JP2018131624A - Print coating film, laminate, method for producing laminate, and packaging, lid material and label, and method for producing solvent type gravure printing ink composition for reverse printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a print coating film produced from a solvent type gravure printing ink composition for reverse printing by a gravure printing method, in which a biomass-derived polyurethane urea resin containing a biomass-derived component is selected as a resin used for the ink composition, stability as the ink composition can be sufficiently kept as characteristics of the resin, the print coating film has blocking resistance, film adhesion, solvent resistance and plate anti-clogging property of the print coating film necessary for reverse printing without impairing printability at the time of printing, has good laminating property, and has hot water treatment property when formed into a laminate on which a laminate layer is formed.SOLUTION: A print coating film contains a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, a glycol-based solvent and an alcohol-based solvent, and a biomass-derived component, where when the solvent type gravure printing ink composition for reverse printing having an amine value of the biomass-derived polyurethane urea resin of 1-13 mgKOH/g and a weight average molecular weight of the biomass-derived polyurethane urea resin of 10,000-100,000 is printed on a film base material layer by a gravure printing method to be formed into a print coating film, a degree of biomass (containing no pigment) in the print coating film is 3-40 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a printed coating film in which a solvent-type gravure printing ink composition for back printing is formed on a film substrate layer by a gravure printing method.

Conventionally, as a gravure printing ink composition that can be printed on a film substrate, one having a polyurethane resin as a main component is known. In particular, polyurethane resins using polymer diols and diisocyanates have moderate polarity and cohesion, and have film properties such as solubility in ester / alcohol solvents that affect printability, and blocking properties such as blocking resistance. Widely used because it is compatible.
In particular, in order to improve film properties such as boil resistance and blocking resistance, those using a specific glycol component as a polymer diol have been proposed.

In Patent Document 1, polyester diols (A), diisocyanates (B) containing 1,3-bis (α, α-dimethylisocyanatomethyl) benzene as essential components, and a chain extender (C) are reacted. A printing ink using a polyurethane urea resin obtained by the above-described method is described, and a one-pack type printing ink excellent in boil resistance and retort processing properties is provided.
However, it is not a biomass-derived polyurethane urea resin, and there is no description or suggestion about the amine number and the weight average molecular weight of the resin. Furthermore, there is no description or suggestion about the degree of biomass in the printed coating when it is used as a printed coating.

Patent Document 2 includes a polyester polyol (A) obtained from a mixed diol (a) composed of two kinds of diols and a dicarboxylic acid (b), an organic diisocyanate compound (B), and a chain extender (C). In the derived polyurethane resin, a toluene-free solvent-based binder for printing ink containing at least 1% by mass of an alkylene oxide adduct of bisphenol A in the polyurethane, and a toluene-free solvent containing the binder as a main binder A printing ink binder for a plastic film is described, and a binder for a printing ink having excellent re-solubility can be provided. In particular, a polyurethane resin useful as a binder for a gravure printing ink or a flexographic printing ink is provided.
However, there is no description or suggestion about the weight average molecular weight of the biomass-derived polyurethane resin. Although the measured value of the amine value of the obtained polyurethane resin is described in the examples, it is not the amine value of the polyurethane urea resin derived from biomass, but there is no detailed description of the amine value, which has special significance. There is no description or suggestion. Furthermore, there is no description or suggestion about the degree of biomass in the printed coating when it is used as a printed coating.

Patent Document 3 describes a binder for printing ink containing polyurethane using 2-ethyl-2-alkyl-1,3-propanediol, which improves boil resistance and retort resistance. No. 4 describes a varnish for printing ink containing a polyurethane resin using 2-butyl-2-ethyl-1,3-propanediol, which improves blocking resistance and retort suitability.
On the other hand, from the viewpoints of environmental problems such as air pollution due to organic solvents, safety and health problems in the work environment, and disaster prevention, in the field of printing inks and paints, alcohol solvents can be selected without using ester solvents. Increasing use of ink.

  Patent Document 5 discloses a method for producing an alcohol-soluble urethane resin obtained by reacting a linear urethane prepolymer having an aliphatic isocyanate group and a diamine in an alcohol solvent, and Patent Document 6 discloses an alcohol solvent / acetic acid. A method for producing an alcohol-soluble urethane resin for gravure printing inks in which a linear urethane prepolymer having an aliphatic isocyanate group and a diamine are reacted in a mixture having an ethyl weight ratio of 99/1 to 83/17. Patent Document 7 describes a method for producing an alcohol-soluble urethane resin in which a specific urethane prepolymer is dissolved in a secondary and / or tertiary alcohol solvent and then reacted with a diamine. Or even if it is a polyurethane resin rich in alcohol solvent system, the printability of ink, Those with excellent like hot water resistance of Surimono have been proposed.

  However, the above Patent Documents 3 to 7 are not biomass-derived polyurethane urea resins, nor do they describe or suggest the amine number and weight average molecular weight of the resins. Moreover, the focus is on the selection of the solvent to be used as the gravure printing ink, printing on the film substrate, evaporating the solvent in the ink, and printing film on the film substrate. There is no description or suggestion about the degree of biomass in the printed coating.

  Patent Document 8 discloses a printing ink composition containing alcohol derived from biomass, and Patent Document 9 discloses a dehydration reaction between acetic acid obtained by oxidizing ethanol derived from biomass and ethanol derived from petroleum. Polyurethane resin varnish using ethyl acetate obtained or ethyl acetate (ester compound) obtained by dehydration reaction of acetic acid and biomass-derived ethanol is described, carbon dioxide emission can be reduced, and excellent printing Those with suitability have been proposed.

  However, the above Patent Documents 8 and 9 both focus on the selection of the solvent to be used as the gravure printing ink, and the film is printed on the film substrate, the solvent in the ink is evaporated, and the film There is no description or suggestion about the degree of biomass in the printed coating when it is used as a printed coating on the substrate. Here, Patent Documents 8 and 9 use biomass-derived alcohol. Biomass is defined as a renewable organic-derived organic resource excluding fossil resources. If derived from the plant, it is considered to be the same amount of carbon dioxide absorbed from the atmosphere as the plant grows, and even if it is incinerated, carbon dioxide generated is counted as zero (carbon neutral), reducing environmental impacts and global warming. However, there is no description or suggestion about the biomass degree of the printed film as described above as well as the biomass degree in the ink composition.

  Patent Document 10 discloses a gravure ink for polyethylene extrusion lamination characterized by containing a polyester polyurethane resin. Patent Document 11 discloses a polyurethane resin as a binder in the case of no-anchor lamination on the printing surface of a base film. Contains a two-part curable gravure ink that is printed on a substrate film containing an isocyanate compound as a curing agent, and can exhibit sufficient adhesion performance without applying an anchor coat to the printed substrate. Has been proposed.

  In Patent Document 12, the binder resin is a polyurethane resin, and when 30 parts of the polyurethane resin is dissolved in 70 parts of an organic solvent, the viscosity of the polyurethane resin solution is 100 to 500 mPa · s / 25 ° C., and the ink An organic solvent-based concentrated ink composition for gravure printing having a viscosity of 10 to 50 mPa · s / 25 ° C. is described, and conventional good ink performance (concentration, printing even when a shallow plate is used) Have been proposed.

  However, Patent Documents 10 to 12 are not a biomass-derived polyurethane urea resin, nor do they describe or suggest the amine value and weight average molecular weight of the resin. Furthermore, there is no description or suggestion about the degree of biomass in the printed coating when it is used as a printed coating.

Patent Document 13 discloses a biopolycarbonate polyol (A) synthesized using a plant-derived short-chain diol component (a) and a petroleum-derived carbonate component (b) or a plant-derived carboxylic acid component (c). ) Or a biopolyester polyol (B), a biopolyether polyol (C) synthesized using a plant-derived short chain diol component (a), and an isocyanate component (d). A biopolyurethane resin, wherein the content of the plant-derived component is 28 to 95% by mass with respect to 100% by mass of the biopolyurethane resin, and the content of the plant-derived component is described Which contributes significantly to carbon neutralization aimed at preventing global warming and reducing environmental impact. It is a urethane resin, and the resin is applied to various coating agents, various paints, printing inks, molded articles, films, sheets, and the required durability and performance are comparable to conventional polyurethane resins, or It has been proposed as a resin that can be improved.
However, there is no description or suggestion about the amine value of the biopolyurethane resin. In addition, the weight average molecular weight is described in the specification as “preferably in the range of 2,000 to 500,000”, but it is clear that the range of the weight average molecular weight suitable for the application varies. In addition, there is no disclosure of the weight average molecular weight in the examples, and there is no description or suggestion about the preferred range for printing ink applications, and it is unclear. In addition, the specification only has the description “Compared to conventional polyurethane resins derived from petroleum raw materials, it was sufficiently usable for various applications.” There was no example of actually producing printing ink, It is unknown. Furthermore, organic solvents that can be used for the synthesis of biopolyurethane resins are exemplified, but the solvent described in the examples is only DMF (dimethylformamide), which is prescribed by the Federation of Printing Ink Industries. Since it is a solvent that falls under the “voluntary regulations concerning printing ink (NL regulations)”, it is common knowledge for those skilled in the art that it is a solvent that is never used. Therefore, it is unlikely that a printing ink using the biopolyurethane resin is assumed, and when gravure printing is performed on a film substrate, the solvent is evaporated, and a printed coating film is formed on the film substrate. There is no description or suggestion about the degree of biomass in the printed coating.

In addition, global warming countermeasures should be addressed globally. At the 21st Conference of the Parties to the Framework Convention on Climate Change (COP21) held in 2015, reduction targets for each country were submitted. Japan has submitted a draft commitment to reduce greenhouse gases by 26% by 2030 compared to 2013. Under these circumstances, companies that deal with foodstuffs should consider measures to reduce the disposal of foodstuffs themselves, explore whether waste can be reduced and used, and consider whether transportation distances can be reduced. Is important. In recent years, it has been emphasized how to improve the corporate image by proposing "environmentally friendly" products as an important business strategy for companies. Because packaging materials used for daily necessities and foods are familiar to general consumers and can be directly touched with the contents of the product, it is also important how to appeal as an “environmentally friendly” package. .
Therefore, the gravure printing method can be used as a “gravity-friendly” package that can be used as a packaging material for film, and can be used as a “green” package without increasing the environmental burden. Thus, when a printed coating film is formed on the film base material layer, a printed coating film that increases the degree of biomass in the printed coating film has been desired.

Japanese Patent Laid-Open No. 03-115373 JP 2004-307786 A JP-A-5-222333 JP 2013-142117 A JP 2002-121250 A JP 2002-201253 A JP 2002-293860 A JP 2008-44982 A JP 2008-81422 A JP 2001-271015 A Japanese Patent Laying-Open No. 2005-307071 JP 2011-252135 A JP 2011-225863 A

  Therefore, the present invention is a printed coating film prepared by a gravure printing method using a solvent-type gravure printing ink composition for back printing, and a biomass-derived polyurethane containing a biomass-derived component as a resin used in the ink composition A urea resin is selected, and the properties of the resin can sufficiently maintain the stability as an ink composition, without impairing the printability at the time of printing, and the blocking resistance and film adhesion of a print coating film necessary for back printing An object of the present invention is to provide a printed coating film having solvent resistance, plate-clogging resistance, good laminating properties, and heat resistant water treatment properties when a laminate having a laminate layer is formed. .

