JP2020128487A - Film gravure printing ink composition, printing method, printed matter, and laminated stack - Google Patents

Abstract

To provide an ink composition which has excellent temporal stability, can prevent printing failure caused by static electricity, and is also excellent in other properties as a film gravure printing ink composition.SOLUTION: A film gravure printing ink composition comprises a pigment, a binder resin, and an organic solvent, and further comprises alkyl imidazoline and/or a compound represented by general formula (1) in the figure in an amount from 0.05 to 2.5 mass% of the film gravure printing ink composition. (Ris a C1-10 hydrocarbon group; R, Rand Rare a C2-10 hydrocarbon group; and Y is Cl, Br, or ROSO, where Ris a C1-4 hydrocarbon group.)SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention mainly relates to a printing ink composition for printing on a film for packaging materials and the like, a printing method, a printed matter obtained by the printing method, and a laminated laminate.

BACKGROUND ART Packaging materials using various plastic films are used for foods, confectionery, household goods, pet foods, etc. from the viewpoint of designability, economy, content protection, transportability, and the like. In addition, many packaging materials are gravure-printed or flexographic-printed for the purpose of giving a design, message or the like that appeals to consumers.
Then, in order to obtain the packaging material, surface printing is performed on the surface of the base material film of the packaging material, or an adhesive or anchor agent is applied to the printed surface of the back surface of the base material film of the packaging material, if necessary. Back printing is performed by laminating on.
In back printing, after printing color ink and white ink on various films such as various general-purpose films (polyester, nylon), aluminum foil, various high-performance films (film coated with an inorganic or organic barrier material), On the printed layer of the white ink, a polyethylene film, a polypropylene film or the like is laminated for the purpose of heat sealing by dry laminating using an adhesive, extrusion laminating using an anchor coating agent, or the like.

In recent years, the printing speed has increased to improve productivity. Therefore, at low humidity, especially in winter (at low temperature and low humidity), the gravure printing ink composition for film is charged with static electricity, which causes ink splashing from the printing surface of the sharp image area during ink transfer. In this case, there is a problem that misting of the ink is likely to occur and the printed matter is contaminated.
Whiskers and misting due to static electricity are affected by printing speed, ink viscosity, printing plate depth, printing site environment (temperature, humidity), and degree of charging of the printing machine. The environment was improved (sprinkling or humidification with a humidifier), and the beard and misting were prevented by physical static elimination with static electricity removal tape, etc., but these measures were not sufficient as preventive measures.
In order to solve the problem, a method using an antistatic agent, for example, coconut alkyl bis(hydroxyethyl)methyl nitrate and coconut alkyl bis(hydroxyethyl)methyl chloride (see, for example, Patent Document 1), quaternary ammonium salt compound ( (For example, see Patent Document 2), a method using a quaternary ammonium salt (hydrochloride) such as monoalkyltrimethylammonium chloride, monoalkylbenzyldimethylammonium chloride, dialkyldimethylammonium chloride (for example, Patent Document 3). There is). However, in recent years, there has been a demand for a higher printing speed, the effect is still insufficient, and there are problems such as deterioration in temporal stability.

JP, 2005-290082, A JP, 2000-169834, A JP, 2011-162663, A

An object of the present invention is to provide an ink composition which is excellent in stability over time, can prevent printing defects due to static electricity, and is also excellent in other properties as a gravure printing ink composition for films.

As a result of intensive studies to solve the above problems, the present inventors have found that alkyl imidazoline and/or the compound represented by formula (1) is added to a film gravure printing ink composition in an amount of 0.05 to 2. By including 5% by mass, it was found that printing stability due to static electricity can be prevented without impairing the stability of ink over time, and the present invention described below has been completed.
That is, the present invention is as follows.
1. A gravure printing ink composition for a film, which comprises a pigment, a binder resin, and an organic solvent, and further comprises an alkyl imidazoline and/or a compound represented by the general formula (1) in a gravure printing ink composition for a film. A gravure printing ink composition for a film, which comprises -2.5% by mass.
(1)
_{(R 1:} a hydrocarbon group having 1 to 10 carbon _{atoms, R 2, R 3, R} 4: a hydrocarbon group having 2 to 10 carbon atoms, Y _{is, Cl, Br, R 5 OSO} 3, provided _{that, R} 5: A hydrocarbon group having 1 to 4 carbon atoms)
2. The gravure printing ink composition for a film according to 1, wherein the binder resin contains a polyurethane resin having an amine value of 1 to 15 mgKOH/g.
3. The gravure printing ink composition for a film according to 1 or 2, which is for lamination.
4. Furthermore, the binder resin is a gravure printing ink composition for a film according to any one of 1 to 3, wherein the binder resin contains a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer.
5. Further, the gravure printing ink composition for a film according to any one of 1 to 4, wherein the gravure printing ink composition for a film contains at least one selected from an adhesion improver and an antiblocking agent.
6. The gravure printing ink composition for a film according to 5, which contains an adhesion improver and an antiblocking agent.
7. The adhesion improver is at least one selected from rosin and its derivatives, chlorinated polypropylene, and dammar resin, and the antiblocking agent is silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, cellulose acetate butyrate resin. The gravure printing ink composition for a film according to 5 or 6, which is at least one selected from nitrified cotton.
8. The organic solvent is a gravure printing ink composition for a film according to any one of 1 to 7, which is a mixed solvent of an ester organic solvent and an alcohol organic solvent.
9. The gravure ink composition for a film as described in any one of 1 to 8, which contains water.
10. A printing method in which a gravure printing ink composition for a film according to any one of 1 to 9 is used to print on a plastic film by a gravure printing machine.
A printed matter obtained by the printing method according to 11.10.
A laminate obtained by laminating the printed matter according to 12.11 and a base material via a laminating adhesive.

Advantageous Effects of Invention According to the present invention, it is possible to obtain an ink composition, a printing method, a printed matter, and a laminate which are excellent in stability over time and can prevent printing defects due to static electricity, and also have excellent other properties as a gravure printing ink composition for films. it can.

The present invention is a gravure printing ink composition for a film, which comprises a pigment, a binder resin and an organic solvent, and further comprises an alkylimidazoline and/or a compound represented by the formula (1) in the gravure printing ink composition for a film. It is a gravure printing ink composition for films containing 0.05 to 2.5 mass%.
Hereinafter, the gravure printing ink composition for a film of the present invention will be specifically described.

