total number of isocyanate groups in all organic diisocyanate compounds, but more preferably It is 30% or less, more preferably 10% or less. Or, in 100 parts by mass of all organic diisocyanate compounds, the amount of other organic diisocyanate compounds is 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 10 parts by mass or less.

(Polymer diol compound)
Examples of the polymer diol compounds include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide, adipic acid, sebacic acid, and anhydride. One or more dibasic acids such as phthalic acid, and one type of glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc. Alternatively, polyester diol compounds such as polyester diols and polycaprolactone diols obtained by condensation reaction of two or more types can be mentioned. These polymeric diol compounds can be used alone or in combination of two or more. Furthermore, in addition to the above polymer diol compounds, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- Low molecular weight diol compounds such as butanediol and 1,3-butanediol may be used alone or in combination of two or more. The above-mentioned polymeric diol compound preferably has a number average molecular weight of 1,000 to 8,000, more preferably 1,000 to 5,500, and still more preferably 1,000 to 4,000. preferable. Further, as the above-mentioned polymeric diol compound, one containing 3-methyl-1,5-pentylene adipate diol can be selected. At this time, the following can be used in combination as other polymeric diol compounds. Polymer diol compounds other than 3-methyl-1,5-pentylene adipate diol include one or more dibasic acids such as adipic acid, sebacic acid, and phthalic anhydride, and ethylene glycol, propylene glycol, Polyester diols, polycaprolactone diols, etc. obtained by condensation reaction with one or more glycols such as 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. Examples include polyester diol compounds, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and polyether diol compounds such as alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide. These polymeric diol compounds can be used alone or in combination of two or more.

Among the above, 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 1,000 to 8,000 is obtained by condensation reaction of adipic acid and 3-methyl-1,5-pentanediol. Preferably, 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 1,000 to 4,000 is more preferable. When other polymeric diol compounds are used together, they can be used together so that the number of hydroxyl groups in the other polymeric diol compounds is 70% or less of the total number of hydroxyl groups in all polymeric diol compounds, but more preferably 55% or less. % or less, more preferably 40% or less. Or, in 100 parts by mass of all polymer diol compounds, the amount of other polymer diol compounds is 50 parts by mass or less, more preferably 35 parts by mass or less, still more preferably 20 parts by mass or less. In addition, when the organic solvent of the laminating printing ink composition for back printing is a mixed solvent system of an ester solvent and an alcohol solvent (hereinafter referred to as "mixed liquid" in some cases), which will be described later, a polymeric diol compound may be used. When a polyether diol compound, preferably polypropylene glycol, is used as a polyurethane resin, the solubility of the resulting polyurethane resin tends to be high, and printability such as gradation reproducibility and fog prevention properties tends to be good. This is preferable because it allows a wide range of printing ink compositions to be designed depending on the required performance.

(Biomass polyurethane polyurea resin)
The polyurethane resin may include a biomass polyurethane polyurea resin in consideration of the environment. The biomass polyurethane polyurea resin will be explained below. In addition, among the explanations of the biomass polyurethane polyurea resin, explanations common to the above-mentioned polyurethane polyurea resins will be omitted as appropriate. Biomass polyurethane polyurea resin is a polyurethane resin containing biomass-derived (plant-derived) components. Biomass polyurethane resin can contribute to preventing global warming and reducing environmental impact compared to the use of other exhaustible resources. Preferably, it is a biomass polyurethane polyurea resin obtained by synthesizing a biomass urethane prepolymer by reacting a biopolyester polyol compound and an organic diisocyanate compound, and reacting this with a chain extender and a reaction terminator as necessary. More preferably, the isocyanate compound is a plant-derived bioisocyanate.

(Isocyanate compound)
In addition to the organic diisocyanates explained for the polyurethane polyurea resins above, diisocyanates derived from vegetable oils can be used. Organic diisocyanate compounds derived from vegetable oils are produced by converting divalent carboxylic acids derived from plants into terminal amino groups by acid amidation and reduction, and then reacting with phosgene to convert the amino groups into isocyanate groups. can get. Examples of biopolyisocyanates derived from plants include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. Furthermore, a plant-derived isocyanate compound can also be obtained by using a plant-derived amino acid as a raw material and converting its amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by methyl esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Furthermore, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group into an isocyanate group.

(Bio polyester polyol compound)
A biopolyester polyol compound (biomass polyester polyol) will be explained. As the biopolyester polyol compound, a biopolyester polyol obtained by reacting a short chain diol compound having 2 to 4 carbon atoms with a carboxylic acid compound can be used. In the biopolyol component, at least one of the short chain diol compound and the carboxylic acid compound is preferably derived from a plant, and even more preferably both are derived from a plant. The plant-derived short chain diol compound having 2 to 4 carbon atoms is not particularly limited. For example, the short chain diol compound may be 1,3-propanediol, 1,4-butanediol, ethylene glycol, etc. obtained from plant materials by the following method. These may be used in combination. 1,3-propanediol can be produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (eg, corn, etc.). The 1,3-propanediol component produced by biomethods such as the fermentation method described above is superior in terms of safety compared to the 1,3-propanediol component produced by the EO production method, and has useful substances such as lactic acid. By-products can be obtained, and production costs can also be kept low. 1,4-butanediol can be produced by producing succinic acid by producing glycol from plant resources and fermenting it, and then hydrogenating this. Furthermore, ethylene glycol can be produced from bioethanol obtained by conventional methods via ethylene.

The plant-derived carboxylic acid compound is not particularly limited. For example, carboxylic acid compounds include sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid, and the like. These may be used in combination. Among these, the carboxylic acid compound preferably contains at least one selected from the group consisting of sebacic acid, succinic acid, and dimer acid. Further, it may contain an organic acid having a molecular weight of 300 or less and having three or more active hydrogen groups in one molecule. Note that such an organic acid component is not particularly limited.
The biopolyester polyol compound is produced as a 100% plant-derived biopolyester polyol by appropriately condensing a plant-derived short chain diol compound and a plant-derived carboxylic acid. Specifically, polytrimethylene sebacate polyol is obtained by direct dehydration condensation of plant-derived sebacic acid and plant-derived 1,3-propanediol. Furthermore, polybutylene succinate polyol can be obtained by direct dehydration condensation of plant-derived succinic acid and plant-derived 1,4-butanediol. One or more of these biopolyester polyol compounds may be used. The urethane prepolymer obtained using these plant-derived components may be contained in an amount of 10% by mass or more, or 40% by mass or more in terms of solid content in the entire urethane prepolymer.