  The inventors include a hydrocarbon-based, ketone-based, ester-based, glycol-based, and alcohol-based solvent and a biomass-derived polyurethane urea resin, and the amine value and weight average molecular weight of the biomass-derived polyurethane urea resin. When the solvent-type gravure printing ink composition for back printing, which has a specific range, is a printed coating film prepared on the film substrate layer by the gravure printing method, the biomass degree in the printed coating film (without pigment) ) Was found to be able to achieve the above-mentioned object by using a printed coating film having a content of 3 to 40% by mass, and the present invention was completed.

That is, the present invention
(1) A biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and biomass-derived components,
The solvent-type gravure printing ink for back printing, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000. The composition
A printed coating film characterized by having a biomass degree (not including pigment) in the printed coating film of 3 to 40% by mass when a printed coating film is formed on the film substrate layer by a gravure printing method,
(2) On one of the film base layer and the film base layer,
Including a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and biomass-derived components;
The solvent-type gravure printing ink for back printing, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000. The composition is
A printing layer formed by applying a gravure printing method;
A laminate layer on the printed layer;
A laminate having a biomass degree (not including a pigment) of the printed layer of 3 to 40% by mass,
(3) A step of preparing a film base layer, and one of the film base layers,
Including a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and biomass-derived components;
The solvent-type gravure printing ink for back printing, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000. A gravure printing step for creating a printed layer comprising the composition;
Forming a laminate layer on the printed layer,
A method for producing a laminate, wherein a biomass degree (not including a pigment) of a printed layer prepared by the gravure printing step is 3 to 40% by mass;
(4) A packaging bag produced using the laminate according to (2),
(5) A lid material produced using the laminate according to (2),
(6) A label produced by using the laminate according to (2),
(7) Biomass containing a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and biomass-derived components A step (1) of preparing a derived polyurethane urea resin solution;
Including a step (2) of mixing and dispersing the biomass-derived polyurethane urea resin solution obtained in the step (1), a coloring material, and a solvent to obtain a solvent-type gravure printing ink composition for back printing,
The solvent is at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents,
The amine value of the polyurethane urea resin in the biomass-derived polyurethane urea resin solution is 1 to 13 mgKOH / g, and the weight average molecular weight of the polyurethane urea resin in the biomass-derived polyurethane urea resin solution is 10,000 to 100 , 000,
When the solvent-type gravure printing ink composition for back printing obtained in the step (2) is formed as a printed coating on the film substrate layer by the gravure printing step, the biomass degree (including pigments) in the printed coating No)) is a printed coating film having a content of 3 to 40% by mass, a method for producing a solvent-type gravure printing ink composition for back printing,
It is about.

  According to the present invention, a polyurethane-derived biomass containing a biomass-derived component as a resin used in the ink composition, which is a printed coating film prepared by a gravure printing method using a solvent-type gravure printing ink composition for back printing A urea resin is selected, and the properties of the resin can sufficiently maintain the stability as an ink composition, without impairing the printability at the time of printing, and the blocking resistance and film adhesion of a print coating film necessary for back printing In addition, it is possible to provide a printed coating film having solvent resistance and plate clogging resistance, good laminating properties, and heat resistant water treatment properties when a laminate having a laminate layer is formed.

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

  The printed coating film of the present invention is a biomass-derived polyurethane containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and a biomass-derived component. For urea printing, containing urea resin, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000 When a solvent-type gravure printing ink composition (hereinafter, also simply referred to as “ink composition”) is formed on a film base layer by a gravure printing method, the biomass degree (pigment (Not including) (hereinafter also simply referred to as “biomass degree”) is preferably 3 to 40% by mass.

  The biomass-derived polyurethane urea resin is obtained by reacting the polyol (I), the polyisocyanate (II), and the chain extender (III), and the polyol (I), the polyisocyanate (II), and the chain extension. It is preferred that at least one of the agents (III) is produced using a biomass material.

<Polyol (I)>
The polyol (I) is a polyol having a hydroxyl group at the terminal, and (A) polyester polyol, (B) polyether polyol, (C) (A), and other high molecular weight polyols other than (B) (polycaprolactone diol). , Polycarbonate diol, polybutadiene diol, acrylic polyol, etc.) and (D) low molecular weight polyol, or a mixture thereof.

  The number average molecular weight of the polyol (I) is preferably in the range of 600 to 10,000, and more preferably 1,000 to 8,000. If the number average molecular weight is less than 600, the hard segment (urethane bond part, urea bond part) in the biomass-derived polyurethane urea resin increases, it becomes difficult to dissolve, printability is inferior (resolubility is inferior, plate clogging is There is a risk). Moreover, when the ink film becomes hard, the adhesiveness is lowered, or the suitability for boiling after lamination is lowered. When the number average molecular weight exceeds 10,000, the number of hard segments is small, the number of soft segments (ester portion, ether portion) is increased, and the blocking resistance is lowered.

<(A) Polyester polyol>
The (A) polyester polyol is preferably a polyester polyol having a hydroxyl group at the terminal, and is obtained by dehydration condensation of the polyol (i) and the polycarboxylic acid (ii) or an anhydride thereof. i) is preferably a glycol or diol, and the polycarboxylic acid (ii) is preferably a dicarboxylic acid. Further, a triol or polyol having three or more hydroxyl groups, a tricarboxylic acid or polyvalent carboxylic acid having three or more carboxyl groups. May be used in combination.
In the case of using a polyol having 3 or more hydroxyl groups or a polyvalent carboxylic acid having 3 or more carboxyl groups, it is preferably 5 mol% or less with respect to the diol and dicarboxylic acid, respectively. When more than this, there exists a possibility of gelatinizing when synthesize | combining biomass origin polyurethane urea resin.
In addition, the polyol (i) and the polycarboxylic acid (ii) may not be one kind, and either one or two or more of each may be used. Alternatively, a specific polyol (i) and a polycarboxylic acid (ii) are used to synthesize separate (A) polyester polyols, and then the separate (A) polyester polyols are blended together. May be.

(A) The number average molecular weight of the polyester polyol is preferably in the range of 600 to 10,000, and more preferably in the range of 1,000 to 6,000. When the number average molecular weight is smaller than 600, the resulting polyurethane urea resin has poor solubility, and when the number average molecular weight exceeds 10,000, the blocking resistance is poor. The number average molecular weight is a value measured by GPC method (polystyrene conversion).
The acid value is preferably 1 mgKOH / g or less. When the acid value is greater than 1 mgKOH / g, the viscosity of the biomass-derived polyurethane urea resin obtained with varnish or ink is increased with time, and the ink stability is poor. The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the resin, and is a value measured according to JIS K0070.
The hydroxyl value is a value obtained by converting the amount of hydroxyl group in 1 g of resin calculated by esterifying or acetylating the hydroxyl group in the resin with an excess of anhydrous acid and back titrating the remaining acid with alkali to the number of mg of potassium hydroxide. The measured value according to JIS K0070.

<(A) Polyol of Polyol Polyol (i)>
As the polyol (i) of the (A) polyester polyol, specifically, as the diol (a), ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 2,5-hexanediol, 1,6-hexanediol, triethylene glycol, 1-methyl-1,3-butylene glycol 2-methyl-1,3-butylene glycol, 2,4-diethyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, tripropylene glycol, 1,2-propylene glycol, 2, -Methyl-1,5-pentanediol, 2-methyl-1,4- Nthanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1, Alkylene oxides such as 3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,6-hexanediol, dimer diol, bisphenol A ethylene oxide, propylene oxide, ethylene propylene oxide Adducts such as butyl ethyl propane diol can be used. Examples of the polyfunctional polyol (b) include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaerythritol and the like. Examples of the diol (c) having an amino group include methyldiethanolamine, methyldiisopropanolamine, phenyldiisopropanolamine, 4-methylphenyldiisopropanolamine, 4-methylphenyldiethanolamine and the like. These can be used alone or in combination.
Among them, examples of biomass origin include ethylene glycol, 1,3-propanediol, 1,4-butanediol, dimer diol and the like.

<(A) Polyester Polycarboxylic Acid (ii)>
As the polycarboxylic acid (ii) of the (A) polyester polyol, specifically, as a dicarboxylic acid (d), adipic acid, glutaric acid, maleic acid, oxalic acid, malonic acid, succinic acid, sebacic acid, azelaic acid , Fumaric acid, terephthalic acid, isophthalic acid, dimer acid, dodecanedioic acid, suberic acid, furandicarboxylic acid, anhydrides of dicarboxylic acid and ester compounds of lower alcohols having 1 to 5 carbon atoms. Examples of the polyvalent carboxylic acid (e) include trimellitic acid and pyromellitic acid. These can be used alone or in combination.
Among them, examples of biomass origin include glutaric acid, succinic acid, sebacic acid, dimer acid, dodecanedioic acid, suberic acid, and furandicarboxylic acid.

<(B) polyether polyol>
Examples of the (B) polyether polyol include polymers such as ethylene oxide, propylene oxide, and tetrahydrofuran, and copolymer polyether polyols. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Etc. These can be used alone or in combination. In particular, polypropylene glycol has good low-temperature stability.
Among them, examples of the biomass origin include polyethylene glycol and polytetramethylene ether glycol.

  The number average molecular weight of the (B) polyether polyol is preferably in the range of 600 to 5,000. When the number average molecular weight exceeds 5,000, the water resistance is poor.

  The (A) polyester polyol and the (B) polyether polyol may be mixed and used. When the (A) polyester polyol and the (B) polyether polyol are mixed, the ratio of the polyester polyol to the polyether polyol is within the range of (A) / (B) = 100/0 to 40/60. Is preferred. (B) Since polyether polyol is excellent in solubility in water and alcohol, it can impart solubility to the biomass-derived polyurethane urea resin of the present invention. When (B) polyether polyol exceeds 60 mass% in polyol (I), it is inferior to blocking resistance or oil resistance.

<(C) Other high molecular weight polyol>
Examples of (C) other high molecular weight polyols include polycaprolactone diols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone), and low molecular polyols. Examples include polycarbonate diol, polybutadiene diol, and acrylic polyol obtained by reaction with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and the like.

<(D) Low molecular weight polyol>
As the polyol (I), (D) a low molecular weight polyol can also be used. Thereby, the amount of urethane bonds and the amount of urea bonds can be adjusted. It is preferable that it is 10 mass% or less in polyol (I). If it exceeds 10% by mass, the number of hard segments increases and the solubility is poor.
As the low molecular weight polyol, the components listed in the polyol (i) can be used.