<Antistatic agent>
The antistatic agent is an alkyl imidazoline and/or a compound represented by the general formula (1), and is 0.05 to 2.5 mass% in the gravure printing ink composition for a film, preferably 0.05 to 1 0.0 mass%, more preferably 0.05 to 0.5 mass% is preferably contained. If the content is less than 0.05% by mass, the effect of preventing printing failure due to static electricity tends to be reduced, while if it exceeds 2.5% by mass, there is no further improvement in performance.
The alkyl imidazoline has a structure in which an alkyl group is bonded to the 2-position of the imidazoline ring, and the alkyl group can be selected from the group consisting of C4-20. Specifically, homogenol L-95 (manufactured by Kao Corporation) can be exemplified.
The compound represented by the general formula (1) is a compound represented by the following general formula (1).
(1)
_{(R 1:} a hydrocarbon group having 1 to 10 carbon _{atoms, R 2, R 3, R} 4: a hydrocarbon group having 2 to 10 carbon atoms, Y _{is, Cl, Br, R 5 OSO} 3, provided _{that, R} 5: A hydrocarbon group having 1 to 4 carbon atoms)
Specific examples include triethylmethylammonium chloride, tetra(decyl)ammonium bromide, tetra(pentyl)ammonium chloride, benzyltributylammonium chloride, N,N-dibutyl-N-ethyl-1-butaneaminium/ethyl sulfate. it can.
By using the alkyl imidazoline of the present invention and/or the compound represented by the general formula (1), it becomes possible to prevent printing defects due to static electricity and to improve the stability of the ink over time, as compared with the prior art. Become.
Further, in order to incorporate the alkyl imidazoline and/or the compound represented by the general formula (1) into the gravure printing ink composition for a film, a method (internal addition) of compounding at the time of producing the gravure printing ink composition for a film or Alternatively, it can be contained by a method of adding to the gravure printing ink composition for a film during printing (external addition).
In addition, an antistatic agent may be used in combination within a range in which the effect of preventing printing failure due to static electricity does not decrease.

(Pigment)
As the pigment, for example, various inorganic pigments, organic pigments or extender pigments that are generally used in printing ink can be used.
As the inorganic pigment, for example, titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, dark blue, ultramarine blue, carbon black, colored pigments such as graphite, as an extender pigment, silica particles, calcium carbonate, kaolin, clay, Examples thereof include barium sulfate, aluminum hydroxide and talc. Among them, it is preferable to use titanium oxide as the white pigment.
Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the like.
The content of these pigments in the ink composition is usually about 1 to 50% by mass.

(Binder resin)
The binder resin is a polyurethane resin, preferably a polyurethane resin having an amine value from the viewpoints of ink stability, adhesiveness and laminating suitability, preferably a polyurethane resin having an amine value, and a vinyl chloride/vinyl acetate copolymer It includes a polymer and/or a vinyl chloride/acrylic copolymer.

<Polyurethane resin>
As the polyurethane resin, a polyurethane resin generally used in printing ink can be used.
Among them, a polyurethane resin having an amino group (having an amine value) is preferable from the viewpoints of stability over time of ink, adhesiveness and suitability for lamination. Among the polyurethane resins having an amino group, a polyurethane resin having one or more selected from a primary amino group, a secondary amino group and a tertiary amino group at the terminal of the molecule is more preferable.
More preferred is a polyurethane resin having a hydroxyl group and having at least one selected from a primary amino group, a secondary amino group and a tertiary amino group at the end of the molecule.

As such a polyurethane resin, a polyurethane resin obtained by synthesizing a urethane prepolymer by a reaction of an organic diisocyanate compound and a high molecular weight diol compound, and reacting a chain extender and a reaction terminator with it, is preferable. Can be used for
Examples of the organic diisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, 1,4-cyclohexane diisocyanate, alicyclic diisocyanate compounds such as isophorone diisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and α, Examples include araliphatic diisocyanate compounds such as α,α′,α′-tetramethylxylylene diisocyanate. These organic diisocyanate compounds may be used either individually or in combination of two or more. Among them, an alicyclic diisocyanate compound, an aliphatic diisocyanate compound and an araliphatic diisocyanate compound are more preferable.

Examples of the polymer diol compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as ethylene oxide of bisphenol A and alkylene oxide adducts such as propylene oxide, adipic acid, sebacic acid, and anhydrous. One or more dibasic acids such as phthalic acid and one of glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and 3-methyl-1,5-pentanediol. Alternatively, polyester diol compounds such as polyester diols and polycaprolactone diols obtained by subjecting two or more kinds to a condensation reaction, and the like can be given. These polymeric diol compounds may be used either individually or in combination of two or more.
Further, in addition to the above-mentioned polymer diol compounds, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- A low molecular weight diol compound such as butanediol and 1,3-butanediol may be used alone or in combination of two or more.
When a mixed solvent system of an ester solvent and an alcohol solvent (hereinafter sometimes referred to as a “mixed liquid”) is used as an organic solvent to be described later during the synthesis of the polyurethane resin, the polymer diol compound is used as a polydiol compound. The use of an ether diol compound, preferably polypropylene glycol, tends to increase the solubility of the resulting polyurethane resin, and also tends to improve printability such as gradation reproducibility and fog prevention property. It is preferable because it allows a wide range of ink designs to be performed according to the desired performance.

Further, the use ratio of the organic diisocyanate compound and the polymer diol compound is preferably such that the equivalent ratio of isocyanate group:hydroxyl group (isocyanate index) is 1.2:1.0 to 3.0:1.0, and more preferably It is 1.3:1.0 to 2.0:1.0. If the above isocyanate index is less than 1.2:1.0, the polyurethane resin tends to be flexible, and the blocking resistance may be low when the ink composition of the present invention is printed. It may be necessary to use it together with a hard resin. When the above isocyanate index is more than 3.0:1.0, the obtained polyurethane resin may be too hard and the adhesiveness and the suitability for lamination may be deteriorated.

As the chain extender, a known chain extender used in a polyurethane resin as a binder for ink can be used, for example, ethylenediamine, propylenediamine, tetramethylenediamine, aliphatic diamines such as hexamethylenediamine, Aliphatic diamines such as isophorone diamine and 4,4′-dicyclohexylmethanediamine, aromatic diamines such as toluylenediamine, araliphatic diamines such as xylenediamine, N-(2-hydroxyethyl)ethylenediamine, N Diamines having a hydroxyl group such as -(2-hydroxyethyl)propylenediamine, N,N'-di(2-hydroxyethyl)ethylenediamine, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, Examples include diol compounds such as triethylene glycol.
Further, polyamines such as diethylenetriamine and triethylenetetramine can be used in combination as long as the polyurethane resin does not gel.

As a reaction terminator for introducing a primary amino group, a secondary amino group and a tertiary amino group into the terminal of a polyurethane resin, aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine and hexamethylenediamine, Aliphatic diamines such as isophoronediamine and 4,4′-dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, and araliphatic diamines such as xylenediamine, Examples thereof include diamines having a hydroxyl group such as N-(2-hydroxyethyl)ethylenediamine and N-(2-hydroxyethyl)propylenediamine. Among these, polyamines having a primary amino group such as diethylenetriamine and triethylenetetratriamine are preferable.
As the reaction terminator for introducing a hydroxyl group into the polyurethane resin, alkanolamines such as monoethanolamine and diethanolamine, diamines having a hydroxyl group such as N-(2-hydroxyethyl)ethylenediamine and N-(2-hydroxyethyl)propylenediamine. Examples thereof can be mentioned. Further, it is possible to use monoamine compounds and monoalcohol compounds which are known reaction terminators, and specifically, monoalkylamines such as n-propylamine and n-butylamine, and dialkylamines such as di-n-butylamine. Examples thereof include monoalcohols such as ethanol and ethanol.