(Chain extender and reaction terminator)
Next, the chain extender and reaction terminator used in the polyurethane polyurea resin and the biomass polyurethane polyurea resin will be explained.
As the chain extender, known chain extenders used in polyurethane polyurea resins as binders for printing ink compositions can be used. For example, among polyamine compounds, ethylene diamine, propylene diamine, tetramethylene diamine, hexane diamine, etc. Aliphatic diamines such as methylene diamine, isophorone diamine, alicyclic diamines such as 4,4'-dicyclohexylmethane diamine, aromatic diamines such as toluylene diamine, aromatic aliphatic diamines such as xylene diamine, N- Diamines with hydroxyl groups such as (2-hydroxyethyl)ethylenediamine (aminoethylethanolamine), N-(2-hydroxyethyl)propylenediamine, N,N'-di(2-hydroxyethyl)ethylenediamine, ethylene glycol, propylene Examples include diol compounds such as glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and triethylene glycol. Furthermore, a polyamine compound such as diethylenetriamine or triethylenetetramine can be used in combination within a range where the polyurethane polyurea resin does not gel. As a reaction terminator for introducing a primary amino group and a secondary amino group into the terminals of a polyurethane polyurea resin, examples of polyamine compounds include aliphatic diamines such as ethylenediamine, propylene diamine, tetramethylene diamine, and hexamethylene diamine, and isophorone. diamine, alicyclic diamines such as 4,4'-dicyclohexylmethane diamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as tolylene diamine, aromatic aliphatic diamines such as xylene diamine, N Examples include diamines having a hydroxyl group such as -(2-hydroxyethyl)ethylenediamine (aminoethylethanolamine) and N-(2-hydroxyethyl)propylenediamine. Among these, polyamines having a primary amino group such as diethylenetriamine and triethylenetetratriamine are preferred. Reaction terminators that introduce hydroxyl groups into polyurethane polyurea resins include alkanolamines such as monoethanolamine and diethanolamine, and those having hydroxyl groups such as N-(2-hydroxyethyl)ethylenediamine and N-(2-hydroxyethyl)propylenediamine. Examples include diamines. In addition, known reaction terminators such as monoamine compounds and monoalcohol compounds can be used. Specifically, monoalkylamines such as n-propylamine and n-butylamine, and dialkylamines such as di-n-butylamine can be used. and monoalcohols such as ethanol.

As a method for producing the above-mentioned polyurethane polyurea resin and biomass polyurethane polyurea resin, a known method for producing polyurethane resin using the above-mentioned materials can be used as is. In addition, if the weight average molecular weight, chemical structure, or equivalent ratio of each component differs, the hardness of the resulting polyurethane resin will also differ, so by appropriately combining these components, it is possible to adjust the printability and lamination suitability. It is. The mass average molecular weight of the polyurethane polyurea resin and biomass polyurethane polyurea resin is preferably 10,000 to 70,000, more preferably 20,000 to 60,000. Furthermore, in order to increase appropriate flexibility and lamination strength, a polyurethane resin having no urea bond and having a mass average molecular weight of 1,000 to 6,000 may be blended as the polyurethane resin.

(Reaction between organic diisocyanate compound and polymer diol compound)
In addition, when the organic diisocyanate compound and the polymer diol compound are reacted, the ratio of each used is such that the equivalent ratio of isocyanate group to hydroxyl group (isocyanate index) is usually 1.2:1.0 to 3.0: The ratio is 1.0, more preferably 1.2:1.0 to 2.2:1.0. When the above-mentioned isocyanate index is smaller than 1.2, it tends to be a flexible polyurethane polyurea resin or biomass polyurethane polyurea resin, and when printing with the printing ink composition, blocking resistance etc. may be low, and in this case, It may be necessary to use it in combination with other hard resins.
A catalyst can be used during the reaction between the organic diisocyanate compound and the polymeric diol compound to obtain the polyurethane polyurea resin and biomass polyurethane polyurea resin used in the present invention. Among them, it is preferable to use organometallic compounds, and examples of such organometallic compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride, dibutyltin sulfide, tributyltin sulfide, and tributyltin oxide. , dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, tributyltin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide , tributyltin trichloroacetate, tin compounds such as tin 2-ethylhexanoate, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate, and iron 2-ethylhexanoate. , iron acetylacetonate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, zirconium naphthenate, and the like. Among these, titanium compounds such as tetrabutyl titanate are preferred. Tertiary amine compounds can also be used, such as triethylamine, triethylenediamine, 1,4-diazabicyclo(2,2,2)octane, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU). can be used.

(Polyurethane polyurea resin obtained using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound, biomass polyurethane polyurea resin obtained using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound)
Polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound, and biomass polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound. Among the above-mentioned chain extenders and/or reaction terminators, a ketimine compound obtained by ketimine-forming a polyamine compound with an excessive amount of a ketone compound is used; c. By employing a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound in an organic solvent and reacting it with a urethane prepolymer and/or a biomass urethane prepolymer, d. A compound in which the amino group of a polyamine compound is ketiminated with a ketone compound in an organic solvent is added to a urethane prepolymer and/or a biomass urethane prepolymer, mixed with stirring, and then water is added, followed by chain elongation and reaction. By performing the stoppage, polyurethane polyurea resin and biomass polyurethane polyurea resin are produced and obtained. In particular, from among the chain extenders and reaction terminators mentioned above, it is preferable to employ one or more selected from isophorone diamine, N-(2-hydroxyethyl)ethylene diamine, and ethylene diamine. A polyamine compound ketiminated with a ketone compound has a structure in which the oxygen atom of the ketone compound is replaced by the nitrogen atom of the amino group of the polyamine compound. Moreover, as the ketone compound to be used, acetone, diethyl ketone, methyl ethyl ketone, diacetone alcohol, and methyl isobutyl ketone are preferable. In this ketimination reaction, it is preferable not to use any solvent other than the ketone compound. However, alcohol compounds can be used as solvents other than ketone compounds. Among them, isopropyl alcohol can be used. This not using any solvent other than the ketone compound is defined as ketimination under solvent-free conditions. Note that a polar organic solvent may be blended instead of under solvent-free conditions as long as it does not inhibit the subsequent chain extension reaction or the fact that the polyurethane polyurea resin and biomass polyurethane polyurea resin have no odor. The present invention relates to a polyurethane polyurea resin and/or a biomass polyurethane polyurea obtained through the step of elongating the chain and terminating the reaction using a ketiminated chain extender and/or a reaction terminator by the method c or d above. It may be a printing ink composition containing a resin, and the printing ink composition and the printed matter do not generate a ketimine odor. Furthermore, the peel strength can be increased when laminated onto a printed surface by means such as dry lamination or extrusion lamination. Note that the ketiminated amine or the like may be used as a chain extender, a reaction terminator, or both a chain extender and a reaction terminator.

(Polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound, and biomass polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound.) synthesis)
For the urethane prepolymer and/or biomass urethane prepolymer obtained by the reaction of an organic diisocyanate compound and a polymeric diol compound, a ketimine compound obtained by ketimine-forming a polyamine compound with an excess amount of a ketone compound is used, ．． By employing a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound in an organic solvent and reacting it with a urethane prepolymer and/or a biomass urethane prepolymer, f. A compound in which the amino group of a polyamine compound is ketiminated with a ketone compound in an organic solvent is used, added to a urethane prepolymer and/or a biomass urethane prepolymer, and mixed with stirring.After adding water, chain elongation and reaction termination are performed. Polyurethane polyurea resin and biomass polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound, and a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound. A polyurethane polyurea resin and a biomass polyurethane polyurea resin can be obtained. When using a solvent during the reaction, an ester solvent and/or an alcohol solvent are preferable, a mixture of an ester solvent and an alcohol solvent is more preferable, a mixture of propyl acetate and isopropyl alcohol is even more preferable, and in mass ratio, The most preferred ratio is propyl acetate:isopropyl alcohol in the range of 1:1 to 5:1.
As the polyurethane resin and biomass polyurethane resin, acid-modified polyurethane resins and/or acid-modified biomass polyurethane resins can also be employed. It may be used together with the above polyurethane resin and/or biomass polyurethane resin, or only acid-modified polyurethane resin and/or acid-modified biomass polyurethane resin may be used.
Acid-modified polyurethane resin and acid-modified biomass polyurethane resin are produced by reacting the polymer diol component with a tetrabasic acid anhydride such as pyromellitic anhydride as a polymer diol compound constituting the polyurethane resin, or , a polymeric diol compound having a free carboxyl group obtained by ring-opening polymerization of lactones using dimethylolpropionic acid or dimethylolbutanoic acid as an initiator, or a polymeric diol compound constituting the polyurethane resin. In addition, by using a hydroxycarboxylic acid such as dimethylolpropionic acid or dimethylolbutanoic acid, those obtained by conventionally known methods can be used. The acid value of the acid-modified polyurethane resin and the acid-modified biomass polyurethane resin is preferably 70 mgKOH/g or less.

(Other binder resins)
Other binder resins that can optionally be used in combination with the polyurethane resin will be described below.
<Vinyl chloride/vinyl acetate copolymer>
As the vinyl chloride/vinyl acetate copolymer that may be blended into the laminating printing ink composition for back printing, the vinyl chloride monomer and vinyl acetate monomer conventionally used in the laminating printing ink composition for back printing are essential. As a component, if necessary, fatty acid vinyl monomers such as vinyl propionate, vinyl monochloroacetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, and monomers having functional groups such as hydroxyl groups are used as copolymerization components. , those manufactured by known methods can be used.
A vinyl chloride/vinyl acetate copolymer having a hydroxyl group can be obtained by saponifying a portion of the acetate ester moiety and introducing a (meth)acrylic monomer having a hydroxyl group.
In the case of a vinyl chloride/vinyl acetate copolymer having a hydroxyl group obtained by saponifying a part of the acetate ester moiety, a structural unit based on the reactive site of vinyl chloride in the molecule (formula 1 below), acetic acid The physical properties and dissolution behavior of the resin film are determined by the ratio of the structural unit based on the vinyl reaction site (formula 2 below) and the structural unit based on the saponification of the vinyl acetate reaction site (formula 3 below). In other words, the structural units based on the reactive sites of vinyl chloride impart toughness and hardness to the resin film, the structural units based on the reactive sites of vinyl acetate impart adhesiveness and flexibility, and the structural units based on the reactive sites of vinyl acetate impart saponification. The structural units based on the above confer good solubility of the environmentally friendly printing ink composition in organic solvent systems.
Formula 1 -CH2-CHCl-
Formula 2 -CH2-CH(OCOCH3)-
Formula 3 -CH2-CH(OH)-
In addition, from the viewpoint of solubility and printability in organic solvents described later, which are used in the laminating printing ink composition for back printing, the vinyl chloride/vinyl acetate copolymer has various functional groups in the molecule. It's okay.
Further, when an environmentally friendly solvent is used as the organic solvent, it is preferable that the vinyl chloride/vinyl acetate copolymer has 50 to 200 mgKOH/g of hydroxyl groups. As such commercially available vinyl chloride/vinyl acetate copolymers, it is preferable to use, for example, Solvine A, AL, TA5R, TA2, TA3, TAO, TAOL, and the like.

<Vinyl chloride/acrylic copolymer>
The vinyl chloride/acrylic copolymer that can be blended into the laminate printing ink composition for back printing has a copolymer of vinyl chloride and an acrylic monomer as a main component, and the form of the copolymer is not particularly limited. For example, the acrylic monomer may be incorporated in the main chain of polyvinyl chloride in a block or random manner, or may be graft copolymerized with the side chain of polyvinyl chloride.
As the acrylic monomer, a (meth)acrylic acid ester, an acrylic monomer having a hydroxyl group, etc. can be used. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, and the alkyl group may be linear, branched, or cyclic, but a linear alkyl group is preferable.
For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylic acid Examples include octadecyl.
Examples of acrylic monomers having hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; , polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycol mono(meth)acrylate such as 1,4-cyclohexanedimethanol mono(meth)acrylate, caprolactone-modified (meth)acrylate, hydroxyethyl acrylamide, etc. Can be mentioned.
Moreover, as the acrylic monomer, an acrylic monomer having a functional group other than a hydroxyl group can also be used. Examples of functional groups other than hydroxyl groups include carboxyl groups, amide bonding groups, amino groups, and alkylene oxide groups.
The vinyl chloride/acrylic copolymer preferably has a mass average molecular weight of 10,000 to 70,000.
In addition, from the viewpoint of solubility in environmentally friendly organic solvents and adhesion to substrates, the vinyl chloride/acrylic copolymer has hydroxyl groups in an amount of 50 to 200 mgKOH/g. Preferably.
When the laminating printing ink composition for back printing contains a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer, the polyurethane resin and (vinyl chloride/vinyl acetate copolymer and / or vinyl chloride/acrylic copolymer) and polyurethane resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) = 98/2 to 45/55 (mass ratio ), preferably from 95/5 to 70/30, more preferably from 92/8 to 80/20.
In addition, the range may be 95/5 to 75/25 for polyurethane resin/(vinyl chloride/vinyl acetate copolymer), and the range may be 95/5 to 85/2 for polyurethane resin/(vinyl chloride/acrylic copolymer). It may be in the range of 15.
By containing a polyurethane resin and a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer in a ratio of 98/2 to 45/55, a laminate printing ink composition for back printing can be obtained. The product will have better printability and adhesion to the film. Furthermore, if lamination processing is performed, it will have better lamination suitability.
If the above polyurethane resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) exceeds 98/2, (vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) The proportion of acrylic copolymer) may decrease, and the adhesion to the film may become insufficient.
On the other hand, if the above polyurethane resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) is less than 45/55, (vinyl chloride/vinyl acetate copolymer and/or chloride copolymer) (vinyl/acrylic copolymer) increases, the printed matter formed using the laminating printing ink composition for back printing becomes hard, and there is also a possibility that the adhesion to the above-mentioned film will be insufficient.
In addition, the combined content of the polyurethane resin and vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer in the laminating printing ink composition for back printing is 5 to 30% by mass. suitable.
In addition, the laminating printing ink composition for back printing can contain one or more types selected from adhesion improvers and antiblocking agents within a range that does not reduce the performance aimed at by the present invention, and preferably, an adhesion improver and an antiblocking agent. It is preferable to use a combination agent and an antiblocking agent.