The biomass-derived polyurethane urea resin can be synthesized by a conventionally known method. For example, polyol (I) and diisocyanate compound (II) are reacted so that isocyanate groups are excessive to obtain a prepolymer of terminal isocyanate groups, and the resulting prepolymer is chain extender in solvent (V). A two-stage process in which (III) and / or reaction terminator (IV) are reacted, or polyol (I), diisocyanate compound (II), chain extender (III) and / or reaction terminator (IV), Although the one-shot method made to react in a solvent (V) is mentioned, The two-step method which can synthesize | combine stably is especially preferable.
In the case of the two-stage method, the chain extension reaction may be a method in which the solvent (V), the chain extender (III) and / or the reaction terminator (IV) is charged in advance and then the prepolymer is added, or the prepolymer solution A method may be used in which the chain extender (III) and / or the reaction terminator (IV) is charged.

  Moreover, when synthesizing the prepolymer, the equivalent ratio of the active hydrogen group and the isocyanate group of the polyol is within the range of [active hydrogen group of polyol] / [isocyanate group] = 1 / 1.1 to 1/3. Is preferred. If the ratio of isocyanate groups is smaller than 1.1, the resulting biomass-derived polyurethane urea resin is inferior in alkali resistance. When the ratio of isocyanate groups exceeds 3, the solubility of the prepolymer tends to decrease.

  The equivalent ratio of the isocyanate groups in the prepolymer and the active hydrogen groups of the chain extender (III) and / or the reaction terminator (IV) is [active hydrogen group of the chain extender and / or reaction terminator] / [isocyanate group]. ] Is preferably within the range of 0.8 / 1 to 3/1, and more preferably within the range of 1/1 to 2/1. If the ratio of [active hydrogen group of chain extender and / or reaction terminator] is less than 0.8, the adhesiveness is not sufficient, and the ratio of [active hydrogen group of chain extender and / or reaction terminator] However, if it exceeds 3, an odor may be generated after printing or the polyurethane urea resin may turn yellow. When the reaction terminator (IV) is used, it is easy to control the molecular weight, but when the amount used is increased, the molecular weight of the resulting polyurethane urea resin may be lowered.

The weight average molecular weight of the biomass-derived polyurethane urea resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 20,000 to 60,000. If it is less than 10,000, the blocking resistance and solvent resistance as a printed coating film are inferior, and if it exceeds 100,000, the viscosity of the resin solution increases and it becomes difficult to make an ink. The resin solid content in the biomass-derived polyurethane urea resin solution is not particularly limited, but it is preferably 10 to 70% by mass in consideration of workability during ink production, and the viscosity of the resin solution is 30 to 100,000 mPa · s / 25. ° C is preferred. The weight average molecular weight is a value measured by the GPC method (polystyrene conversion). The measurement sample is prepared by precisely weighing the sample (0.04 g in terms of solid content) and adding 5 ml of tetrahydrofuran to dissolve it.
The amine value of the biomass-derived polyurethane urea resin is preferably 1 to 13 mgKOH / g. If it is less than 1, the adhesion to the film is inferior, and if it exceeds 13, there is a risk of thickening when an isocyanate curing agent is added, and there is also a risk of plate clogging.
The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin. The amine value is measured by accurately weighing 10 g or 20 g of the resin solution sample in an Erlenmeyer flask and adding 50 ml of a solvent (methyl ethyl ketone / isopropyl alcohol = 1/1 weight ratio) with a graduated cylinder to dissolve it. Add 1 ml of 0.4% bromcresol green and titrate with 1 / 10N aqueous hydrochloric acid. When the color of the solution changes from blue or blue-green to yellow-green and becomes yellow with the last drop, the resin solution amine value is calculated according to the following formula.
Amine value = A × f × 5.661 / S
However, A = 1 / 10N hydrochloric acid aqueous solution consumption (ml),
f = 1 / 10N hydrochloric acid aqueous solution titer,
S = Sample collection amount (g)
The amine value of the biomass-derived polyurethane urea resin can be calculated by the following formula.
Resin amine value = resin solution amine value × 100 / resin solid content

<Diisocyanate compound (II)>
Examples of the diisocyanate compound (II) include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate, 1,4-cyclohexane disocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and methylcyclohexylene diisocyanate. Cycloaliphatic diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexaethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine Diisocyanate, dimer isocyanate, 2-methylpentane-1,5-diisocyanate, 3-methyl Aliphatic diisocyanates such as tilpentane-1,5-diisocyanate, butane-1,4-diisocyanate, pentane-1,5-diisocyanate, xylylene diisocyanate (XDI), tolylene diisocyanate (TDI), α, α, α ′, α′-tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-dibenzyldiisocyanate, 1,5-naphthyl Range isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diiso Examples thereof include aromatic diisocyanates such as cyanate and tetraalkyldiphenylmethane diisocyanate, and modified products thereof. These can be used alone or in admixture of two or more.
Among them, examples of the biomass origin include dimer isocyanate, pentane-1,5-diisocyanate, and lysine diisocyanate.

<Chain extender (III)>
The chain extender (III) can introduce a urea bond into the polyurethane resin. A compound having 2 or more active hydrogen atoms having reactivity with respect to the isocyanate group of the prepolymer is preferred. Examples of such a chain extender (III) include polyamine compounds containing two or more primary or secondary amino groups in one molecule, hydrazide compounds, or low molecular weight polyols having a molecular weight of less than 600. .

  Polyamine compounds include hydrazine, methylene diamine, ethylene diamine, propylene diamine, 1,4-butylene diamine, trimethylene diamine, hexamethylene diamine, octamethylene diamine, 2-methyl-1,5-pentane diamine, dimer diamine and isophorone diamine. , Piperazine, 2,5-dimethylpiperazine, diaminodiphenylmethane, tolylenediamine, xylylenediamine, dicyclohexylmethane-4,4'-diamine, hydrogenated diphenylmethanediamine, norboranediamine, 3,3'-dichloro-4,4 '-Diaminodiphenylmethane, 4,4'-methylenebis (phenylamine), 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, cyclopentanediamine, cyclohexane Silamine, 4,4-diaminodicyclohexylmethane, diamine components such as 1,4-diaminocyclohexane, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylene Diamine component having a hydroxyl group such as diamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, diethylenetriamine, triethylenetetramine, polyamide polyamine, polyethyleneimine, triaminobenzene, triamino Examples include polyamine components such as phenol and tetraaminobenzene.

  Examples of the hydrazide compound include succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, malonic acid dihydrazide and the like.

As the low molecular weight polyol having a molecular weight of less than 600, the components listed in the polyol (i) can be used. These can be used alone or in admixture of two or more.
Among these, biomass-derived components include dimer diamine, succinic acid dihydrazide, sebacic acid dihydrazide and biomass-derived components of the polyol (i).

<Reaction terminator (IV)>
In order to stop the reaction when synthesizing the biomass-derived polyurethane urea resin solution, it is preferable to use a compound having monovalent active hydrogen as the reaction terminator (IV). The reaction terminator (IV) may be added at the same time as the chain extender (III) or after the chain extension reaction is advanced to some extent with the chain extender. Examples of the reaction terminator (IV) include methanol, ethanol, isopropanol, normal propanol, normal butanol, isobutyl alcohol, tert-butyl alcohol and other monoalcohols, ethylamine, diethylamine, dipropylamine, butylamine, dibutylamine and the like. Monoamine, monoethanolamine, diethanolamine, alkanolamines such as propanolamine and isopropanolamine, carboxyl group-containing amines such as glycine and alanine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2- Examples include hydroxyl-containing amines such as amino-2-ethyl-1,3-propanediol. These can be used alone or in admixture of two or more.

<Catalyst>
A catalyst can be used in the urethanization reaction. Examples of the catalyst include amine catalysts such as triethylamine, N-ethylmorpholine, N-methylmorpholine, triethylenediamine, and dimethylaniline, dibutyltin dilaurate, dioctyltin dilaurate, tin octylate, dibutyltin dioctanoate, dibutyltin oxide, dibutyl Examples include tin-based catalysts such as tin acetate, titanium-based catalysts such as tetrabutyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetraoctyl titanate, diisopropoxybis (ethylacetoacetate) titanium, and diazabicycloundecene catalysts. It is done. These can be used alone or in admixture of two or more.
The addition amount is usually preferably within a range of 0.001 to 1 mol% with respect to the polyol (I).

<Solvent (V)>
In the urethanization reaction, it is preferable to use a solvent (V) for reaction control, and it is more preferable that the solvent is inactive with respect to the isocyanate group or a low activity. Examples of the solvent (V) that can be used include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, glycol solvents such as propylene glycol monomethyl ether , Alcohol solvents such as methanol, ethanol, isopropanol, normal propanol and butanol. These can be used alone or in admixture of two or more.
Among these, it is preferable not to include an aromatic hydrocarbon solvent in consideration of the printing work environment.

  Additives may be added to the biomass-derived polyurethane urea resin solution as necessary. Examples of the additive include an antioxidant, a light stabilizer, a hydrolysis inhibitor, an ultraviolet absorber, a metal deactivator, and a reaction retarder. These may be added alone or in combination of two or more. Further, it can be appropriately added before or after the reaction or during the reaction.

  In the solvent-type gravure ink composition for back printing of the present invention, the biomass-derived polyurethane urea resin is preferably contained in an amount of 3 to 50% by mass, more preferably 5 to 40% by mass. When the amount is less than 3% by mass, the film forming property of the ink is inferior, and when it is more than 50% by mass, the fluidity of the ink is poor and the ink production suitability is inferior.

  As the coloring material of the ink composition of the present invention, a pigment or a dye can be used, but a pigment is preferred from the viewpoint of durability. As the pigment, inorganic pigments and organic pigments can be used, but these may be used alone or in combination of two or more. The addition amount of the color material is appropriately determined according to the ink concentration, coloring power, and hiding power, but it is preferably contained in the ink composition in an amount of 0.1 to 50% by mass.

  Examples of the inorganic pigment include titanium oxide, iron oxide, barium sulfate, zinc oxide, calcium carbonate, silica, aluminum, pearl pigment, brass, and mica.

  Examples of the organic pigment include soluble azo, insoluble azo, condensed azo, phthalocyanine, dioxazine, quinacridone, perylene, perinone, thioindigo, ansanthrone, isoindolinone, selenium, anthraquinone Quinophthalone, azomethine, diketopyrrolopyrrole, carbon black and the like.

In the ink composition of the present invention, other resins may be used in combination with the biomass-derived polyurethane urea resin as necessary. Other resins include petroleum-derived polyurethane urea resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyamide resin, acrylic resin, ethylene-vinyl acetate copolymer resin, chlorinated olefin resin, alkyd resin, cellulose Resin (nitrified cotton, cellulose acetate propionate, cellulose acetate butyrate, etc.), vinyl acetate resin, rosin resin (rosin, cured rosin, polymerized rosin, rosin ester, rosin modified maleic acid resin, etc.), ketone resin, poly Examples include butyral resin, cyclized rubber resin, chlorinated rubber resin, petroleum resin, olefin resin, polyester resin, and polylactic acid resin. These resins may be used alone or in combination of two or more with a polyurethane urea resin derived from biomass, and are preferably in the range of 30% by mass or less in the ink composition.
Among these, as a resin derived from biomass, a cellulose resin, a polyamide resin, a rosin resin, a polylactic acid resin, and the like can be given.