When the above-mentioned preferred polyurethane resin has a specific functional group, the gravure printing ink composition for a film of the present invention has excellent printability and adhesiveness to a film.
Particularly when it is a gravure printing ink composition for a backing film, the polyurethane resin contains at least one selected from the group consisting of a primary amino group, a secondary amino group and a tertiary amino group at the terminal of the molecule. It is desirable to have at least one selected from a primary amino group and a secondary amino group at the terminal, and it is preferable to have a hydroxyl group.
Further, the amine value of the polyurethane resin is preferably 1.0 to 15.0 mgKOH/g, and more preferably 2.0 to 8.0 mgKOH/g. If the amine value is less than 1.0 mgKOH/g, the adhesiveness of the printing ink composition for a film of the present invention to a film may be lowered, and further the suitability for lamination may be lowered, and the amine value may be 15. If it exceeds 0 mgKOH/g, the blocking resistance may decrease.
In the present invention, the amine value means an amine value per 1 g of a solid content, and a 0.1N hydrochloric acid aqueous solution is used to conduct a potentiometric titration method (for example, COMMITTE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK. -900), manufactured by Hiranuma Sangyo Co., Ltd., and then converted to the equivalent of potassium hydroxide.

Moreover, as the polyurethane resin, a biomass polyurethane resin may be contained in consideration of the environment. The biomass polyurethane resin will be described. In the description of the biomass polyurethane resin, the description common to the above polyurethane resin will be appropriately omitted.
The biomass polyurethane resin is a polyurethane resin containing a biomass-derived (plant-derived) component. Biomass polyurethane resin can contribute to the prevention of global warming and the reduction of environmental load as compared with the case of using other exhaustible resources.Therefore, urethane prepolymer was synthesized by reaction with biopolyol component and isocyanate component. It is preferably a biomass polyurethane resin obtained by reacting a chain extender and a reaction terminator as needed, and more preferably the isocyanate component is a plant-derived bioisocyanate.

The biopolyol component is preferably a biopolyester polyol obtained by reacting a short chain diol component having 2 to 4 carbon atoms with a carboxylic acid component. It is more preferable that at least one of the short-chain diol component and the carboxylic acid component of the biopolyol component is plant-derived, and it is further preferable that both are plant-derived.
The plant-derived short-chain diol component having 2 to 4 carbon atoms is not particularly limited. As an example, the short-chain diol component may be 1,3-propanediol, 1,4-butanediol, ethylene glycol or the like obtained from a plant raw material by the following method, and these may be used in combination. Good.
1,3-Propanediol can be produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (such as corn). 1,3-Propanediol produced by a bio-method such as the above-mentioned fermentation method produces useful by-products such as lactic acid and has a lower production cost than 1,3-propanediol produced by the EO production method. It is possible to keep it low.
1,4-butanediol can be produced by hydrogenating succinic acid obtained by producing glycol from a plant resource and fermenting it. In addition, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene.

The plant-derived carboxylic acid component is not particularly limited. For example, the carboxylic acid component is sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid and the like. These may be used in combination. Among these, it is preferable that the carboxylic acid component contains at least one selected from the group consisting of sebacic acid, succinic acid, and dimer acid.
The biopolyol component can be produced as a 100% plant-derived biopolyester polyol by appropriately subjecting a plant-derived short-chain diol component and a plant-derived carboxylic acid component to a condensation reaction. Specifically, polytrimethylene sebacate polyol is obtained by directly dehydrating and condensing plant-derived sebacic acid and plant-derived 1,3-propanediol. Further, polybutylene succinate polyol is obtained by directly dehydrating and condensing plant-derived succinic acid and plant-derived 1,4-butanediol, and these may be used in combination.

From the environmental aspect, the biomass polyurethane resin is preferably contained in the polyurethane resin in a solid content of 10% by mass or more, more preferably 40% by mass or more, and further preferably 100% by mass.
As a method for producing the biomass polyurethane resin, a known method for producing a polyurethane resin can be used as it is by using the above material. Further, when the molecular weight and the chemical structure of each component and the equivalent ratio are different, the hardness of the resulting polyurethane resin is also different. Therefore, by appropriately combining these components, it is possible to adjust the printability and the lamination suitability. ..
The mass average molecular weight of the polyurethane resin is preferably 10,000 to 70,000, and more preferably 20,000 to 60,000.
Further, in order to enhance appropriate flexibility and laminate strength, a polyurethane resin having no urea bond can be blended as the above polyurethane resin.

<Vinyl chloride/vinyl acetate copolymer>
As a vinyl chloride/vinyl acetate copolymer, vinyl chloride monomer and vinyl acetate monomer, which have been conventionally used in gravure printing ink compositions, are essential components, and if necessary, vinyl propionate, vinyl monochloroacetate, and versatic As the copolymerization component, a fatty acid vinyl monomer such as vinyl acetate, vinyl laurate, vinyl stearate or vinyl benzoate, or a monomer having a functional group such as a hydroxyl group can be used, which is produced by a known method.
Such a vinyl chloride/vinyl acetate copolymer having a hydroxyl group can be obtained by saponifying a part of the acetic ester portion and introducing a (meth)acrylic monomer having a hydroxyl group.
In the case of a vinyl chloride/vinyl acetate-based copolymer having a hydroxyl group obtained by saponifying a part of the acetate portion, a structural unit (the following formula 1) based on the reaction site of vinyl chloride in the molecule, acetic acid The physical properties and dissolution behavior of the resin film are determined by the ratio of the constitutional unit based on the reaction site of vinyl (the following formula 2) and the constitutional unit based on the saponification of the reaction site of vinyl acetate (the following formula 3). That is, the structural unit based on the reaction site of vinyl chloride imparts the toughness and hardness of the resin film, and the structural unit based on the reaction site of vinyl acetate imparts adhesiveness and flexibility, and saponifies the reaction site of vinyl acetate. The constitutional unit based on gives good solubility to the organic solvent system of the ink in consideration of the environment.
Equation 1 _-CH 2 -CHCl-
Equation _{2 -CH 2 -CH (OCOCH 3)} -
Equation 3 _-CH 2 _-CH (OH) -

The vinyl chloride/vinyl acetate-based copolymer used in the film gravure printing ink composition of the present invention has various functional groups in its molecule from the viewpoint of solubility in organic solvents and printability described below. You can do it.
When an environmentally friendly solvent is used as the organic solvent, the vinyl chloride/vinyl acetate copolymer preferably has a hydroxyl group of 50 to 200 mgKOH/g. As commercial products of such vinyl chloride/vinyl acetate copolymers, it is preferable to use, for example, Solvain A, AL, TA5R, TA2, TA3, TAO, TAOL and the like.