(Adhesion improver)
Examples of the adhesion improver that can be blended into the laminating printing ink composition for back printing include rosin and its derivatives, chlorinated polypropylene, and dammar resin, and at least one kind selected from rosin and its derivatives, more preferably two kinds. It is desirable to contain more than one species.

(Rosin and its derivatives)
Examples of the rosin include gum rosin, tall oil rosin, and wood rosin. Generally, rosin is an amber-colored, amorphous resin obtained from pine, and because it is obtained from nature, it is a mixture, but it includes abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, The dehydroabietic acid component may be isolated and used, and in the present invention, these are also defined as rosin.
Rosin derivatives are compounds obtained by modifying the above-mentioned rosin, and are specifically listed below.
(1) Hydrogenated rosin: A rosin with improved weather resistance by adding hydrogen to conjugated double bonds (hydrogenation).
(2) Disproportionation of rosin: Disproportionation means that two molecules of rosin react, and two molecules of abietic acid with a conjugated double bond are converted into aromatics, one with a single double bond, and the other with a single double bond. It is a denaturation that becomes a molecule. Generally, it has poorer weather resistance than hydrogenated rosin, but it has better weather resistance than untreated rosin.
(3) Rosin-modified phenolic resin: A rosin-modified phenolic resin is sometimes used as the main binder. Rosin-modified phenolic resin can be obtained by a known manufacturing method.
(4) Rosin ester: This is an ester resin derived from rosin, and has been used as a tackifier for adhesives and adhesives since ancient times.
(5) Rosin-modified maleic acid resin: A product obtained by addition-reacting maleic anhydride to rosin, and also includes a product obtained by esterifying and grafting a hydroxyl group-containing compound such as glycerin with an anhydride group as necessary.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from a natural resin rosin.
In addition, known rosin and rosin derivatives can also be used, and these can be used not only alone but also in combination.
Further, the acid value of rosin and its rosin derivative is preferably 120 mgKOH/g or more. When the acid value is 120 mgKOH/g or more, the laminate strength improves. More preferably, the acid value is 160 mgKOH/g or more. Further, the total amount of rosin and its derivatives used when blending is preferably 0.1 to 3.0% by mass based on the total solid content of the laminating printing ink composition for back printing.

(chlorinated polypropylene)
As the chlorinated polypropylene, those having a degree of chlorination of 20 to 50 can be used. Chlorinated polypropylene with a chlorination degree of less than 20 tends to have reduced compatibility with organic solvents. On the other hand, when the degree of chlorination exceeds 50, the adhesion of the chlorinated polypropylene to the film tends to decrease. In the present invention, the degree of chlorination is defined as the mass % of chlorine atoms in the chlorinated polypropylene resin. Further, the chlorinated polypropylene is preferably a modified or unmodified chlorinated polypropylene having a mass average molecular weight of 5,000 to 200,000. When the weight average molecular weight is less than 5,000, the chlorinated polypropylene tends to have lower adhesive properties. On the other hand, when the mass average molecular weight exceeds 200,000, the chlorinated polypropylene tends to have reduced solubility in organic solvents. The amount of chlorinated polypropylene used when blending is preferably 0.01 to 3.0% by mass based on the total solid content of the laminating printing ink composition for back printing.

(Dammar resin)
Dammar resin, also written as dammar or dammar, is a type of natural resin derived from plants. Specifically, it is a type of natural resin obtained from plants of the family Dipterocarpaceae or Orchidaceae that grow in Southeast Asia such as Malaysia and Indonesia. When used, it is dissolved in a suitable organic solvent to form a varnish. Since Dammar resin does not contain chlorine, chlorine can be eliminated or reduced compared to when chlorinated polypropylene is used in the printing ink composition. Further, the amount used when blending the dammar resin is preferably 3.0% by mass or less based on the total solid content of the laminating printing ink composition for back printing.

(Anti-blocking agent)
Examples of the anti-blocking agent include silica particles, polyethylene wax, fatty acid amide, cellulose acetate butyrate resin, cellulose acetate propionate resin, and nitrified cotton, and one or more of silica particles, polyethylene wax, and fatty acid amide, preferably It is preferable to contain two or more kinds of pigments, and depending on the type of pigment, it is preferable to further contain cellulose acetate butyrate resin, cellulose acetate propionate resin, and nitrified cotton.

<Silica particles>
It may or may not be included in the laminating printing ink composition for back printing of the present invention. Examples of the silica particles include natural products, synthetic products, crystalline, non-crystalline, hydrophobic, and hydrophilic ones. The silica particles preferably have an average particle diameter of 1.0 to 5.0 μm (the average particle diameter of the silica particles means the particle diameter at 50% (D50) of the integrated value in the particle size distribution, and is calculated using the Coulter Counter method. ). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or may be hydrophobic silica made hydrophobic by modifying the hydrophilic functional group with alkylsilane etc., but hydrophilic particles are preferable; A printing ink composition containing silica particles also has the effect of promoting wetting and spreading of the printing ink composition during overprinting and improving the overprinting effect (hereinafter sometimes referred to as "trapping property"). The amount of silica particles used in the laminating printing ink composition for back printing is preferably 0.0 to 3.0% by mass, more preferably 0.1 to 1.0% by mass. Note that 0.0% by mass indicates that no silica particles are contained.

(hydrocarbon wax)
The hydrocarbon wax used in the present invention has an average particle size in the range of 3.0 to 10.0 μm (the average particle size refers to the particle size measured with Honeywell Microtrac UPA). It is.
It is preferable to use polyethylene wax as the hydrocarbon wax.
The average particle diameter of the hydrocarbon wax is preferably 3.0 μm or more, more preferably 4.0 μm or more. Further, the thickness is preferably 10.0 μm or less, more preferably 7.0 μm or less.
If the average particle size of the hydrocarbon wax is smaller than 3.0 μm, slip properties and blocking resistance will decrease, and if the average particle size is larger than 10.0 μm, adhesive wettability and blocking resistance will be poor, making it difficult to remove the guide roll. There is a possibility that this may occur. Such problems tend to become noticeable when the average particle diameter is 12.0 μm or more.
Further, the laminating printing ink composition for back printing contains 0.05 to 5.0% by mass of hydrocarbon wax based on the total solid content, preferably 0.1% by mass or more. Further, it is preferably 3.0% by mass or less. If the content is less than 0.05% by mass, the desired effect will not be obtained, and if the content is more than 5.0% by mass, adhesive wettability, guide rolls may be removed, and retort resistance may deteriorate. There is.
The penetration degree (hardness) of the hydrocarbon wax is a value measured at 25°C as specified by JIS K 2207, and is 4.0 or more, more preferably 5.0 or more, and even more preferably 6.0 or more. . Moreover, it is 14.0 or less, preferably 10.0 or less, and more preferably 8.0 or less. If the penetration is less than 4.0, abrasion resistance, doctor cut, and guide roll may deteriorate; if it is greater than 14.0, adhesive wettability, guide wax removal, and retort resistance may be reduced. may decrease.
In the present invention, the average particle diameter of the hydrocarbon wax is the volume-based cumulative 50% particle diameter (median diameter (D50)) measured by laser diffraction/light scattering method.