The cellulose resin can be used as a biomass-derived resin. Nitrocellulose is obtained by nitration of the hydroxyl group of cellulose with nitric acid. The average degree of polymerization is about 35 to 480, and the degree of biomass varies depending on the degree of substitution with nitro groups, but about 50% by mass is derived from biomass.
Cellulose acetate propionate resin and cellulose acetate butyrate resin can be obtained by reacting cellulose with a suitable organic acid and / or acid anhydride. The cellulose acetate propionate resin is obtained by triesterifying cellulose with acetic acid and propionic acid and then hydrolyzing. In general, acetylation is 0.6 to 2.5% by mass, propionylation is 42.5 to 46% by mass, hydroxyl groups are 1.8 to 5% by mass, and the degree of biomass is about 50% by mass. The cellulose acetate butyrate resin is obtained by triesterifying cellulose with acetic acid and butyric acid and then hydrolyzing it. Generally, acetylation is 2 to 29.5% by mass, butyrylation is 17 to 53% by mass, hydroxyl group is 0.8 to 4.8% by mass, and the degree of biomass is about 50% by mass.

  By using these cellulosic resins in combination with biomass-derived polyurethane urea resins, blocking resistance can be improved. When the cellulose resin is used in combination with the biomass-derived polyurethane urea resin, the content is preferably 10% by mass or less in the entire resin solid content of the ink composition. When it is larger than 10% by mass, the adhesion to the film and the laminate strength are lowered. Moreover, these cellulose resins can be used alone or in combination of two or more.

  The vinyl chloride-vinyl acetate copolymer resin may be used in combination. Especially, as a vinyl chloride-vinyl acetate copolymer resin, what has a hydroxyl group is good. A vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group is obtained by copolymerizing a vinyl chloride monomer, a vinyl acetate monomer and a hydroxyl group-containing monomer such as vinyl alcohol or hydroxyalkyl acrylate at an appropriate ratio, There is a method obtained by copolymerizing a vinyl acetate monomer and then partially saponifying vinyl acetate. The vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group is provided with toughness and hardness of the resin film by the vinyl chloride component, the vinyl acetate component is imparted with adhesiveness and flexibility, and the hydroxyl group-containing monomer is added to the polar solvent. Good solubility is imparted. The monomer ratio of the vinyl chloride monomer / vinyl acetate monomer / hydroxyl group-containing monomer of the resin is such that the vinyl chloride monomer is 70 to 95% by mass, the vinyl acetate monomer is 1 to 15% by mass, and the hydroxyl group-containing monomer is 1 to 15% by mass. It is preferable to be within. The number average molecular weight is preferably in the range of 10,000 to 45,000.

  By using the vinyl chloride-vinyl acetate copolymer resin in combination with a biomass-derived polyurethane urea resin, blocking resistance can be improved. When the vinyl chloride-vinyl acetate copolymer resin is used in combination with the biomass-derived polyurethane urea resin, it is preferably 50% by mass or less of the total resin solid content of the ink composition. When it is larger than 50% by mass, the adhesion to the film is lowered. The vinyl chloride-vinyl acetate copolymer resin can be used alone or in combination, but can also be used in combination with the cellulose resin.

  In the ink composition of the present invention, if necessary, an anti-friction enhancer, an anti-blocking agent, a pigment dispersant, an antistatic agent, a lubricant, a crosslinking agent, an antifoaming agent, a drying regulator, a plasticizer, and a tackifier. An agent, an adhesion improver, a leveling agent, an antioxidant and the like can be added. Of these, an additive derived from biomass is even better.

In the ink composition of the present invention, a solvent usually used for gravure ink can be used, and those in which the biomass-derived polyurethane urea resin is dissolved or dispersed in the solvent are preferable. Solvents used in gravure inks include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, methanol, ethanol, isopropanol, normal propanol, butanol , Alcohol solvents such as isobutanol and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, Ester solvents such as tert-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene Examples include glycol solvents such as recall monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and esterified products thereof. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. . These can be used alone or in admixture of two or more.
The solvent is preferably in the range of 30 to 95% by mass in the ink composition. If it is less than 30% by mass, the solid content increases and the fluidity is lost. When it is more than 95% by mass, the viscosity becomes low, and the pigment tends to settle. Moreover, ethanol etc. can be used as a solvent derived from biomass.
In particular, it is preferable not to include an aromatic hydrocarbon solvent in consideration of the printing work environment.

The degree of biomass (not including pigment) in the printed coating film prepared using the solvent-type gravure ink composition for back printing containing a polyurethane urea resin derived from biomass may be 3 to 40% by mass, and the degree of biomass is The larger it is, the more effective it is for reducing the environmental burden. The degree of biomass of the biomass-derived polyurethane urea resin is not limited, and polyol (I), polyisocyanate (II), chain extender (III) and / or reaction terminator (IV) in synthesizing the biomass-derived polyurethane urea resin ) Among these components, a biomass-derived component may be used.
The printed coating film is formed on the film base material layer by a printing method or the like which will be described later on the ink composition, but the solvent contained in the ink composition is volatilized in the drying process at the time of printing. As a result, a resin component, a pigment component, and the like remain as solids on the film base layer, and this is referred to as a printed coating film in this specification.
Here, the degree of biomass (excluding pigment) is the biomass-derived solid content contained in the resin solid component excluding the solid content of the pigment component in the printed coating film for the printed coating film prepared on the film substrate layer. The ratio is expressed by the following equation (1).
Biomass degree (%) = (biomass-derived resin solid content / resin solid content) × 100 (1)
If the biomass of the ink composition (not including the pigment) is 3% or more, the biomass of the printed coating produced by using a printing plate used in normal gravure printing is It is considered to be 3% or more. In the case of overprinting, it is sufficient that there is at least one printed coating film having a biomass degree of 3% or more.

The biomass-derived component is obtained from a biomass (biologically-derived renewable resource) material, and is mainly derived from plants. Plants can be obtained from anywhere in Japan and overseas, but from the perspective of food mileage, many of them are domestically produced compared to those imported from soybeans, corn, cottonseed, rapeseed, etc. It is preferable that
Here, food mileage means that the longer the distance between the production area and the consumption area, the higher the energy consumption necessary for transporting foods and the greater the amount of carbon dioxide emissions. This is a concept proposed as an indicator of load. The food mileage can be expressed by a numerical value calculated by L × W, where L is the transport distance when the product is transported from the production area to the sales place, and W is the weight of the product. Food mileage will be smaller if the product's production location and sales location are close, and even if the same product is shipped, if the product is transported from a farther production location, the food mileage will be larger, leading to efforts for local pond consumption. Come.

  The production of the printed coating film is preferably a gravure printing method from the viewpoint of high quality and high productivity. In particular, a gravure printing method using a multicolor gravure printing machine is more preferable.

  The laminate of the present invention has at least one selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, a glycol-based solvent, and an alcohol-based solvent on one of the film substrate layer and the film substrate layer. And a biomass-derived polyurethane urea resin containing a biomass-derived component, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight The solvent-type gravure printing ink composition for back printing having a thickness of 10,000 to 100,000 has a printing layer formed by coating by a gravure printing method, and a laminate layer on the printing layer, It is preferable that the degree of biomass of the printed layer (not including the pigment) is 3 to 40% by mass.

The film base layer is preferably at least one selected from a plastic film or sheet and a laminate thereof. For example, polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, polybutylene terephthalate, polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, polystyrene films, alcohol-based films such as ethylene-vinyl alcohol, polyvinyl alcohol, polyamide films Or transparent polyamide film with a barrier layer placed between them, polycarbonate film, polyacrylonitrile film, polyimide film, cellophane, moisture-proof cellophane, PET film or polyamide film with a deposition layer such as alumina or silica or transparent Evaporated polyamide film, polyvinylidene chloride resin, polyvinyl alcohol tree , Various coating films obtained by coating such as polyacrylic acid resins, co-extruded film of PET and nylon, such as polylactic acid film. These may be either stretched or unstretched, and one kind or two or more kinds may be laminated. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. Further, in order to improve the adhesion of the anchor coat layer or the laminate layer on the printing surface, corona treatment, low temperature plasma treatment, flame treatment, solvent treatment, coating treatment, or the like can be selected. Although there will be no restriction | limiting in particular if the thickness of a film base material layer is in the range which does not have trouble in printability, winding-up property, etc., 5-300 micrometers is preferable and 6-250 micrometers is more preferable.
Moreover, you may use the resin-coated film using paper as a printing surface, or the laminated body of paper and the said plastic film as a film base material layer.
Among them, polyethylene terephthalate, polyethylene, paper, polylactic acid, cellophane, and the like are commercially available as biomass-derived printing base materials.

The printed layer is a layer made of the solvent-type gravure printing ink composition for back printing on one of the film base layers, and the printed layer is coated by a gravure printing method because of high quality and high productivity. It is preferable to be formed. In particular, it is more preferable to prepare by a gravure printing method using a multicolor gravure printing machine. It is preferable that the degree of biomass (excluding pigment) of the printed layer is 3 to 40% by mass.
The printing layer is printed by a gravure printing machine using a corrosive plate called a laser plate or an engraved plate dug by a diamond needle. The printing speed is usually in the range of 30 to 350 m / min.
The printing layer is preferably formed by applying a biomass-derived ink composition to all printing units in a printing unit capable of multicolor printing, but the application, physical properties, design, cost, workability, In consideration of functions and the like, it is not necessary to use the biomass-derived ink composition of the present invention for all printing units, and other general-purpose gravure ink compositions and / or various functional ink compositions, design-related ink compositions, etc. Ink compositions that are not may be used, and may be a printed layer formed by applying these by overprinting or reversal printing.

  The laminate layer is preferably provided on the print layer. The laminate layer may be, for example, a laminate provided with heat sealability or a known sealant film, a resin coating by extrusion lamination, a seal layer by application of a heat sealant or a hot melt agent, rigidity, waist, It means an intermediate layer for imparting or enhancing performances such as gas barrier properties, fragrance retention properties, moisture proof properties, pinhole resistance properties, dead hole properties, light shielding properties and straight line cut properties.

As the sealing layer, as long as the sealing strength can be sufficiently ensured, the bonding method is appropriately selected according to the film base material layer, application, configuration, and the like. For example, bonding with a known sealant film via an adhesive (dry laminating method, non-solvent laminating method, wet laminating method) to the printing layer on the film base layer or the intermediate layer, and laminating by heat (heat Laminating method), resin coating by extrusion laminating process (extrusion laminating method, coextrusion laminating method, PE sandwich laminating method), heat sealing agent and hot melt coating, resin coating that directly presses molten polypropylene to the printing surface (direct laminating) Method) and the like can be preferably used. These methods can be used alone or in combination to produce a laminate.
Although there is no restriction | limiting in particular in the thickness of a sealing layer, 0.2-300 micrometers is preferable and 0.5-300 micrometers is more preferable.

Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, co-pressed films and colored films thereof, polystyrene films, polyacrylonitrile films, and ethylene-vinyl alcohol resin films. It may be mentioned, may be stretched or unstretched, and may be a single type or two or more types laminated.
In particular, as a polyethylene film, a film derived from biomass is commercially available.