<Vinyl chloride/acrylic copolymer>
The vinyl chloride/acrylic copolymer mainly contains a copolymer of vinyl chloride and an acrylic monomer, and the form of the copolymer is not particularly limited. For example, the acrylic monomer may be incorporated into the main chain of polyvinyl chloride in a block or random manner, or may be graft-copolymerized to the side chain of polyvinyl chloride.

As the acrylic monomer, a (meth)acrylic acid ester, an acrylic monomer having a hydroxyl group, or the like can be used. Examples of the (meth)acrylic acid ester include a (meth)acrylic acid alkyl ester, and the alkyl group may be linear, branched, or cyclic, but is preferably a linear alkyl group.
For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylic acid Examples include octadecyl.

Examples of the acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (Meth)acrylic acid hydroxyalkyl ester such as (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl, (meth)acrylic acid 6-hydroxyhexyl, and (meth)acrylic acid 8-hydroxyoctyl. , Polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycol mono(meth)acrylate such as 1,4-cyclohexanedimethanol mono(meth)acrylate, caprolactone modified (meth)acrylate, hydroxyethyl acrylamide, etc. Can be mentioned.
Further, as the acrylic monomer, an acrylic monomer having a functional group other than a hydroxyl group can be used. Examples of the functional group other than the hydroxyl group include a carboxyl group, an amide bond group, an amino group and an alkylene oxide group.
The vinyl chloride/acrylic copolymer preferably has a mass average molecular weight of 10,000 to 70,000.
Further, from the viewpoint of solubility in an environment-friendly solvent as the organic solvent and adhesiveness to a substrate, the vinyl chloride/acrylic copolymer has a hydroxyl group so as to be 50 to 200 mgKOH/g. Is preferred.

The gravure printing ink composition for a film of the present invention comprises a polyurethane resin and (a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer), a polyurethane resin/(a vinyl chloride/vinyl acetate copolymer). Copolymer and/or vinyl chloride/acrylic copolymer)=95/5 to 45/55 (mass ratio), and preferably 92/8 to 70/30.
The polyurethane resin/(vinyl chloride/vinyl acetate copolymer) may be in the range of 90/10 to 75/25, and the polyurethane resin/(vinyl chloride/acrylic copolymer) may be in the range of 95/5 to 85/ The range may be fifteen.
The laminate printing ink composition of the present invention contains the polyurethane resin and the vinyl chloride/vinyl acetate copolymer and/or the vinyl chloride/acrylic copolymer at a ratio of 95/5 to 45/55. The article will have better printability and adhesion to the film. Further, when laminating is performed, it has more excellent laminating suitability.
When the above polyurethane resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) exceeds 95/5, (vinyl chloride/vinyl acetate copolymer and/or vinyl chloride. The proportion of the acrylic copolymer) may decrease, and the adhesiveness to the film becomes insufficient.
On the other hand, when the above polyurethane resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) is less than 45/55, (vinyl chloride/vinyl acetate copolymer and/or chloride) There is a possibility that the ratio of the vinyl/acrylic copolymer) is increased, the printed matter formed by using the ink composition of the present invention becomes hard, and the adhesiveness to the film is also insufficient.

Therefore, in the present invention, when the (vinyl chloride/vinyl acetate copolymer and/or the vinyl chloride/acrylic copolymer) is contained, the above polyurethane resin/(vinyl chloride/vinyl acetate copolymer and/or The vinyl chloride/acrylic copolymer) is preferably 95/5 to 45/55 (mass ratio).
Further, the total content of the polyurethane resin and the vinyl chloride/vinyl acetate copolymer and/or the vinyl chloride/acrylic copolymer in the ink composition of the present invention is preferably 5 to 30% by mass. is there.
Further, in the present invention, one kind selected from an adhesion improver and an antiblocking agent, preferably an adhesiveness improver and an antiblocking agent may be used in combination within a range not deteriorating the intended performance of the present invention. preferable.

(Adhesion improver)
Examples of the adhesion improver include rosin and its derivative, chlorinated polypropylene, dammar resin and the like, and it is desirable to contain at least one or more, more preferably two or more selected from rosin and its derivative.

<Rosin and its derivatives>
Examples of the rosin include gum rosin, tall oil rosin, wood rosin and the like. Generally, rosin is an amber, amorphous resin obtained from pine, and is a mixture because it is obtained from nature, but abietic acid, neoabietic acid, parastoric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, Dehydroabietic acid may be isolated and used for each component, which is also defined as rosin in the present invention.
The rosin derivative is a compound obtained by modifying the above rosin, and is specifically listed below.
(1) Hydrogenated rosin: A rosin in which hydrogen is added to a conjugated double bond (hydrogenation) to improve weather resistance.
(2) Disproportionation rosin: Disproportionation means that two molecules of rosin react and two molecules of abietic acid having a conjugated double bond are converted into aromatic one and the other one of a single double bond. It is a modification that becomes a molecule. Generally, the weather resistance is inferior to hydrogenated rosin, but the weather resistance is improved to the untreated one.
(3) Rosin-modified phenolic resin: In the ink for offset printing, a rosin-modified phenolic resin is often used as a main binder. The rosin-modified phenol resin can be obtained by a known production method.
(4) Rosin ester: An ester resin derived from rosin, which has long been used as a tackifier for tackiness/adhesives.
(5) Rosin-modified maleic acid resin: A resin obtained by addition-reacting maleic anhydride with rosin, and also includes a resin obtained by esterifying a hydroxyl group-containing compound such as glycerin with a non-hydroxyl group and grafting the compound.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from rosin which is a natural resin.
In addition, known rosins and rosin derivatives can be used, and these can be used alone or in combination.
Further, the acid value of rosin and its rosin derivative is preferably 120 mgKOH/g or more. When the acid value is 120 mgKOH/g or more, the laminate strength is improved. More preferably, the acid value is 160 mgKOH/g or more. In addition, the total amount of rosin and its derivative to be used is preferably 0.1 to 3.0% by mass based on the solid content of the gravure printing ink composition for film.

<Chlorinated polypropylene>
As the chlorinated polypropylene, those having a chlorination degree of 20 to 50 can be used. Chlorinated polypropylene having a chlorination degree of less than 20 tends to have low compatibility with organic solvents. On the other hand, when the degree of chlorination exceeds 50, the chlorinated polypropylene tends to have low adhesion to the film. In the present invention, the degree of chlorination is defined by the mass% of chlorine atoms in the chlorinated polypropylene resin. The chlorinated polypropylene is preferably a modified or unmodified chlorinated polypropylene having a mass average molecular weight of 5,000 to 200,000. When the mass average molecular weight is less than 5,000, the chlorinated polypropylene tends to have low adhesiveness. On the other hand, when the mass average molecular weight exceeds 200,000, the chlorinated polypropylene tends to have low solubility in an organic solvent. The amount of chlorinated polypropylene used in the composition is preferably 0.1 to 3.0% by mass in terms of solid content% by mass of the gravure printing ink composition for film.