(nitrified cotton)
It may or may not be included in the laminating printing ink composition for back printing of the present invention. As the nitrified cotton, nitrified cotton conventionally used in gravure printing ink compositions can be used. Nitrified cotton is obtained as a nitric acid ester by reacting natural cellulose with nitric acid to replace three hydroxyl groups in the six-membered ring of the anhydrous glucopyranose group in natural cellulose with nitric acid groups. The nitrified cotton used in the present invention preferably has a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90. Specific examples include SS1/2, SS1/4, SS1/8, TR1/16, NCRS-2, (KOREA CNC LTD), and the like. The amount of nitrified cotton used in the laminating printing ink composition for back printing is preferably in the range of 0.1 to 2.0% by mass, depending on the type of pigment.

(cellulose acetate propionate resin)
It may or may not be included in the laminating printing ink composition for back printing of the present invention. As the cellulose acetate propionate resin, resins conventionally used in gravure printing ink compositions can be used.
Cellulose acetate propionate resin is obtained by triesterifying cellulose with acetic acid and propionic acid and then hydrolyzing it. Generally, resins containing 0.6 to 2.5% by weight of acetylation, 42 to 46% by weight of propionylation, and 1.8 to 5.0% by weight of hydroxyl groups are commercially available. The cellulose acetate propionate resin is preferably used in the laminating printing ink composition for back printing in an amount of 0.1 to 3.0% by mass, depending on the type of pigment.

(cellulose acetate butyrate resin)
It may or may not be included in the laminating printing ink composition for back printing of the present invention. As the cellulose acetate butyrate resin, resins conventionally used in gravure printing ink compositions can be used.
Cellulose acetate butyrate resin is obtained by triesterifying cellulose with acetic acid and butyric acid and then hydrolyzing it. Generally, resins containing 2 to 30% by weight of acetylation, 17 to 53% by weight of butyrylation, and 1 to 5% by weight of hydroxyl groups are commercially available. The amount of cellulose acetate butyrate resin to be used in the laminating printing ink composition for back printing is preferably in the range of 0.1 to 3.0% by mass, depending on the type of pigment.

(fatty acid amide)
It may or may not be included in the laminating printing ink composition for back printing of the present invention. The fatty acid amide is not particularly limited as long as it has a residue obtained by removing an acid group from a fatty acid and an amide group. Examples of fatty acid amides include monoamides, substituted amides, bisamides, methylolamides, and esteramides, and at least one selected from the group consisting of monoamides, substituted amides, and bisamides because blocking resistance is improved. It is preferable. The amount of fatty acid amide used in the laminating printing ink composition for back printing is preferably in the range of 0.01 to 1.0% by mass.
- Monoamide: Monoamide is represented by the following general formula (1).
General formula (1) R ₁ -CONH ₂
(In the formula, _R1 represents a residue obtained by removing COOH from a fatty acid.)
Specific examples of monoamides 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: The substituted amide 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 residues obtained by removing COOH from fatty acids, and may be the same or different.)
Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and the like.
- Bisamide: Bisamide 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
(In the formula, R ₄ , R ₆ , R ₇ , and R ₉ represent residues obtained by removing COOH from a fatty acid, and may be the same or different, and R ₅ and R ₈ are alkylene groups having 1 to 10 carbon atoms. or represents an arylene group)
Specific examples of bisamides include methylene bisstearamide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, and hexamethylene bisstearic acid amide. , hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N,N'-distearyladipic 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: Methylolamide is represented by the following general formula (5).
General formula (5) R ₁₀ -CONHCH ₂ OH
(In the formula, _R10 represents a residue obtained by removing COOH from a fatty acid.)
Specific examples of methylolamide include methylol palmitic acid amide, methylol stearic acid amide, methylol behenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, methylol erucic acid amide, and the like.
- Esteramide: Esteramide 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 represent a residue obtained by removing COOH from a fatty acid, and may be the same or different, and R ₁₂ represents an alkylene group or arylene group having 1 to 10 carbon atoms.)
Specific examples of esteramides include stearylamide ethyl stearate, oleylamide ethyl stearate, and the like.
The melting point of the fatty acid amide is preferably 50 to 150°C.
Further, as the fatty acid constituting the fatty acid amide, saturated fatty acids having 12 to 22 carbon atoms and/or unsaturated fatty acids having 16 to 25 carbon atoms are preferable, and saturated fatty acids having 16 to 18 carbon atoms and/or saturated fatty acids having 18 to 22 carbon atoms are preferable. More preferred are unsaturated fatty acids. Particularly preferred saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, and hydroxystearic acid, and particularly preferred unsaturated fatty acids are oleic acid and erucic acid.

(Organic solvent)
Examples of the organic solvent used in the laminating printing ink composition for back printing of the present invention include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, normal propanol, butanol, isobutanol, and tert-butanol, toluene, xylene, etc. Aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, isopropyl acetate , ester solvents such as butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono Examples include glycol solvents such as ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and their esterified products. As the esterified products, acetates are mainly selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol Examples include monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. These can be used alone or in combination of two or more.
From an environmental standpoint, use a mixed solvent of an ester organic solvent, an alcohol organic solvent, and a ketone organic solvent, or a mixed solvent of an ester organic solvent and an alcohol organic solvent, which are more environmentally friendly. It is preferable to do so.

(water)
The laminating printing ink composition for back printing does not need to contain water, but it may contain water in order to alleviate printing defects caused by static electricity, prevent plate fogging, and eliminate problems with cell reproducibility. It's okay. The content of water in this case is 10% by mass or less, or in the range of 0.1 to 5.0% by mass in the laminating printing ink composition for back printing.

(Other materials)
If necessary, various additives such as a pigment dispersant, an antistatic agent, and a plasticizer can be added to the laminating printing ink composition for back printing.
A known method can be used to produce a laminating printing ink composition for back printing using the above constituent materials. Specifically, for example, a mixture of a pigment, a binder resin, an organic solvent, and if necessary a pigment dispersant is milled using a high-speed mixer, a ball mill, a sand mill, an attritor, etc., and then a hydrocarbon wax is mixed. , by adding and mixing the rest of the materials such as predetermined additives.
Further, a metal tetraalkoxide and/or a hydroxy acid may or may not be contained.

(Printing method using laminate printing ink composition for back printing and laminate obtained thereby)
Next, a method for obtaining a laminated printed matter using the laminating printing ink composition for back printing of the present invention will be explained.
The method for obtaining the laminated printed matter includes at least the following printing method.
For example, the laminate printing ink composition for back printing of the present invention is printed by a gravure printing method on a resin film serving as a known base material for lamination as a resin base material, and then dried with a dryer.
As the resin base material in the present invention, a base film made of a known resin conventionally used in laminate printing can be employed. Such resin base materials include polyester films such as polyethylene terephthalate (PET), polyolefin films such as polyethylene (PE) films, polypropylene (PP), resin films such as polyamide films such as nylon, and metal layers such as aluminum. The above resin film and the above resin film having a transparent vapor deposition layer can be exemplified.