  Examples of resins that can be used for the resin coating by extrusion lamination include polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, ethylene-acrylic acid copolymers, and ethylene-acrylic acids. Ethyl copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene and polypropylene can be mixed with maleic acid or fumar Examples thereof include thermoplastic resins such as acid-modified polyolefin resins modified with acids, polystyrene resins, polybutylene terephthalate resins, and the like, and these resins may be laminated in one kind or two or more kinds. Especially, the thing derived from biomass is marketed in polyethylene-type resin.

  Examples of heat sealant resins include shellacs, rosins, rosin-modified maleic resins, rosin-modified phenolic resins, nitrified cotton, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, rings Rubber, polyamide resin, vinyl chloride-vinyl acetate copolymer, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, (meth) acrylic Examples thereof include thermoplastic resins such as resin, urethane resin, ethylene-vinyl alcohol resin, styrene maleic acid resin, casein, and alkyd resin, and these may be used alone or in combination of two or more. Examples include those in which these resins are dissolved in a solvent, those in which they are dissolved in water, or those in which they are dispersed in water, such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, and polypropylene emulsions.

The intermediate layer can impart or reinforce performance such as rigidity, waist, gas barrier property, aroma retention, moisture resistance, pinhole resistance, dead hole property, light shielding property, linear cut property, etc. to the laminate.
Examples of the intermediate layer include plastic films, sheets, paper, aluminum foil, and laminates thereof. Examples of plastic films include polyester films such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate, polystyrene films, alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol, and polyamides. Barium polyamide film, polycarbonate film, polyacrylonitrile film, polyimide film, cellophane, moisture-proof cellophane, PET film or polyamide film with an aluminum deposition layer on the film or barrier layer in the middle Film or PET film or polyamide Transparent coated polyester film or transparent deposited polyamide film with a deposited layer of alumina or silica on the film, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc., uniaxial stretching such as HDPE and PP A film, a polylactic acid film, etc. are mentioned. These may be either stretched or unstretched, and one kind or two or more kinds may be laminated. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. In order to improve the adhesion of the anchor coat layer and the laminate layer to the bonding surface, corona treatment, low temperature plasma treatment, flame treatment, solvent treatment, coating treatment, or the like can be selected. The treatment is preferably a double-sided treatment. Among them, examples of the biomass-derived intermediate layer include polyethylene terephthalate, aluminum vapor-deposited PET, polyethylene, paper, polylactic acid, and cellophane, and are commercially available.
Moreover, in the laminated body of this invention, it is not necessary to give a printing layer to a film base material layer, and can also provide a printing layer in an intermediate | middle layer.

The thickness of the laminate layer is not particularly limited, but depends on the thickness of the sealing layer and / or the intermediate layer. From the viewpoint of sealability, cost, and productivity, the seal layer is 2 to 200 μm for the sealant film, 1 to 100 μm for the resin coating by extrusion lamination, 1 to 50 μm for the application of the hot melt adhesive, In coating, the thickness is preferably 0.01 to 30 μm.
The intermediate layer may be in a range that does not hinder printing suitability, winding suitability, and the like, and preferably has a thickness of 5 to 300 μm, more preferably 6 to 250 μm.

  In the case of using an adhesive or an anchor coat agent for the dry lamination method, non-solvent lamination method, wet lamination method, extrusion lamination method, etc., commercially available ones may be used, for example, a two-component or one-component urethane resin adhesive Acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, aqueous urethane, isocyanate, organic titanium, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsions. As an application method of the adhesive for forming the adhesive layer for laminating, a known application method can be used. For example, a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, A wire bar coater, a die coater, a dip coater or the like can be used. The thickness of the adhesive or anchor coating agent is not particularly limited, but is preferably in the range of about 0.001 to 10 μm, and particularly preferably in the range of 0.01 to 5 μm.

  The method for producing a laminate of the present invention comprises a step of preparing a film base layer and a hydrocarbon solvent, a ketone solvent, an ester solvent, a glycol solvent and an alcohol solvent in one of the film base layers. A biomass-derived polyurethane urea resin containing at least one selected from the group consisting of a biomass-derived component, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and is derived from the biomass A gravure printing step of creating a printing layer comprising a solvent-type gravure printing ink composition for back printing, wherein the polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000, and a laminate layer is formed on the printing layer And the degree of biomass (including pigments) of the printed layer produced by the gravure printing process. No) is preferably 3 to 40 wt%. In particular, the gravure printing process is preferably a printing process by a multicolor gravure printing machine.

  The process of creating a laminate layer is a dry lamination process where a heat-sealed laminate or a known sealant film is bonded using a dry laminating machine or a non-sol laminating process where a non-sol laminating machine is used. It is a process of creating a sealing layer by an extrusion laminating process that coats molten resin using an extrusion laminating machine, etc., and a process of creating an intermediate layer by the dry laminating process, non-sol laminating process, extrusion laminating process, etc. Is preferred.

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

  Forms produced using the laminate of the present invention include two-side seals, three-side seals, four-side seals, pillow seals, standing pouches, envelope stickers, joint stick stickers, gussets, fusing stickers, square bottom bags, tubes, caramel packaging , Overhold, fin seal, bun packaging, twist, rocket, triangle pack, gable top, brick, shibori, cup, tray, bottle, brick, container, box, case, watch weight, cover, lid, cap, label, Any of well-known forms used for packaging applications such as an in-mold cup may be used. Moreover, a spout, a zipper for opening / closing, etc. can be arbitrarily attached to a packaging bag as needed.

  As a sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

  The ink composition comprises a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents, and alcohol solvents, and a biomass-derived component. Step (1) of preparing a biomass-derived polyurethane urea resin solution containing the biomass-derived polyurethane urea resin solution obtained in the step (1), the presence of the colorant and various additives in the solvent (V) It can manufacture by a well-known method by including the process (2) uniformly mixed and disperse | distributed below. When dispersing, it can be produced by making the aggregated colorant fine particles until the average particle diameter becomes about 0.01 to 1 μm to obtain a dispersion. When the solvent-type gravure printing ink composition for back printing obtained by the production method is formed as a printed coating film on the film substrate layer by a gravure printing step, the degree of biomass in the printed coating film (not including pigment) Becomes a printed coating film with 3 to 40% by mass.

In the mixing and dispersing step (2), various stirrers or dispersing machines can be used. Dispersers, ball mills, sand mills, attritors, bead mills, roll mills, pebble mills, paint shakers, agitators, Henschel mixers, colloid mills, pearl mills, Examples thereof include an ultrasonic homogenizer, a wet jet mill, a kneader, and a homomixer. The production method when using the bead mill is not particularly limited, but may be a pass method or a circulation method, and the pass method may be a multiple pass method in which a dispersion is passed through a plurality of times.
The average particle size of the colorant in the dispersion is the bead separation mechanism of the bead mill, the bead type, the bead particle size, the bead filling rate, the shape and number of stirring blades, the rotational speed, the viscosity of the dispersion, the discharge rate, the premix time, etc. Can be adjusted as appropriate.
Coarse particles and bubbles in the ink composition can be removed by a known filter or centrifuge.

The viscosity of the ink composition is preferably in the range of 10 to 1,000 mPa · s / 25 ° C. If the viscosity is less than 10 mPa · s, the viscosity is too low and the pigment tends to settle. If the viscosity is more than 1,000 mPa · s, the fluidity is poor, causing troubles during ink production, and filling the container is difficult. It becomes. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone plate viscometer.
As solid content in an ink composition, it is preferable to exist in the range of 2-80 mass%. If it is lower than 2% by mass, the coating amount at the time of printing is not sufficient, and if it exceeds 80% by mass, the fluidity is poor and it becomes difficult to make ink.

The hue of the ink composition includes yellow, red, indigo, black, and white color materials as process inks, as well as color materials such as grass, purple, and gold red as intermediate colors, and peony, brown, and transparent. Color materials such as yellow, gold, silver and pearl are also used. Moreover, these can be mixed suitably and can also be used as a toning product. Moreover, it is preferable to prepare a transparent ink composition called medium for concentration adjustment.
When heat-sealing, select a colorant appropriately considering the tint discoloration resistance for applications that hit the seal bar, migration resistance and heat resistance for boil / retort applications, and light resistance for outdoor applications. It is preferable to do. The various ink compositions are subjected to printing by appropriately diluting with a diluting solvent to a viscosity and concentration suitable for printing conditions.

The dilution solvent may be any as long as it can be used after adjusting the viscosity and concentration of the ink composition, and examples thereof include the ink solvent, and a commercially available one can be used without any particular limitation. Examples of commercially available products include PU533 solvent (toluene-containing system), PU515 solvent (non-toluene system), SL9164 solvent (non-ketone system), SL9170 solvent (non-ketone system) (all of which are manufactured by Tokyo Ink Co., Ltd.). .
Of these, non-toluene-based or non-ketone-based diluting solvents are preferable in consideration of the printing work environment. In addition, it is preferable to use an organic solvent derived from biomass.

  The viscosity when the ink composition is used for printing is Zahn Cup No. 3 (manufactured by Kosei Co., Ltd.), preferably within a range of 13 to 25 seconds at 25 ° C. If it is shorter than 13 seconds, it is easy to swim, and if it is longer than 25 seconds, the transferability at the time of printing becomes worse.

At the time of printing, a curing agent can be added to the ink composition as necessary. For example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexyl diisocyanate, pentane-1,5 -Polyisocyanate type curing agents such as aliphatic diisocyanates such as diisocyanate (Stavio PDI) and modified products thereof such as trimethylolpropane trimer, isocyanurate, burette, and allophanate. These can be used alone or in admixture of two or more.
Among these, pentane-1,5-diisocyanate and modified products thereof are preferable as biomass.

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

[(A) Preparation of polyester diol]
PES1
In a round bottom flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas introduction tube, 20.69 parts of petroleum-derived 3-methyl-1,5-pentanediol, 18.24 parts of petroleum-derived neopentyl glycol. Part, 5.44 parts of ethylene-derived ethylene glycol, 55.63 parts of petroleum-derived adipic acid, 0.0003 parts of tetrabutyl titanate, and esterification while removing water generated by condensation at 230 ° C. under a nitrogen stream Was performed for 8 hours, and after confirming that the acid value of the polyester diol was 15 or less, the degree of vacuum was gradually increased by a vacuum pump to complete the reaction. As a result, a biomass-derived polyester diol PES1 having a hydroxyl value of 56.1 mgKOH / g, an acid value of 0.3 mgKOH / g, a number average molecular weight of 2,000, and a biomass degree of 5.4% was obtained.
Similarly, according to the composition of Tables 1 to 4, biomass-derived polyester diols PES2 to 23 and petroleum-derived polyester diols (biomass degree 0%) PES24 to 31 were obtained. Moreover, polyester diol PES32 (biomass degree 100%) similar to the polyester polyol of patent document 3 was obtained.

The biomass degree, hydroxyl value, acid value, and number average molecular weight in the table were measured by the following methods.
The biomass degree was calculated by the following formula (2).
Biomass degree (%) = (biomass-derived resin solid content / resin solid content) × 100 (2)
The hydroxyl value is a value obtained by converting the amount of hydroxyl group in 1 g of resin calculated by esterifying or acetylating the hydroxyl group in the resin with an excess of anhydrous acid and back titrating the remaining acid with alkali to the number of mg of potassium hydroxide. In accordance with JIS K0070.
The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the resin, and was measured according to JIS K0070.
The number average molecular weight was measured by the GPC method (polystyrene conversion).