<Danmaru resin>
Dammar resin, which is also referred to as damar or dammer, is a kind of natural resin derived from plants. Specifically, it is a kind of natural resin obtained from plants of the Dipterocarpaceae or citrus family growing in Southeast Asia such as Malaysia and Indonesia. When used, it is dissolved in a suitable organic solvent to form a varnish. Since the dammar resin does not contain chlorine, chlorine can be eliminated/reduced as compared with the case where chlorinated polypropylene is used in the printing ink composition. In addition, the amount of the dammar resin used when blended is preferably 3.0% by mass or less based on the solid content of the laminated printing ink composition for film gravure flexible packaging.

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

<Silica particles>
Examples of silica particles include naturally-occurring, synthetic, crystalline, non-crystalline, hydrophobic, and hydrophilic particles. The silica particles preferably have an average particle size of 1.0 to 5.0 μm (note that the average particle size of the silica particles means a particle size at an integrated value of 50% (D50) in the particle size distribution, which is measured by the Coulter counter method). Can be sought by). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or may be hydrophobic silica obtained by modifying the hydrophilic functional group with alkylsilane or the like to make it hydrophobic, but hydrophilic ones are preferable, and hydrophilic silica is hydrophilic. The ink containing silica particles also has an effect of promoting wetting/spreading of the ink during overprinting and improving the overprinting effect (hereinafter sometimes referred to as “trapping property”). The amount of silica particles used is preferably 0.0 to 3.0% by mass, and more preferably 0.1 to 1.0% by mass in the film gravure printing ink composition.

<Polyethylene wax>
As the polyethylene wax, one having an average particle diameter in the range of 1.0 to 3.0 μm (the average particle diameter means a particle diameter measured by Microtrac UPA manufactured by Honeywell Co. #1) is used. When the particle size of polyethylene wax is smaller than 1.0 μm, the slip property and blocking property are deteriorated, and when the particle size is larger than 3.0 μm, the trapping property is deteriorated. Further, the content of the polyethylene wax in the gravure printing ink composition for a film is preferably in the range of 0.1 to 1.5% by mass. If the content is less than 0.1% by mass, the intended effect cannot be obtained, and if the content is more than 1.5% by mass, the gloss tends to decrease.

<Nitrated cotton>
As the nitrified cotton, nitrified cotton conventionally used in gravure printing ink compositions can be used. The nitrified cotton is obtained by reacting natural cellulose with nitric acid to obtain a nitrate ester in which the three hydroxyl groups in the 6-membered ring of the anhydrous glucopyranose group in natural cellulose are replaced with nitrate groups. The nitrification cotton used in the present invention preferably has a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90. Specific examples include SS1/2, SS1/4, SS1/8, TR1/16, NCRS-2, (manufactured by KOREA CNC LTD), and the like. The amount of nitrification cotton used is preferably 0.1 to 2.0% by mass in the gravure printing ink composition for a film, depending on the type of pigment.

<Cellulose acetate propionate resin>
As the cellulose acetate propionate resin, a resin conventionally used in a gravure printing ink composition can be used.
The cellulose acetate propionate resin is obtained by triestering cellulose with acetic acid and propionic acid and then hydrolyzing it. Generally, a resin having 0.6 to 2.5% by weight of acetylation, 42 to 46% by weight of propionylation, and 1.8 to 5% by weight of hydroxyl group is commercially available. The cellulose acetate propionate resin is preferably used in the range of 0.1 to 3.0 mass% in the gravure printing ink composition for a film, depending on the type of pigment.

<Cellulose acetate butyrate resin>
As the cellulose acetate butyrate resin, resins conventionally used in gravure printing ink compositions can be used.
The cellulose acetate butyrate resin is obtained by triesterifying cellulose with acetic acid and butyric acid, followed by hydrolysis. Generally, a resin having a degree of acetylation of 2 to 30% by mass, a degree of butyrylation of 17 to 53% by mass, and a degree of hydroxyl groups of 1 to 5% by mass is commercially available. The amount of the cellulose acetate butyrate resin used is preferably 0.1 to 3.0% by mass in the gravure printing ink composition for a film, depending on the type of pigment.

<Fatty acid amide>
The fatty acid amide is not particularly limited as long as it has a residue obtained by removing an acid group from fatty acid and an amide group. Examples of the fatty acid amides include monoamides, substituted amides, bisamides, methylolamides, and esteramides, and at least one selected from the group consisting of monoamides, substituted amides, and bisamides for improving blocking resistance. It is preferable. The amount of the fatty acid amide used is preferably in the range of 0.01 to 1% by mass in the gravure printing ink composition for a film.

-Monoamide: Monoamide is represented by the following general formula (2).
General formula (2) R ₁ -CONH ₂
(In the formula, R ₁ represents a residue obtained by removing COOH from fatty acid.)
Specific examples of the monoamide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, and erucic acid amide.

Substituted amide: The substituted amide is represented by the following general formula (2).
Formula _{(2) R 2 -CONH-R} 3
(In the formula, R ₂ and R ₃ represent a residue obtained by removing COOH from fatty acid, and may be the same or different.)
Specific examples of the substituted amide include N-oleylpalmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl erucic acid amide.

Bisamide: Bisamide is represented by the following general formula (3) or general formula (4).
Formula _{(3) R 4 -CONH-R} 5 -HNCO-R 6
Formula _{(4) R 7 -NHCO-R} 8 -CONH-R 9
(In the formula, R ₄ , R ₆ , R ₇ , and R ₉ represent a residue obtained by removing COOH from a fatty acid, and may be the same or different, and R ₅ and R ₈ are alkylene groups having 1 to 10 carbon atoms. Or represents an arylene group.)
Specific examples of the bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, and hexamethylenebisstearic acid amide. , Hexamethylene bis-behenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N,N'-distearyl adipic acid amide, N,N'- Examples thereof include distearyl sebacic acid amide, N,N'-dioleyl adipamic acid amide, N,N'-dioleyl sebacic acid amide and the like.

Methylolamide: Methylolamide is represented by the following general formula (5).
Formula ₍₅₎ R 10 -CONHCH ₂ OH
(In the formula, R ₁₀ represents a residue obtained by removing COOH from a fatty acid.)
Specific examples of the methylolamide include methylolpalmitic acid amide, methylolstearic acid amide, methylolbehenic acid amide, methylolhydroxystearic acid amide, methylololeic acid amide, and methylolerucic acid amide.

-Esteramide: Esteramide is represented by the following general formula (6).
General formula (6) R< ₁₁ >-CONH-R< ₁₂ >-OCO-R< ₁₃ >.
(In the formula, R ₁₁ and R ₁₃ represent a residue obtained by removing COOH from a fatty acid, which may be the same or different, and R ₁₂ represents an alkylene group having 1 to 10 carbon atoms or an arylene group.)
Specific examples of the ester amide include stearyl amide ethyl stearate and oleyl amide ethyl stearate.
The melting point of the fatty acid amide is preferably 50°C to 150°C.
As the fatty acid constituting the fatty acid amide, a saturated fatty acid having 12 to 22 carbon atoms and/or an unsaturated fatty acid having 16 to 25 carbon atoms are preferable, and a saturated fatty acid having 16 to 18 carbon atoms and/or 18 to 22 carbon atoms. Of unsaturated fatty acids are more preferred. The saturated fatty acid is particularly preferably lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, and the unsaturated fatty acid is particularly preferably oleic acid or erucic acid.