A sealant layer is formed by laminating a resin film or the like by various methods on the side of the layer of the back-printing laminating printing ink composition of the printed matter obtained by the above method, thereby obtaining a laminated printed matter for packaging bags, etc. be able to. This lamination method includes the extrusion lamination method, in which a molten polymer is laminated after coating the surface of the printed matter with an anchor coating agent or without coating, and the extrusion lamination method, in which the surface of the printed matter is coated with an adhesive, and then a film-like A dry lamination method for bonding polymers can be used.
The above extrusion lamination method is carried out after coating an anchor coating agent such as a titanium-based, urethane-based, imine-based, or polybutadiene-based anchor coating agent on the surface of a printed matter containing a layer of a printing ink composition, or without applying the coating. This is a method in which molten polymers are laminated using a known extrusion laminating machine, and the molten resin can also be used as an intermediate layer to laminate other materials in the form of a sandwich.
As the molten polymer used in the extrusion lamination method, conventionally used resins such as low density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, etc. can be used. Among these, the effect of the present invention is enhanced when low density polyethylene is used, which tends to generate carbonyl groups by oxidation during melting.
The dry lamination method described above is a method in which a urethane-based adhesive, an isocyanate-based adhesive, etc. is applied to the surface of a layer made of a laminating printing ink composition for back printing, and then a resin film is laminated using a known dry laminating machine. be. In particular, in order to obtain a packaging material used for retort applications, aluminum foil may be sandwiched between the base material and the resin film to be laminated. Such laminated products can also be used for boiling and retort applications after being made into bags and filled with contents.
Examples of the resin film used at this time include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, and vinylon. Furthermore, regarding these resin films, it is also possible to use films obtained by processing in advance such as coating with an antifogging agent, kneading in, surface coating with a matting agent, kneading, etc.
Further, as the resin film, a film formed by laminating a barrier layer formed by metal vapor deposition and coating with a barrier resin on various printing plastic films, etc. can be used.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass." In addition, the numbers for the quantities of each material in the table are also "parts by mass."

(pigment)
・PB15:4 (Pigment Blue 15:4)
・Titanium oxide (rutile type titanium oxide, silica alumina treatment, average particle size 0.3 μm)

<Production example of polyurethane resin varnish 1 (biomass polyurethane, amine value 5.66 mgKOH/g, hydroxyl value 4.37 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 396.10 parts by mass of ethyl acetate and 169.80 parts by mass of isopropyl alcohol, 7.09 parts by mass of isophoronediamine, 0.31 parts by mass of monoethanolamine, N-(2-hydroxy 1.44 parts by mass of (ethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 1 (solid content: 30% by mass).

<Production example of polyurethane resin varnish 2 (biomass polyurethane, amine value 3.36 mgKOH/g, hydroxyl value 6.12 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.40 parts by mass of ethyl acetate and 168.60 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophoronediamine, 0.92 parts by mass of monoethanolamine, N-(2-hydroxy 1.18 parts by mass of (ethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 2 (solid content 30% by mass).

<Production example of polyurethane resin varnish 3 (biomass polyurethane, amine value 2.20 mgKOH/g, hydroxyl value 7.01 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.80 parts by mass of ethyl acetate and 168.80 parts by mass of isopropyl alcohol, 5.17 parts by mass of isophoronediamine, 1.22 parts by mass of monoethanolamine, N-(2-hydroxy 1.05 parts by mass of (ethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 3 (solid content 30% by mass).

<Production example of polyurethane resin varnish 4 (biomass polyurethane, amine value 12.86 mgKOH/g, hydroxyl value 5.52 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 399.30 parts by mass of ethyl acetate and 171.10 parts by mass of isopropyl alcohol, 8.41 parts by mass of isophoronediamine, 0.31 parts by mass of monoethanolamine, N-(2-hydroxy 1.98 parts by mass of (ethyl)ethylenediamine and 0.49 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 4 (solid content 30% by mass).

<Production example of polyurethane resin varnish 5 (biomass polyurethane, amine value 6.16 mgKOH/g, hydroxyl value 10.37 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 423.10 parts by mass of ethyl acetate and 181.30 parts by mass of isopropyl alcohol, 8.09 parts by mass of isophoronediamine, 0.61 parts by mass of monoethanolamine, N-(2-hydroxy 4.94 parts by mass of (ethyl)ethylenediamine and 0.98 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 5 (solid content 30% by mass).

<Production example of polyurethane resin varnish 6 (biomass polyurethane, amine value 1.39 mgKOH/g, hydroxyl value 2.35 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 375.2 parts by mass of ethyl acetate and 160.80 parts by mass of isopropyl alcohol, 1.94 parts by mass of isophoronediamine, 0.12 parts by mass of monoethanolamine, N-(2-hydroxy 0.79 parts by mass of (ethyl)ethylenediamine and 0.20 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 6 (solid content: 30% by mass).

<Production example of polyurethane resin varnish 7 that is not biomass polyurethane resin (polyurethane that is not biomass, amine value 5.66 mgKOH/g, hydroxyl value 4.37 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 140 parts by mass of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 2000 and 60 parts by mass of polypropylene glycol with a number average molecular weight of 2000 were added. , 16.67 parts by mass of isophorone diisocyanate, and 19.67 parts by mass of hydrogenated MDI (dicyclohexylmethane 4,4'-diisocyanate) were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 406.6 parts by mass of ethyl acetate and 174.26 parts by mass of isopropyl alcohol, 7.09 parts by mass of isophoronediamine, 0.31 parts by mass of monoethanolamine, N-(2-hydroxy The reaction was stopped by adding 1.44 parts by mass of (ethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine to obtain polyurethane resin varnish 7 (solid content: 30% by mass).

<Production example of polyurethane resin varnish 8 that is not biomass polyurethane resin (polyurethane that is not biomass, amine value 4.51 mgKOH/g, hydroxyl value 5.24 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 140 parts by mass of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 2000 and 60 parts by mass of polypropylene glycol with a number average molecular weight of 2000 were added. , 16.67 parts by mass of isophorone diisocyanate, and 19.67 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 4404.80 parts by mass of ethyl acetate and 173.49 parts by mass of isopropyl alcohol, 6.45 parts by mass of isophoronediamine, 0.61 parts by mass of monoethanolamine, N-(2 -Hydroxyethyl)ethylenediamine (1.31 parts by mass) and diethylenetriamine (0.29 parts by mass) were added and reacted to obtain polyurethane resin varnish 8 (solid content: 30% by mass).