[Preparation of polyurethane urea resin solution]
PUU1
In a round bottom flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 21.76 parts of synthesized biomass-derived polyetherdiol PES1 having a number average molecular weight of 2,000 and having a number average molecular weight of 2,000 1.15 parts of petroleum-derived polypropylene glycol and 5.09 parts of petroleum-derived isophorone diisocyanate were charged and reacted at 105 ° C. for 6 hours under a nitrogen stream to produce a biomass-derived urethane prepolymer, and then 18.67 parts of ethyl acetate. In addition, 46.67 parts of a biomass-derived urethane prepolymer homogeneous solution was obtained. Subsequently, the biomass-derived urethane prepolymer solution 46. was added to a mixture comprising 1.97 parts of petroleum-derived isophoronediamine, 0.03 part of n-dibutylamine, 30.33 parts of n-propyl acetate, and 21.00 parts of isopropyl alcohol. 67 parts were added and reacted at 60 ° C. for 3 hours. As a result, a biomass-derived polyurethane urea resin solution PUU1 having a resin solid content of 30.0%, a viscosity of 990 mPa · s / 25 ° C., a weight average molecular weight of 32,200, a resin solution amine value of 1.07, and a biomass degree of 3.9% is obtained. It was.
Similarly, according to the composition of Tables 5 to 8, biomass-derived polyurethane urea resin solutions PUU2 to 24 and petroleum-derived polyurethane urea resin solutions (biomass degree 0%) PUU25 to 32 were obtained. Similarly, according to the formulation of Table 9, biomass-derived polyurethane urea resin solutions PUU 33 and 34 having different weight average molecular weights or amine values, polyurethane urea resin solution PUU 35 similar to Patent Document 3 (use of biomass degree 100% PES 32), patent Polyurethane urea resin solution PUU36 (biomass degree 0%) similar to literature 1 and polyurethane urea resin solution PUU37 (biomass degree 0%) similar to patent document 2 were obtained.

The biomass degree, weight average molecular weight, resin solution amine value, and resin amine value in the table were measured by the following methods.
The degree of biomass was calculated by the following formula (3).
Biomass degree (%) = (biomass-derived resin solid content / resin solid content) × 100 (3)
The weight average molecular weight was measured by GPC method (polystyrene conversion). As the column, Gelpack GL-A160, GL-A150, and GL-A130 (manufactured by Hitachi Chemical Co., Ltd.) were used. The measurement sample was prepared by precisely weighing the sample (0.04 g in terms of solid content) and dissolving 5 ml of tetrahydrofuran.
The resin solution amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid necessary to neutralize the amino group contained in 1 g of the resin. The amine value is measured by accurately weighing 10 g or 20 g of the resin solution sample in an Erlenmeyer flask and adding 50 ml of a solvent (methyl ethyl ketone / isopropyl alcohol = 1/1 weight ratio) with a graduated cylinder to dissolve it. Add 1 ml of 0.4% bromcresol green and titrate with 1 / 10N aqueous hydrochloric acid. The time when the color of the solution changed from blue or blue-green to yellow-green and turned yellow with the last drop was taken as the end point, and the resin solution amine value was calculated according to the following formula.
Amine value = A × f × 5.661 / S
However, A = 1 / 10N hydrochloric acid aqueous solution consumption (ml),
f = 1 / 10N hydrochloric acid aqueous solution titer,
S = Sample collection amount (g)
The amine value of the biomass-derived polyurethane urea resin can be calculated by the following formula.
Resin amine value = resin solution amine value × 100 / resin solid content

[Preparation of other resin solutions]
CAP varnish 90 parts of ethyl acetate was charged into a round bottom flask equipped with a stirrer, and 10 parts of cellulose acetate propionate CAP-482-20 (manufactured by Eastman Chemical Co., Ltd.) was added while stirring to create a CAP varnish. did. The resin solid content of CAP varnish was 10%, and the degree of biomass was 49.7%.

CAB varnish 90 parts of ethyl acetate was charged in a round bottom flask equipped with a stirrer, and 10 parts of cellulose acetate butyrate CAB-381-20 (manufactured by Eastman Chemical Co., Ltd.) was added while stirring to prepare a CAB varnish. . The resin solid content of CAB varnish was 10%, and the degree of biomass was 47.7%.

NC varnish Charge 85.7 parts of ethyl acetate to a round bottom flask equipped with a stirrer, and add 14.3 parts of nitrified cotton RS1 / 16 (IPA 30% wet cotton) (manufactured by TNC) while stirring. It was created. The resin solid content of NC varnish was 10%, and the degree of biomass was 49.1%.

CL varnish Charge 90 parts of ethyl acetate into a round bottom flask equipped with a stirrer and add 10 parts of sorbine AL (vinyl chloride-vinyl acetate copolymer resin, manufactured by Nissin Chemical Industry Co., Ltd.) while stirring. CL varnish was created. The resin solid content of CL varnish was 10%, and the degree of biomass was 0%.

[Preparation of white ink]
After mixing and stirring 35 parts of titanium oxide (CI Pigment W-7), 32 parts of biomass-derived polyurethane urea resin PUU1, 5 parts of CAP varnish, 20 parts of n-propyl acetate, and 8 parts of isopropyl alcohol, a paint shaker is used. To obtain 100 parts of white ink W1. The biomass degree of W1 (excluding pigment) was 6.2%.
Similarly, according to the composition of Table 10, the biomass-derived polyurethane urea resin PUU1 is replaced with PUU7, PUU13, PUU19, PUU25, PUU26, PUU33, PUU34, PUU35, PUU36, PUU37, white ink W2, W3, W4, W5, W6 , W7, W8, W9, W10, W11 were obtained.

[Production of yellow ink]
After mixing and stirring 10 parts of disazo yellow (CI Pigment Y-14), 35 parts of biomass-derived polyurethane urea resin PUU2, 5 parts of CAB varnish, 20 parts of methyl ethyl ketone, 20 parts of n-propyl acetate, and 10 parts of isopropyl alcohol, paint 100 parts of yellow ink Y1 was obtained by dispersing with a shaker. The degree of biomass of Y1 (excluding pigment) was 10.4%.
Similarly, in accordance with the composition of Table 11, the biomass-derived polyurethane urea resin PUU2 was replaced with PUU8, PUU14, PUU27, and yellow inks Y2, Y3, Y5 were obtained.

Similarly, according to the composition of Table 11, disazo yellow (CI Pigment Y-14) is replaced with benzimidazolone (CI Pigment Y-180), and biomass-derived polyurethane urea resin PUU20 is used. 100 parts of ink Y4 were obtained.
Furthermore, according to the composition of Table 11, the biomass-derived polyurethane urea resin PUU20 was replaced with PUU28 to obtain 100 parts of yellow ink Y6.

[Production of red ink]
Mixing and stirring 10 parts of Watching Red (CI Pigment R-48: 3), 35 parts of biomass-derived polyurethane urea resin PUU3, 5 parts of NC varnish, 20 parts of n-propyl acetate, 20 parts of methyl ethyl ketone, and 10 parts of biomass-derived ethanol After that, it was dispersed with a paint shaker to obtain 100 parts of red ink R1. The biomass degree of R1 (excluding pigment) was 11.0%.
Similarly, according to the composition of Table 12, the biomass-derived polyurethane urea resin PUU3 was replaced with PUU9, PUU15, PUU21, PUU29, and red inks R2, R3, R4, R9 were obtained.

Similarly, using the biomass-derived polyurethane urea resin PUU6 in place of Watching Red (CI Pigment R-48: 3) instead of Naphthol AS (CI Pigment R-146) according to the formulation of Table 12. 100 parts of red ink R5 was obtained.
Furthermore, according to the composition of Table 12, the biomass-derived polyurethane urea resin PUU6 was replaced with PUU12, PUU18 and PUU25, PUU24, PUU30 to obtain red inks R6, R7, R8, R10.

[Production of indigo ink]
12 parts of copper phthalocyanine blue (CI Pigment B-15: 3), 30 parts of biomass-derived polyurethane urea resin PUU4, 10 parts of CL varnish, 18 parts of n-propyl acetate, 20 parts of methyl ethyl ketone, 10 parts of isopropyl alcohol are mixed and stirred. After that, it was dispersed in a paint shaker to obtain 100 parts of indigo ink C1. The degree of biomass of C1 (excluding pigment) was 17.5%.
Similarly, indigo inks C2, C3, C4, and C5 were obtained by replacing the biomass-derived polyurethane urea resin PUU4 with PUU10, PUU16, PUU22, and PUU31 in accordance with the formulation shown in Table 13.

[Production of black ink]
After mixing and stirring 12 parts of carbon black (CI Pigment BL-7), 35 parts of biomass-derived polyurethane urea resin PUU5, 10 parts of CL varnish, 17 parts of ethyl acetate, 17 parts of n-propyl acetate, and 9 parts of isopropyl alcohol The ink was dispersed with a paint shaker to obtain 100 parts of black ink B1. The biomass degree of B1 (excluding pigment) was 11.9%.
Similarly, black ink B2, B3, B4, and B5 were obtained by replacing the biomass-derived polyurethane urea resin PUU5 with PUU11, PUU17, PUU23, and PUU32 in accordance with the formulation shown in Table 14.

  Ink stability was evaluated for white inks W1 to W11, yellow inks Y1 to Y6, red inks R1 to R10, indigo inks C1 to C5, and black inks B1 to B5, and the results are shown in Tables 10 to 14, respectively.

<Ink stability>
The state of the ink one week after the ink production was visually observed and evaluated. The ink having no sedimentation of the coloring material component was judged to have good ink stability. Regarding sedimentation of color material components, ○: no change from immediately after production, Δ: slight sedimentation of color material components is observed (no problem in practical use), x: all color material components are sedimented, xx: inking It was evaluated in 4 grades.

  The white ink W8 did not produce a printed matter because the biomass-derived polyurethane urea resin had a high weight average molecular weight and a low amine value, so it gelled and was difficult to ink.

[Production of printed matter]
For each unit of 1 to 5 color printing of 8-color gravure printing machine (Fuji Kikai Kogyo Co., Ltd.), ceramic doctor (manufactured by Tokyo Seisakusho Co., Ltd.), engraving helio plate with chromium hardness of 1050Hv / stylus 130 degrees (Co., Ltd.) Towa Process Co., Ltd.), a finisher roll was attached, and B1 ink, C1 ink, R1 ink, Y1 ink, and W1 ink were respectively diluted with a dilution solvent PU515 (manufactured by Tokyo Ink Co., Ltd.) with Zaan Cup No. 3 to adjust the viscosity to 15 seconds, B1 ink in the first unit ink pan, C1 ink in the second unit ink pan, R1 ink in the third unit ink pan, Y1 ink in the fourth unit ink pan, W1 ink was put into each ink pan. In all units, a biomass-derived PET (polyethylene terephthalate) film (abbreviation: bio-PET, Toyobo) with a doctor pressure of 2 kgf / cm ² , a drying temperature of 60 ° C., a printing pressure of 2 kg / cm ² and a printing speed of 200 m / min and a thickness of 12 μm. 8,000 m of a print PR1 of biomass-derived PET film / biomass-derived ink was obtained. During printing, the viscosity was kept constant with a viscosity controller (manufactured by Meisei Corporation).
Similarly, B1, C1, R1, Y1, and W1 inks from the first unit to the fifth unit were respectively replaced with B2, C2, R2, Y2, and W2 inks as shown in Table 15 to obtain a printed material PR2. Similarly, as shown in Table 15, in place of the B5, C5, R9, Y5, and W7 inks, a printed material PR21 was obtained.