(Organic solvent)
Examples of the organic solvent include ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester-based organic solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate, methanol, ethanol, and the like. Alcohol-based organic solvents such as n-propanol, isopropanol and butanol, and hydrocarbon-based solvents such as toluene and methylcyclohexane can be used.
From the perspective of environmental issues, ester-based organic solvents, mixed solvents of alcohol-based organic solvents and ketone-based organic solvents, or ester-based organic solvents that have advanced to further environmental issues, and mixed solvents of alcohol-based organic solvents Preference is given to using.
Further, the gravure printing ink composition for a film of the present invention preferably contains 0.1 to 20% by weight of a glycol ether organic solvent in 100% by weight of the organic solvent in order to improve wettability and spreadability. Specific examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol. Examples include monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol mono n-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.

(water)
The gravure printing ink composition for a film of the present invention preferably contains water from the viewpoints of alleviating printing defects due to static electricity, preventing plate fogging, and cell reproducibility. The amount of water used in the gravure printing ink composition for film is preferably 10% by mass or less, more preferably 0.1 to 5.0% by mass.

<Other materials>
Various additives such as a pigment dispersant, an antistatic agent, and a plasticizer can be further added to the gravure printing ink composition for a film of the present invention.
As a method for producing an ink composition using the above constituent materials, known methods can be used. Specifically, for example, a mixture of a pigment, a binder resin, an organic solvent and optionally a pigment dispersant is kneaded using a high speed mixer, a ball mill, a sand mill, an attritor, etc., and then thiocyanate, a predetermined amount It can be obtained by adding and mixing the rest of the materials such as the additive of.
When the alkyl imidazoline and/or N,N-dibutyl-N-ethyl-1-butaneaminium/ethyl sulfate is not added by the above-mentioned production method, it can be added at the time of printing.

(Printing method using gravure printing ink composition for film, and laminate obtained thereby)
Next, a method of performing printing using the gravure printing ink composition for a film of the present invention to obtain a laminate will be described.
The laminate of the present invention is, for example, firstly printed on a resin film one or more times by a gravure printing method with a gravure printing ink composition for a film other than white. Then, on the surface side of the colored ink layer formed by these printings (after the final lamination, the lower layer side as viewed from the surface layer), printing is optionally performed by a gravure printing white ink composition for a film in a gravure printing method, and a dryer is used. dry.
A laminate for a packaging bag or the like can be obtained by laminating a resin film or the like on the side of the white ink composition layer of the obtained printed matter by various laminating methods.
Examples of the laminating method include an extrusion laminating method in which an anchor coating agent is applied on the surface of a printed matter and then a molten polymer is laminated, and a laminating adhesive is applied on the surface of a printed matter, and then a film-like polymer is laminated. A laminating method can be used. The extrusion laminating method is a method in which a titanium-based, urethane-based, imine-based, polybutadiene-based, or the like anchor coating agent is applied to the surface of a printed matter, and then a molten polymer is laminated by a known extrusion laminating machine. Further, it is also possible to laminate the molten resin as an intermediate layer with other materials in a sandwich form.

As the molten polymer used in the extrusion laminating method, conventionally used resins such as low density polyethylene, ethylene-vinyl acetate copolymer and polypropylene can be used. Above all, the effect of the present invention is enhanced in the constitution with low density polyethylene in which carbonyl groups are easily generated by oxidation during melting.
The dry laminating method is a method in which a urethane-based or isocyanate-based laminating adhesive is applied to the surface of a layer of a white ink composition, and then a polymer film is laminated by a known dry laminating apparatus. As the resin for the film used in the dry laminating method, polyethylene, unstretched polypropylene or the like can be used, and particularly in the packaging material used for retort applications, an aluminum foil is placed between the base material and the resin film to be laminated. You can also laminate with. Such a laminated product can be used for boil/retort applications after bag-making and filling the contents. It is also excellent in boil resistance, electrical suitability (whisker, misting), cell reproducibility, and plate fog prevention.
The resin film used at this time is not particularly limited, and various printing plastic films such as polyester films such as polyethylene terephthalate (PET), polylactic acid, polycaprolactone, nylon, vinylon, and various printing plastic films can be used. A film obtained by laminating metal vapor deposition, a barrier layer coated with a barrier resin, or the like can be used.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, "%" means "mass %" and "part" means "part by mass" unless otherwise specified.
(Polyurethane resin)
・Polyurethane resin varnish 1
100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and isophorone were placed in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introducing pipe. 44.4 parts by mass of diisocyanate was charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 518 parts by mass of ethyl acetate and 91 parts by mass of isopropyl alcohol were added, and then 15.6 parts by mass of isophoronediamine was added to extend the chain, and 0.49 parts by mass of monoethanolamine and 0. The reaction was stopped by adding 48 parts by mass to obtain a polyurethane resin varnish 1 (solid content: 30% by mass, amine value: 3.4 mgKOH/g).

・Polyurethane resin varnish 2
100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and isophorone were placed in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introducing pipe. 44.4 parts by mass of diisocyanate was charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 518 parts by mass of ethyl acetate and 91 parts by mass of isopropyl alcohol were added, and then 15.6 parts by mass of isophoronediamine was added to extend the chain, and 0.24 parts by mass of monoethanolamine and 0. The reaction was stopped by adding 7 parts by mass to obtain a polyurethane resin varnish 2 (solid content: 30% by mass, amine value: 5.2 mgKOH/g).

・Polyurethane resin varnish 3
In a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 35.2 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. The mixture is allowed to cool to near room temperature, 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol are added, 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.35 parts by mass of monoethanolamine is further added to react. After that, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction to obtain a polyurethane resin varnish 3 (solid content: 30% by mass, amine value: 6.4 mgKOH/g).

・Polyurethane resin varnish 4
In a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 17.6 parts by mass of isophorone diisocyanate and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. The mixture is allowed to cool to near room temperature, 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol are added, 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.35 parts by mass of monoethanolamine is further added to react. Then, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction to obtain a polyurethane resin varnish 4 (solid content 30% by mass, amine value 6.4).

・Polyurethane resin varnish 5
In a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from sebacic acid (derived from castor oil) and 1,3-propanediol (derived from plant), 17.6 parts by mass of isophorone diisocyanate and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol were added, and then 8.2 parts by mass of isophoronediamine was added to extend the chain, and 0.35 parts by mass of monoethanolamine was further added. A biopolyurethane resin varnish 5 (solid content 30 mass %, amine value 6. 4) was obtained.