<Production example of polyurethane resin varnish 9 that is not biomass polyurethane resin (non-biomass polyurethane, amine value 2.20 mgKOH/g, hydroxyl value 7.01 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 140 parts by mass of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 2000 and 60 parts by mass of polypropylene glycol with a number average molecular weight of 2000 were added. , 16.67 parts by mass of isophorone diisocyanate, and hydrogenated MDI of 19.67 were charged, and the mixture was reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 396.41 parts by mass of ethyl acetate and 170.00 parts by mass of isopropyl alcohol, 5.17 parts by mass of isophoronediamine, 1.22 parts by mass of monoethanolamine, N-(2-hydroxy 1.05 parts by mass of (ethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 9 (solid content 30% by mass).

<Production example of ketiminated polyurethane resin 10 that is not biomass (ketiminated polyurethane resin varnish 10 that is not biomass polyurethane resin, amine value 2.42 mgKOH/g, hydroxyl value 3.90 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas. After adding 810 parts of propyl acetate and 201 parts of isopropyl alcohol, cool to near room temperature, add 0.3 parts of monoethanolamine and stir for 15 minutes, then further add 29.30 parts of ketimine solution 1 below and stir for 20 minutes. Then, 3 parts of water was added and stirred for 15 minutes to obtain polyurethane resin varnish 10 (solid content: 30% by mass).

<Method for producing the above ketimine solution 1>
35.12 parts by mass of isophoronediamine, 21.36 parts by mass of N-(2-hydroxyethyl)ethylenediamine, 3.12 parts by mass of diethylenetriamine, and 174.8 parts by mass of acetone were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 1. I got it.

<Production example of polyurethane resin varnish 11 (polyurethane resin that is not biomass polyurethane resin, amine value 0)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 140 parts by mass of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 2000 and 60 parts by mass of polypropylene glycol with a number average molecular weight of 2000 were added. , and 44.4 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 518 parts by mass of ethyl acetate and 91 parts by mass of isopropyl alcohol, 15.6 parts by mass of isophoronediamine was added to elongate the chain, and further 1.1 parts by mass of monoethanolamine was added for reaction. The process was stopped, and polyurethane resin varnish 11 (solid content: 30% by mass) was obtained.
<Production example of polyurethane resin varnish 12 (biomass polyurethane resin, amine value 0)> Sebacic acid (derived from castor oil)/succinic acid (derived from plants) was placed in a four-necked flask equipped with a stirrer, cooling tube, and nitrogen gas introduction tube. = 30/70 (mass ratio) and 200 parts by mass of polyester diol with a number average molecular weight of 2000 obtained from 1,3-propanediol (derived from plants) and 44.4 parts by mass of isophorone diisocyanate were charged, and nitrogen gas was introduced. The mixture was reacted for 6 hours at 100 to 105°C. After cooling to near room temperature and adding 518 parts by mass of ethyl acetate and 91 parts by mass of isopropyl alcohol, 15.6 parts by mass of isophoronediamine was added to elongate the chain, and further 1.1 parts by mass of monoethanolamine was added for reaction. The process was stopped, and polyurethane resin varnish 12 (solid content: 30% by mass) was obtained.

<Vinyl chloride/vinyl acetate copolymer>
Solvine TA-3, manufactured by Nissin Chemical Industry Co., Ltd. <wax>

(wax)
Waxes used in Examples and Comparative Examples are shown in Table 1 below.
Each wax was used after adjusting the average particle size as necessary. Due to differences in the conditions for its preparation, one product name may have multiple average particle sizes after preparation. In particular, the following "110P", "220P", and "320P" were prepared and used in multiple types with different average particle diameters.

<Production example of laminating printing ink composition for back printing>
Pigments, polyurethane resin varnishes 1 to 12, and if necessary vinyl chloride/vinyl acetate copolymer are kneaded using a paint conditioner manufactured by Red Devil Co., Ltd., and then a hydrocarbon wax and a mixed solution (example below) are kneaded. A mixed solvent of ethyl acetate/propyl acetate/isopropyl alcohol = 50/25/25) and water were added to each of the mixed solutions to obtain a laminate printing ink composition for back printing.

Performance evaluation was performed using the following method.
(Printing method/printing conditions)
Room environment during printing: temperature 25℃, humidity 50%
Coating machine: Gravure printing machine Coating speed: 150m/min
Printing plate: Direct 175 line 28μm solid plate Drying temperature: 55℃

<About the film>
PET: Polyethylene terephthalate film with corona discharge treatment on one side,
Manufactured by Toyobo Co., Ltd., E-5102, thickness 12μm
OPP: corona discharged biaxially oriented polypropylene film,
Manufactured by Toyobo Co., Ltd., P-2161, thickness 25 μm
NY: Nylon film manufactured by Toyobo Co., Ltd., N-1102, thickness 15 μm

(Ink storage stability)
The laminating printing ink composition for back printing obtained above was collected in a glass bottle and stored at an ambient temperature of 60° C. for 14 days, and the storage stability of the ink was evaluated based on the presence or absence of pigment sedimentation.
〇: No sedimentation is observed, and the storage stability of the ink composition base material is good. ×: Sedimentation is observed, and the storage stability of the ink composition base material is poor.

(Evaluation of doctor sharpness)
The evaluation of the doctor sharpness was based on the state of the printed surface when the laminating printing ink compositions for back printing according to the Examples and Comparative Examples obtained above were used in a gravure printing machine at a printing speed of 150 m/min. , was evaluated in the following three stages.
〇: Plate fog, solid streaks, two-two stains (linear stains), etc. do not occur. △: Plate fog, solid streaks, two-two stains (linear stains), etc. occur slightly. ×: Plate fog, solid streaks, two-two stains (linear stains), etc. occur. ) etc. occur frequently.

(Adhesive wettability)
After printing each test ink on PET and NY film with each lamination printing ink composition for back printing, organic solvent-based isocyanate adhesive (Takeda Pharmaceutical, Takenate A-950: ether type/Takelac A-4 ethyl acetate solution), A-616: Ester type/A-65 was applied, and a CPP film was laminated using a dry laminating machine to obtain a laminated product. Judgment was made based on the presence or absence of shading in the appearance.
〇: No shading at all △: Some shading occurs ×: Many shadings occur

(blocking resistance)
The printed side of each film print one day after printing with each laminating printing ink composition for back printing and the untreated side of each film were combined, and a load of 400 g/cm ² was applied and the mixture was left at 40°C for 12 hours. The blocking resistance was evaluated based on the appearance when each film was peeled off.
〇: There is no resistance when the film is peeled off, and the ink does not peel off from the printed surface. △: There is resistance when the film is peeled off, but the ink does not peel off from the printed surface. ×: There is no resistance when the film is peeled off. , and the ink peels off from the printed surface.