Furthermore, the film base material was changed from biomass-derived PET to PET film E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm, from B1 to B5, C5, R9, Y5, A printed material PR11 was obtained in place of the W5 ink.
Similarly, as shown in Table 15, the printed matter PR12 was obtained by replacing the W5 ink with the W6 ink. Further, as shown in Table 15, from the first unit to the fifth unit, printed materials PR22, PR23, and PR24 were obtained using each ink.

  Similarly, instead of using a film base of 15 μm thick nylon film Bonil RX (abbreviation: nylon, manufactured by Kojin Film & Chemicals Co., Ltd.), as shown in Table 15, each ink was used to print PR3, PR5, PR13, PR15, PR25 were obtained.

  Similarly, instead of Pyrene P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.), which is a stretched polypropylene film having a thickness of 20 μm, the printed materials PR4 and PR14 using each ink as shown in Table 15, respectively. Got.

  Similarly, instead of Super Neil SP-R (abbreviation: barrier nylon, manufactured by Mitsubishi Chemical Corporation) of a barrier nylon film having a thickness of 15 μm as a film substrate, printed materials using each ink as shown in Table 15 respectively. PR6 and PR16 were obtained.

  Similarly, instead of FOS-BT (abbreviation: OPP, manufactured by Futamura Chemical Co., Ltd.), which is a stretched polypropylene film having a thickness of 30 μm, the printed materials PR7 and PR17 using each ink as shown in Table 15, respectively. Got.

Similarly, in place of E-5102 of a PET film having a thickness of 12 μm, the ink is used as shown in Table 15. In this case, for each of these inks, 100 parts of the ink, the biomass-derived isocyanate curing agent was used. 3 parts of LG curing agent G (manufactured by Tokyo Ink Co., Ltd.) was added to obtain a printed material PR8.
Similarly, as shown in Table 15, each ink is used, and at that time, 3 parts of LG curing agent C (manufactured by Tokyo Ink Co., Ltd.), a petroleum-derived isocyanate curing agent, is added to each of these inks with respect to 100 parts of ink. As a result, a printed material PR18 was obtained.

Similarly, instead of GL-ARH (abbreviation: transparent vapor-deposited PET, manufactured by Toppan Printing Co., Ltd.) of a transparent vapor-deposited PET film having a thickness of 12 μm, inks were used as shown in Table 15, in which case 3 parts of LG curing agent G (manufactured by Tokyo Ink Co., Ltd.), a biomass-derived isocyanate curing agent, was added to each ink to 100 parts of ink to obtain a printed matter PR9.
Similarly, as shown in Table 15, each ink is used, and at that time, 3 parts of LG curing agent C (manufactured by Tokyo Ink Co., Ltd.), a petroleum-derived isocyanate curing agent, is added to each of these inks with respect to 100 parts of ink. As a result, a printed material PR19 was obtained.

  Similarly, instead of OP U-1 (abbreviation: OPP, manufactured by Mitsui Chemicals, Inc.) of a stretched polypropylene film having a thickness of 20 μm, the printed material PR10 was printed using each ink as shown in Table 15. And PR20 were obtained.

  For the printed materials PR1 to PR25, the degree of biomass in the printed coating film, plate fogging resistance during printing, blocking resistance of the printed coating film, film adhesion, solvent resistance, and plate clogging resistance were evaluated. Indicated.

The biomass degree (not including pigment) in the printed coating is calculated by calculating the biomass degree (not including pigment) of the ink according to the following formula (4), and is regarded as equivalent to the biomass degree, and evaluated in Table 15. Indicated. (Circle): The degree of biomass was evaluated in two steps, that is, 3% or more, and x: the degree of biomass was less than 3%.
Biomass degree (%) = (biomass-derived resin solid content / resin solid content) × 100 (4)

<Plate resistant fog>
The printed matter was pasted on black or white paper, and the degree of ink adhered to the non-image area was visually observed and evaluated. It was judged that the plate-proof fog resistance was good when the ink was not attached to the non-image area. The ink adhesion on the non-image area was evaluated in three stages: ○: no adhesion at all, Δ: slight adhesion (no problem in practical use), x: adhesion on the entire surface.

<Blocking resistance>
The printed material is cut into a size of 3 cm × 3 cm, the printed surface and the non-printed surface are overlapped, a load of 500 g / cm ² is applied at 50 ° C. for 24 hours, and the printed surface and the non-printed surface are overlapped. The state of ink peeling when the film was peeled was observed, and the peeling resistance at that time was evaluated. Those having no ink peeling and no peeling resistance were judged to have good blocking resistance. About ink peeling and peeling resistance, ○: No ink peeling, no peeling resistance, Δ: Slight ink peeling is observed, there is peeling resistance, ×: Ink peeling is recognized throughout, and there is considerable peeling resistance, It was evaluated in three stages.

<Film adhesion>
Adhesive tape (cellophane tape, 28 mm, manufactured by Nichiban Co., Ltd.) is affixed to the printed surface of the printed material, and after rubbing it strongly with the thumb five times, the adhesive tape is slowly peeled off, and then quickly peeled off from the middle. The degree of removal of the printed surface on the adhesive tape was visually observed and evaluated. A film having a small degree of being taken on the adhesive tape was judged to have good film adhesion. ◎: not taken at all, ○: slightly taken (0 to less than 10% per area as peeled area), Δ: taken slightly (from 10% to less than 20% per area as peeled area) No problem in practical use), x: Evaluation was made in four stages: almost all (20% or more per area as the peeled area).

<Solvent resistance>
One drop of ethyl acetate was dropped on the printed surface of the printed matter with a dropper, and after 10 seconds, the ethyl acetate was wiped off with a soft cloth, and the state of the printed surface was observed and evaluated. Those in which the printed surface was not dissolved were judged to have good solvent resistance. ○: Evaluation was made in two stages: almost no dissolution of the printed surface, and X: dissolution of the printed surface was observed.

<Plate resistant clogging>
With respect to 100 parts of W1 ink, Zahn Cup No. 1 was prepared with 5 parts of isocyanate curing agent (LG curing agent C, manufactured by Tokyo Ink Co., Ltd.) and PU515 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.). 3 was used to prepare a printing ink adjusted to a viscosity of 15 seconds. A ceramic doctor (manufactured by Tokyo Seisakusho Co., Ltd.) and a sculpture helio plate (made by Towa Process Co., Ltd.) with a chrome hardness of 1050 Hv / stylus 130 degrees are applied to a printing unit of an 8-color gravure printing machine (manufactured by Fuji Machine Industry Co., Ltd.). The W1 ink mixed with the curing agent was put into the ink pan of the first unit. In the unit, a biomass-derived PET (polyethylene terephthalate) film (abbreviation: Bio-PET, Toyobo Co., Ltd.) with a doctor pressure of 2 kgf / cm ² , a drying temperature of 60 ° C., a printing pressure of 2 kg / cm ² , a printing speed of 200 m / min, and a printing speed of 200 m / min. )), And a printed material PR1 of biomass-derived PET film / biomass-derived ink was printed.
After 5 minutes from the start of printing, the printing machine was stopped, left as it was for 5 minutes, and then printing was resumed. The printability after resuming printing was confirmed and evaluated. After printing was resumed, it was judged that those capable of printing had good resistance to plate clogging. Similarly, with respect to W2 ink to W11 ink (excluding W8 ink), the plate clogging resistance was evaluated. ◯: Evaluation was made in two stages: printable, x: unprintable.

[Production of laminated laminate]
On the printed layer of the printed material PR1, a polyethyleneimine anchor coat agent Citabond T-100 (manufactured by Nippon Soda Co., Ltd.) having a solid content of 1% by weight was applied, and the line speed was 100 m / min with an extrusion laminator. Then, molten polyethylene LC600A (abbreviation: LD, manufactured by Nippon Polyethylene Co., Ltd.) was melted at 315 ° C. and laminated at 15 μm, and VM-PET MWR2 (abbreviation: VM-PET, which is a 12 μm aluminum-deposited PET film). In the same manner, 15 μm of molten polyethylene is laminated and LIX-NP L4102 (abbreviation: LLDPE, manufactured by Toyobo Co., Ltd.), which is a 50 μm linear low density polyethylene film, is laminated. The laminate LAM1 of PR1 / LD / VM-PET / LD / LLDPE was obtained by bonding.
Similarly, PR11 / LD / VM-PET / LD / LLDPE laminate LAM11 was obtained by replacing the printed material PR1 with PR11. Moreover, it replaced with PR21-PR24 and obtained laminated body LAM21-LAM24.

A polybutadiene-based anchor coating agent T-180E (manufactured by Nippon Soda Co., Ltd.) having a solid content of 1% by weight was applied onto the printed layer of the printed matter PR2, and the line speed was 100 m / min with an extrusion laminator. Molten polyethylene SBC818 (abbreviation: Biomass LD, manufactured by Braskem) was melted at 320 ° C. and laminated at 15 μm, and a linear low density polyethylene film of 30 μm, LL-XMTN (abbreviation: LLDPE, Futamura Chemical Co., Ltd.) )) Was pasted together to obtain a laminate LAM2 of PR2 / biomass LD / LLDPE.
Similarly, PR12 / LD / LLDPE laminate LAM12 was obtained by replacing the printed material PR2 with PR12 and the molten polyethylene SBC818 with LC600A.

On the printing layer of the printed matter PR3, an isocyanate anchor coating agent Oliveine EL540 / CAT-RT32 (manufactured by Toyo Morton Co., Ltd.) having a solid content of 8.5% by weight was applied, and the line speed was measured with an extrusion laminator. Molten polyethylene LC600A was melted at 325 ° C. at 100 m / min and laminated at 18 μm, and TUX-FCD (abbreviation: LLDPE, manufactured by Mitsui Chemicals Tosero Co., Ltd.), which is a 40 μm linear low density polyethylene film, was pasted. After combining, aging was performed at 38 ° C. for 48 hours to obtain a laminate LAM3 of PR3 / LD / LLDPE.
Similarly, PR13 / LD / LLDPE laminate LAM13 was obtained by replacing the printed material PR3 with PR13.

On the printed layer of the printed matter PR4, Takelac A-969V / Takenate A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was applied with a dry laminating machine at a line speed of 150 m / min and an application amount of 2.6 g / m. ² and tosello CP GLC (abbreviation: CPP, manufactured by Mitsui Chemicals, Inc.), which is an unstretched polypropylene film having a thickness of 30 μm, and then aged at 40 ° C. for 24 hours. PR4 / DL / CPP laminate LAM4 was obtained.
Similarly, PR14 / DL / CPP laminate LAM14 was obtained by replacing the printed material PR4 with PR14.