・Polyurethane resin varnish 6
100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and isophorone were placed in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introducing pipe. 44.4 parts by mass of diisocyanate was charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 518 parts by mass of ethyl acetate and 91 parts by mass of isopropyl alcohol were added, 15.6 parts by mass of isophoronediamine was added to extend the chain, and 1.1 parts by mass of monoethanolamine was further added to react. After stopping, a polyurethane resin varnish 6 (solid content 30% by mass, amine value 0 mgKOH/g) was obtained.

(Antistatic agent (compound that prevents printing defects due to static electricity))
Alkyl imidazoline (homogenol L-95 (manufactured by Kao Corporation))
N,N-dibutyl-N-ethyl-1-butanaminium/ethyl sulfate polyoxyethylene polyoxypropylene block polymer alkylbenzyldimethylammonium chloride

(Vinyl chloride/vinyl acetate resin)
Vinyl chloride/vinyl acetate copolymer (Solvane TA-3, manufactured by Nissin Chemical Industry Co., Ltd.)
(Vinyl chloride/acrylic copolymer)
A vinyl chloride/acrylic copolymer (vinyl chloride/2-hydroxypropyl acrylate=84/16, weight average molecular weight 45000) was dissolved in propyl acetate to give a varnish having a solid content of 30% by mass.

(Pigment)
Carbon black C.I. I. PY14 (Pigment Yellow 14)
Titanium oxide (R-960, manufactured by DuPont)
(Adhesion improver)
<Rosin and its derivatives>
Polymerized rosin: Acid value 160mgKOH/g
<Chlorinated polypropylene>
40 parts by mass of chlorine polypropylene (solid content 50%) having a chlorination degree of 40% and a number average molecular weight of 100,000 and 60 parts by mass of methylcyclohexane were mixed and stirred to obtain a chlorinated polypropylene varnish having a solid content of 20%.
<Danmaru resin>
50 parts by mass of a commercially available natural dammar resin (solid) was dissolved in 50 parts by mass of methylcyclohexane to obtain a dammar resin solution having a solid content of 50%.
(Anti-blocking agent)
<Silica particles>
Average particle size 4.5 μm
<Polyethylene wax>
Average particle size: 2.11 μm
<Fatty acid amide>
Ethylenebisstearic acid amide <mixture 1, mixture 2>
By mass ratio, ethyl acetate/propyl acetate/IPA (isopropyl alcohol)=50/25/25

<Production example of gravure black ink composition base material for film>
The pigment (carbon black), polyurethane resin varnish 1 to 6, vinyl chloride/vinyl acetate copolymer or vinyl chloride/acrylic copolymer is kneaded using a paint conditioner manufactured by Red Devil Co., and further by static electricity. A compound for preventing printing defects, an adhesion improver, an antiblocking agent, a mixed solution 1, and water were added to the gravure printing black ink composition for films of Examples B1 to B15 and Comparative Examples B1 to B6 shown in Table 1. A base material was obtained.

<Production Example of Yellow Ink Composition Base Material for Laminate for Flexible Packaging>
The pigment (CI.PY14), polyurethane resin 2, vinyl chloride/vinyl acetate copolymer are kneaded using a paint conditioner manufactured by Red Devil Co., and a compound that prevents printing defects due to static electricity and adhesion. The improver, the antiblocking agent, the mixed solution 1, and water were added to obtain laminate printing yellow ink composition base materials for Examples Y1 to Y3 and Comparative Examples Y1 to Y4 shown in Table 1.

<Production example of gravure white ink composition substrate for film>
The pigment (titanium oxide R-960, manufactured by DuPont), the polyurethane resin varnish 2 and the vinyl chloride/vinyl acetate copolymer are kneaded using a paint conditioner manufactured by Red Devil Co. to prevent printing failure due to static electricity. The compound, the adhesion improver, the antiblocking agent, the mixed solution 1, and water were added to obtain a white ink composition substrate for film gravure printing of Example W1 shown in Table 1.

(Ink storage stability)
The gravure ink composition base material for a film obtained above was sampled in a glass bottle, and the storage stability of the ink was evaluated from the presence or absence of sedimentation of the pigment when stored at an ambient temperature of 60° C. for 14 days.
In addition, Example B14 was evaluated after externally adding an alkyl imidazoline to the black ink composition base material for gravure printing for film.
A: No sedimentation was observed, and the storage stability of the ink composition substrate was good. B: Sedimentation was observed, and the storage stability of the ink composition substrate was poor.

<Printing conditions when evaluating printability by static electricity>
For 100 parts by mass of each of the gravure ink black ink composition base material for film (excluding Example B14), the gravure printing yellow ink composition base material for film, and the gravure printing white ink composition base material for film, Dilute with the mixture 2 according to the formulation, and for Example B14, add 100 parts by mass of the alkyl imidazoline according to the formulation of Table 1, dilute with the mixture 2 and adjust the viscosity with Zan Cup No. 3 manufactured by Ryusha Co., Ltd. for 15 seconds. To prepare an ink composition. PET film (polyethylene terephthalate film having one side subjected to corona discharge treatment, Toyobo Co., Ltd., E-5101, thickness 12 μm) is used for the gravure printing machine using a gravure printing machine, a gravure ink composition for film, a gravure for film The printing yellow ink composition and the gravure printing white ink composition for film were printed and dried under the following conditions to evaluate the printability by static electricity.
(Printing method and printing conditions)
Room environment when printing: Temperature 25℃, humidity 50%
Coating machine: Gravure printing machine
Coating speed: 150m/min
Printing plate: Helio 175 line/inch
(Design: gradation plate with gradation of halftone dot density 5 to 100%)
Drying temperature: 55℃

<Production of laminated body 1>
100 parts by mass of each of the gravure black ink composition for film (excluding Example B14), the gravure yellow ink printing composition for film, and the white gravure printing ink composition for film were mixed in accordance with the composition shown in Table 1. After diluting, for Example B14, sodium thiocyanate was added according to the formulation shown in Table 1, diluted with the mixed solution, and the viscosity was adjusted to 15 seconds by Zahn Cup No. 3 manufactured by Ryukyu Co., Ltd. Using a gravure printing machine on the treated surface of various films, a film gravure ink ink composition, a film gravure yellow ink composition, or a film gravure white ink composition is printed under the following conditions and dried, A printed matter for lamination was obtained. At the time of printing, the guide roll was evaluated. Further, the obtained laminated printed matter was used to evaluate blocking resistance, adhesiveness, boil suitability, and retort suitability. The specific evaluation method is shown below.
(Printing method and printing conditions)
Room environment when printing: Temperature 25℃, humidity 50%
Coating machine: Gravure printing machine
Coating speed: 150m/min
Printing plate: Helio 175 line/inch
Drying temperature: 55℃