(Abrasion resistance evaluation)
Using a Gakushin type friction fastness tester (product name "RT200", manufactured by Daiei Kagaku Seiki Co., Ltd.), the printed film of each printed material was tested on bleached cloth (product name "White cloth Kanakin No. 3 attached for dyeing fastness test"). The film was rubbed 100 times under a load of 200 g, and the degree of peeling of the printed film from the film was evaluated on the following three scales.
〇: There is no peeling of the printed film from the film. △: There is peeling of the printed film from the film, but the peeled area is less than 30%. ×: There is peeling of the printed film from the film, and the peeled area is 30% or more. is

(Guide roll removed evaluation)
The slipperiness was evaluated by removing the guide roll.
The following method was used to test whether ink adhered to the guide roll after printing (the guide roll was removed) to evaluate printing suitability. Note that the ink once attached to the guide roll transfers to the printing surface again and causes stains, so if "guide roll removal" occurs, it will have an adverse effect on the ability to obtain decorative printed matter.
Visually evaluate whether the printed ink coating has fallen off due to the guide roll of the gravure printing machine.
〇: No shedding △: Slight shedding ×: Some shedding

(Retort resistance)
Apply urethane adhesive (Takelac A-616/Takenate A-65, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) in an amount of 2.0 g/m ² in solid content to each printed matter of PET film and NY film one day after printing. After coating, a non-stretched polypropylene film (RXC-3, thickness 60 μm, manufactured by Tohcello Co., Ltd.) was laminated using a dry laminating machine and left at 40° C. for 3 days to obtain a dry laminate. This dry laminate is made into a bag, filled with a mixture of 90% water and 10% salad oil, and after being melt-sealed, it is pressurized at 135°C for PET film and 120°C for films other than PET film. Retort resistance was evaluated based on the appearance of the laminate film when it was immersed in hot water for 30 minutes.
〇: Items with no appearance defects due to laminate lifting or wetting, etc. ×: Items with appearance defects due to laminate lifting, wetting, etc.

According to Examples, which are examples in accordance with the present invention, the ink storage stability, adhesive wettability, blocking resistance, abrasion resistance, doctor cut resistance, and retort resistance are all good, and the guide roll is removed. did not occur. On the other hand, Comparative Examples 1 and 8, which have a low content of hydrocarbon wax, have poor abrasion resistance and guide roll removal, and Comparative Examples 2 and 9, which have a high content of hydrocarbon wax. According to , adhesive wettability, blocking resistance, doctor cutting resistance, and retort resistance were poor, and guide rolls were removed.
Comparative Examples 3 and 10, in which the average particle diameter of the hydrocarbon wax is small, cause guide roll removal, and Comparative Examples 4 and 11, in which the penetration degree is large, are poor in adhesive wettability, blocking resistance, and resistance. According to Comparative Examples 5 and 12, which have poor retortability, guide roll removal, and large penetration degree and average particle size, they have poor adhesive wettability, blocking resistance, doctor cut resistance, and retort resistance, and have a large penetration degree and average particle size. A roll was taken.
Comparative Examples 6, 7, 13, and 14, in which the wax penetration was low, were poor in abrasion resistance and doctor cutting ability, and guide rolls were removed.
Comparative Examples 15 and 16, which used polyurethane resins with an amine value of 0, had poor ink storage stability and were unsuitable for printing.

Claims (7)

pigment and
As a binder resin , a polyurethane resin having an amino group and a hydroxyl group and a hydroxyl value of 0.5 mgKOH/g or more, and a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer ,
organic solvent and
A hydrocarbon wax having a penetration degree at 25° C. of 4.0 to 14.0 and an average particle size of 3.0 to 10.0 μm as specified in JIS K 2207 ;
A laminating printing ink composition for back printing, comprising :
The hydrocarbon wax is contained in an amount of 0.05 to 5.0% by mass based on the total solid content of the laminating printing ink composition for back printing ,
Content mass ratio of the polyurethane resin and the vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer (polyurethane resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer)) Acrylic copolymer)) is 92/8 to 75/25 ,
Laminating printing ink composition for back printing.
(However, except when the above polyurethane resin is a water-based urethane resin,
In addition, the following cases are excluded.
Contains the following polyurethane polyurea resin (A) and/or (B),
An organic solvent-based high solid ink composition for gravure printing, wherein the pigment and the binder resin satisfy the following conditions 1 to 3.
(A) One or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (A-1) and (A-2) (A-1) by reacting a diol compound and a diisocyanate compound. A polyurethane polyurea resin (A-2) obtained by chain elongating and terminating the reaction of the obtained urethane prepolymer and a compound in which the amino group of a polyamine compound has been ketiminated with a ketone compound in an organic solvent.(A-2) Diol compound and diisocyanate A urethane prepolymer obtained by reacting a compound is reacted with a reaction terminator in an organic solvent, and then chain elongation and reaction termination are performed with a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound. Obtained polyurethane polyurea resin (B) One or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (B-1) and (B-2) (B-1) Diol compound and diisocyanate A compound in which the amino groups of a polyamine compound have been ketiminated with a ketone compound is added to a urethane prepolymer solution of a urethane prepolymer obtained by reacting the compounds with an organic solvent, and the mixture is stirred. A reaction terminator is added to a urethane prepolymer solution of a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound and an organic solvent to a polyurethane polyurea resin (B-2) obtained by elongation and reaction termination, and the reaction is caused to occur. Next, a compound in which the amino group of the polyamine compound has been ketiminated with a ketone compound is added and mixed with stirring, and further, after adding water, chain extension and reaction termination are performed to obtain a polyurethane polyurea resin (condition 1) as described above for the pigment. is an organic pigment, the content of the organic pigment in the organic solvent-based high solid ink composition for gravure printing is 5 to 20% by mass (Condition 2) When the pigment is an inorganic pigment, the organic solvent-based The content of the inorganic pigment in the high solid ink composition for gravure printing is 30 to 70% by mass (condition 3) When the pigment contains both an organic pigment and an inorganic pigment, an organic solvent-based high solid ink composition for gravure printing is used. The content of the organic pigment in the ink composition is 5 to 20% by mass, and the mass ratio of the inorganic pigment to the organic pigment {inorganic pigment (mass)/organic pigment (mass)} is 0<inorganic pigment (mass) /organic pigment (mass)<7.0. ) The laminating printing ink composition for back printing according to claim 1, wherein the hydrocarbon wax is a polyethylene wax. The laminating printing ink composition for back printing according to claim 1 or 2, wherein the polyurethane resin has an amine value of 1.0 to 13.0 mgKOH/g and a hydroxyl value of 0.5 to 12.0 mgKOH/g. 3. The polyurethane resin is a polyurethane resin having at least one of a primary amino group or a secondary amino group at the end, and a hydroxyl group at the end of the molecule and at a site other than the end of the molecule. A laminating printing ink composition for back printing. The laminating printing ink composition for back printing according to claim 1 or 2, wherein the vinyl chloride/vinyl acetate copolymer resin and /or the vinyl chloride/acrylic copolymer resin have a hydroxyl group. The laminate printing ink composition for back printing according to claim 1 or 2, wherein the organic solvent is a mixed solvent containing an ester organic solvent and an alcohol organic solvent. The laminating printing ink composition for back printing according to claim 1 or 2, further comprising water.