On the printed layer of the printed material RR5, Dick Dry LX-401A / SP-60 (abbreviation: DL, manufactured by DIC Corporation) is applied at a line speed of 150 m / min and a coating amount of 3 g / m ² with a dry laminating machine. After coating and bonding TUX-HC (abbreviation: LLDPE, manufactured by Mitsui Chemicals Tosero Co., Ltd.), which is a linear low-density polyethylene film having a thickness of 60 μm, aging is performed at 40 ° C. for 72 hours. PR5 / DL / LLDPE laminate LAM5 was obtained.
Similarly, PR15 / DL / LLDPE laminate LAM15 was obtained by replacing the printed material PR5 with PR15. Moreover, it replaced with PR25 and obtained laminated body LAM25.

On the printed layer of the printed matter PR6, Takelac A-620 / Takenate A-65 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was applied with a dry laminating machine at a line speed of 150 m / min and an application amount of 3 g / m ² . After coating CMPS008C (abbreviation: EP film, manufactured by Mitsui Chemicals Tosero Co., Ltd.), which is a co-pressed film having a thickness of 30 μm, aging is performed at 35 ° C. for 48 hours, and PR6 / A laminate LAM6 for a lid material of DL / EP film was obtained.
Similarly, PR16 / DL / EP film cover laminate LAM16 was obtained by replacing printed material PR6 with PR16.

On the printed layer of the printed matter PR7, Takerak A-620 / Takenate A-65 was applied by a dry laminating machine at a line speed of 150 m / min so as to have a coating amount of 3 g / m ^2, and an aluminum having a thickness of 12 μm. After bonding VM-PET MWR2, which is a vapor-deposited PET film, and also bonding FOR-MHW2 (abbreviation: OPP, manufactured by Phutamura Chemical Co., Ltd.), which is a stretched polypropylene film having a thickness of 30 μm, at 35 ° C. Aging was performed for 48 hours to obtain an in-mold label laminate LAM7 of PR7 / DL / VM-PET / DL / OPP.
Similarly, PR17 / DL / VM-PET / DL / OPP in-mold label laminate LAM17 was obtained by replacing the printed material PR7 with PR17.

On the printed layer of printed matter PR8, Takelac A-525 / Takenate A-52 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was applied with a dry laminating machine at a line speed of 150 m / min and an application amount of 3.3 g / m. ² and affixed with 9 μm thick aluminum foil (abbreviation: AL, manufactured by Toyo Aluminum Co., Ltd.), and similarly, emblem ONMB-RT (abbreviation: nylon) which is a 15 μm thick nylon film. , Unitika Co., Ltd.) and Trefan NO ZK93KM (abbreviation: CPP, manufactured by Toray Film Processing Co., Ltd.), which is an unstretched polypropylene film with a thickness of 60 μm, and 72 hours at 50 ° C. Aging was performed to obtain a laminate LAM8 of PR8 / DL / AL / DL / nylon / DL / CPP.
Similarly, PR18 / DL / AL / DL / nylon / DL / CPP laminate LAM18 was obtained by replacing the printed material PR8 with PR18.

On the printed layer of the printed matter PR9, Takelac A-525 / Takenate A-52 was applied by a dry laminating machine at a line speed of 150 m / min so that the coating amount was 3.3 g / m ^2, and the thickness was 15 μm. Nylon film emblem ONMB-RT was bonded together, and in the same way, 60 mm thick unstretched polypropylene film Trefan NO ZK93KM was bonded, and then aged at 50 ° C. for 72 hours, PR9 / DL / A nylon / DL / CPP laminate LAM9 was obtained.
Similarly, PR19 / DL / nylon / DL / CPP laminate LAM19 was obtained by replacing the printed material PR9 with PR19.

On the printed layer of the printed material PR10, ECOAD EA-N370A / B (abbreviation: NS, manufactured by Toyo Morton Co., Ltd.) is a non-sol laminating machine at a line speed of 100 m / min and an application amount of 1.2 g / m ² . After being coated, VM-CPP2203 (abbreviation: VM-CPP, manufactured by Toray Film Processing Co., Ltd.), which is a 20 μm-thick vapor-deposited unstretched polypropylene film, is bonded and then aged at 38 ° C. for 24 hours. Thus, a laminate LAM10 of PR10 / NS / VM-CPP was obtained.
Similarly, PR20 / NS / VM-CPP laminate LAM20 was obtained by replacing the printed material PR10 with PR20.

  Regarding laminates LAM1 to LAM25, laminate strength of laminates, laminates LAM3, LAM5, LAM8, LAM9, LAM13, LAM15, LAM18, LAM19 and LAM25 are evaluated for hot water resistance (boil resistance, retort resistance). The results are shown in Table 15.

<Lamination strength>
The laminate is made into a strip with a width of 15 mm and used as a test piece. This test piece is subjected to T-type peeling at a tensile speed of 300 mm / min using a universal tensile tester (RTE-1210, manufactured by Orientec Co., Ltd.). The maximum load during pulling and peeling was measured as the laminate strength. The greater the laminate strength, the better the laminate properties. The laminate strength was evaluated in three stages: ◯: 80 g or more, Δ: 50 g or more, less than 80 g, x: less than 50 g.

<Boil resistance>
The laminates LAM3, LAM5, LAM13, LAM15, and LAM25 were bonded by heat sealing at 180 ° C. for 1 second to obtain a 10 × 10 cm packaging bag having an opening. After filling the packaging bag with a mixture of ketchup / vinegar / salad oil = 1/1/1, the opening was sealed by heat sealing in the same manner as above to produce a pouch-shaped packaging bag. . This packaging bag was boiled at 98 ° C. for 30 minutes, and the appearance of the pouch was visually observed and evaluated. A pouch with no floating appearance was judged to have good boil resistance. The appearance of the pouch was evaluated in three stages: ○: no change at all, Δ: slight lift was observed, and x: lift was observed over the entire surface.

<Retort resistance>
The laminates LAM8, LAM9, LAM18, and LAM19 were bonded by heat sealing at 220 ° C. for 1 second to obtain a 10 × 20 cm packaging bag having an opening. After filling the packaging bag with a mixture of ketchup / vinegar / salad oil = 1/1/1, the opening was sealed by heat sealing in the same manner as above to produce a pouch-shaped packaging bag. . This packaging bag was retorted at 121 ° C. for 30 minutes, and the appearance of the pouch was visually observed and evaluated. A pouch that did not float was judged to have good retort resistance. The appearance of the pouch was evaluated in three stages: ○: no change at all, Δ: slight lift was observed, and x: lift was observed over the entire surface.

  From the results of Tables 10 to 15, the printed coating film prepared by the gravure printing method of the solvent-based gravure printing ink composition for back printing of the present invention has a higher degree of biomass in the printed coating film than the conventional one. Good ink stability, anti-fogging resistance during printing, anti-blocking property of printed film, film adhesion, solvent resistance, plate-clogging resistance, laminate laminate property, and hot water resistance It is clear that there is. Since the laminate of Comparative Example 24 uses a biomass-derived polyurethane urea resin having a small weight average molecular weight and a high amine value, the printed coating film has poor blocking resistance and solvent resistance, and the laminate has laminate properties. Inferior. For the back-printing solvent-type gravure printing ink composition (W9) using a biopolyurethane resin similar to Patent Document 13 of Comparative Example 25 and using dimethylformamide (DMF) as a solvent, DMF is used. Thus, printing was originally performed but printing was performed on a trial basis (PR22). PR22 is capable of printing, but has a odor peculiar to DMF at the time of printing, and abandoned printing halfway. As a precaution, the printed film and laminate (LAM22) were evaluated before the abandonment, but although the degree of biomass was high, the plate resistance during printing, the film adhesion of the printed film, Insufficient solvent resistance and plate clogging, and cannot be laminated. Since Comparative Example 26 similar to Patent Document 1 uses 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, the stability of the ink is good, the plate resistance fogging during printing, and the printing Although the blocking resistance, film adhesion, solvent resistance, and plate-clogging resistance of the coating film are good, it does not become a printed coating film having a biomass degree of 3 to 40% by mass in the printed coating film. Since Comparative Example 27 similar to Patent Document 2 uses an alkylene oxide adduct of bisphenol A (BA-10 glycol (EO-10)), the stability of the ink is good and the plate resistance fogging resistance during printing. The printing coating film has good blocking resistance and plate clogging resistance, but has poor solvent resistance and does not become a printing coating film having a biomass degree of 3 to 40% by mass. Because it uses a biomass-derived polyurethane urea resin with a low weight average molecular weight and a high amine value, it has poor blocking resistance and solvent resistance of the printed coating film, poor laminate properties when used as a laminate, and hot water There is no processability.

Claims (7)

Including a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and biomass-derived components;
The solvent-type gravure printing ink for back printing, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000. The composition
A printed coating film characterized by having a biomass degree (not including a pigment) in the printed coating film of 3 to 40% by mass when a printed coating film is formed on the film substrate layer by a gravure printing method. On one of the film base layer and the film base layer,
Including a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and biomass-derived components;
The solvent-type gravure printing ink for back printing, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000. The composition is
A printing layer formed by applying a gravure printing method;
A laminate layer on the printed layer;
A laminate having a biomass degree (not including a pigment) of the printed layer of 3 to 40% by mass. A step of preparing a film base layer, and one of the film base layers,
Including a biomass-derived polyurethane urea resin containing at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents, and biomass-derived components;
The solvent-type gravure printing ink for back printing, wherein the biomass-derived polyurethane urea resin has an amine value of 1 to 13 mgKOH / g, and the biomass-derived polyurethane urea resin has a weight average molecular weight of 10,000 to 100,000. A gravure printing step for creating a printed layer comprising the composition;
Forming a laminate layer on the printed layer,
The manufacturing method of the laminated body characterized by the biomass degree (a pigment is not included) of the printing layer produced by the said gravure printing process being 3-40 mass%.   A packaging bag produced using the laminate according to claim 2.   A lid material produced using the laminate according to claim 2.   A label produced using the laminate according to claim 2. Biomass-derived polyurethane-urea resin containing at least one selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, glycol-based solvents and alcohol-based solvents, and biomass-derived components A step (1) of preparing a polyurethane urea resin solution;
Including a step (2) of mixing and dispersing the biomass-derived polyurethane urea resin solution obtained in the step (1), a coloring material, and a solvent to obtain a solvent-type gravure printing ink composition for back printing,
The solvent is at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, glycol solvents and alcohol solvents,
The amine value of the polyurethane urea resin in the biomass-derived polyurethane urea resin solution is 1 to 13 mgKOH / g, and the weight average molecular weight of the polyurethane urea resin in the biomass-derived polyurethane urea resin solution is 10,000 to 100 , 000,
When the solvent-type gravure printing ink composition for back printing obtained in the step (2) is formed as a printed coating on the film substrate layer by the gravure printing step, the biomass degree (including pigments) in the printed coating No) is a printed coating film having a content of 3 to 40% by mass. A method for producing a solvent-type gravure printing ink composition for back printing.