<Production of laminated body 2>
A liquid mixture according to the formulation of Table 1 with respect to 100 parts by mass of each of the black gravure ink composition for film (excluding Example B14), the yellow gravure ink composition for film, and the white gravure ink composition for film. With respect to Example B14, sodium thiocyanate was added according to the formulation in Table 1, diluted with the mixed solution, and the viscosity was adjusted to 15 seconds using Zahn Cup No. 3 manufactured by Ryukyu Co., Ltd. Using a gravure printing machine on the treated surface of various films, a gravure printing ink ink composition for film or a gravure printing yellow ink composition for film is printed and dried under the following conditions, and then a gravure printing white ink composition for film Was printed and dried under the following conditions to obtain a printed matter for lamination, and the suitability for overprinting was evaluated. The specific evaluation method is shown below.
(Printing method and printing conditions)
Coating machine: Gravure printing machine
Coating speed: 150m/min
Printing plate: Black or yellow printing plate: Direct 175 line solid plate
Printing plate that prints white: Helio 175 line/inch
(Design: gradation plate with gradation of halftone dot density 5 to 100%)
Drying temperature: 55℃

<About film>
PET (film): Polyethylene terephthalate film having one side subjected to corona discharge treatment, Toyobo Co., Ltd. E-5101, thickness 12 μm
OPP: Corona discharge treated biaxially oriented polypropylene film, Toyobo Co., Ltd., P-2161, thickness 25 μm
NY: Nylon film, Toyobo, N-1102, thickness 15 μm
Fine barrier: PET film with alumina vapor deposition on one side (trade name: Fine Barrier AT-R, Reiko Co., Ltd.)
Tech barrier: PET film with silica vapor deposition on one side (trade name: Tech barrier TXR, manufactured by Mitsubishi Chemical Corporation)
A-OP: Stretched polypropylene film coated with polyvinyl alcohol on one side (trade name: A-OPBH, manufactured by Mitsui Chemicals Tohcello)
Emblem: Stretched nylon film coated with polyvinylidene chloride on one side (Product name: Emblem-DC DCR, Unitika Ltd.)
IB-PET (PET film processed by aluminum vapor deposition, trade name: IB-PET-PUB, manufactured by Dai Nippon Printing Co., Ltd.)
Besera: PET film coated with acrylic polymer on one side (Besera ET140R, manufactured by Toppan Printing Co., Ltd.)
GL: PET film with alumina vapor deposition treatment on one side (product name: GL-ARH, manufactured by Toppan Printing Co., Ltd.)

(Printability due to static electricity: mustache/misting)
The state of occurrence of beard and misting was evaluated.
A: Static electricity is not generated at all B: Static electricity is rarely generated C: Static electricity is slightly generated D: Significant static electricity is generated

(Adhesiveness)
Adhesion was evaluated from the ratio of the area where the ink film was peeled off from the adherend when the printed surface immediately after printing of the obtained printed matter was rubbed twice with the abdomen of the thumb and then cellophane tape was attached. ..
A: No peeling is possible B: Peeling area is less than 20% C: Peeling area is 20% or more

(Blocking resistance)
The printed surface of each film printed one day after printing each test ink and the untreated surface of each film were put together, left under a load of 15 kg/cm ² for 12 hours at 40° C., and then the films were peeled off. The blocking resistance was evaluated from the appearance of time.
A: There is no resistance when peeling the film, and the ink does not peel from the printed surface. B: There is resistance when peeling the film, but the ink does not peel from the printed surface. C: Resistance when peeling the film. And there is ink peeling from the printed surface

(Guide roll taken)
The slipperiness was evaluated by taking a guide roll.
After printing, a test was performed to determine whether ink adheres to the guide roll (taken out from the guide roll) by the following method to evaluate printability. The ink once adhered to the guide rolls is re-transferred to the printing surface and stains occur. Therefore, when the “guide roll is removed” occurs, it has an adverse effect on obtaining a cosmetic printed matter.
The presence or absence of falling of the ink coating film on the printed matter by the guide roll of the gravure printing machine was visually evaluated.
A: Nothing C: Yes

(Retort resistance)
One day after printing, each printed matter was coated with a urethane-based adhesive (Takelac A-616/Takenate A-65, manufactured by Mitsui Chemicals, Inc.) in an amount of 2.0 g/m ^{2 in} solid content, and then dry laminated. A non-stretched polypropylene film (RXC-3, thickness 60 μm, manufactured by Tohcello Co., Ltd.) was attached by a machine and left at 40° C. for 3 days to obtain a dry laminate. This dry laminated product is made into a bag, filled with a mixture of 90% by weight of water and 10% by weight of salad oil, sealed, and then pressed at 135°C for PET film and 120°C for films other than PET film. The retort resistance was evaluated based on whether or not the laminate film floated when immersed in hot water for 30 minutes.
A: No laminating float is seen at all B: Pinhole-shaped or thin lami float is seen in part -: The retort suitability test cannot be performed because the film itself used for printing does not have retort suitability

According to each of the above examples, the gravure printing ink composition for a film of the present invention has excellent storage stability, adhesiveness to various films, blocking resistance, and excellent retort resistance, and at the same time, occurrence of beard misting is reduced. It has a well-balanced characteristic that the guide roll is not removed.
On the other hand, according to Comparative Examples B1, B3 to 6 and Comparative Examples Y1 to 4, containing neither the alkyl imidazoline nor the compound represented by the general formula (1), or containing only a very small amount, The storage stability deteriorates and/or beard/misting occurs on the PET film.

Claims (12)

A gravure printing ink composition for a film, which comprises a pigment, a binder resin, and an organic solvent, and further comprises an alkyl imidazoline and/or a compound represented by the general formula (1) in a gravure printing ink composition for a film. A gravure printing ink composition for a film, which comprises -2.5% by mass.
(1)
_{(R 1:} a hydrocarbon group having 1 to 10 carbon _{atoms, R 2, R 3, R} 4: a hydrocarbon group having 2 to 10 carbon atoms, Y _{is, Cl, Br, R 5 OSO} 3, provided _{that, R} 5: A hydrocarbon group having 1 to 4 carbon atoms) The gravure printing ink composition for a film according to claim 1, wherein the binder resin contains a polyurethane resin having an amine value of 1 to 15 mgKOH/g. The gravure printing ink composition for a film according to claim 1, which is for lamination. The gravure printing ink composition for a film according to claim 1, wherein the binder resin contains a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer. The gravure printing ink composition for a film according to claim 1, wherein the gravure printing ink composition for a film contains at least one selected from an adhesion improver and an antiblocking agent. The gravure printing ink composition for a film according to claim 5, which contains an adhesion improver and an antiblocking agent. The adhesion improver is at least one selected from rosin and its derivatives, chlorinated polypropylene, and dammar resin, and the antiblocking agent is silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, cellulose acetate butyrate resin. The gravure printing ink composition for a film according to claim 5 or 6, which is at least one selected from nitrified cotton. The gravure printing ink composition for a film according to claim 1, wherein the organic solvent is a mixed solvent of an ester organic solvent and an alcohol organic solvent. The gravure printing ink composition for a film according to claim 1, which contains water. A printing method for printing on a plastic film using the gravure printing ink composition for a film according to claim 1 with a gravure printing machine. A printed matter obtained by the printing method according to claim 10. A laminate obtained by laminating the printed matter according to claim 11 and a base material via a laminating adhesive.