JP2021088669A - Gravure ink for lamination, printed matter, and laminate - Google Patents

Abstract

To provide a gravure or flexographic ink having excellent printability and sufficient adhesiveness to a substrate and lamination strength by use of a polyurethane resin having no urea bond unit derived from polyamine.SOLUTION: A gravure ink for lamination is provided, comprising a polyurethane resin, a binder resin comprising a vinyl chloride copolymer resin and/or a cellulosic resin, and an organic solvent. The gravure ink for lamination contains a polyurethane resin (A) having no urea bond derived from polyamine of 60 mass% or more in the total mass of the polyurethane resin. The organic solvent comprises an ester-based organic solvent; the organic solvent contains the ester-based organic solvent of 50 mass% or more in the total mass of the organic solvent; or when the organic solvent contains an aromatic organic solvent, the sum of the ester-based organic solvent and the aromatic organic solvent is 50 mass% or more in the total mass of the organic solvent.SELECTED DRAWING: None

Description

The present invention relates to a gravure ink for laminating, a printed matter having a printed layer made of the ink on the base material 1, and a laminated body obtained by further laminating the base material 2 on the printed matter having the printed matter.

More specifically, in printing on a film substrate such as a polyopropylene (OPP) film, a polyethylene terephthalate (PET) film, or a nylon (NY) film, printing such as plate fogability and fillet property (also referred to as transferability) is performed. The present invention relates to the above-mentioned gravure ink having excellent aptitude properties, and a printed matter and a laminate using the same.

In general, the ink used in the gravure printing method or the like is often composed of a polyurethane resin, a vinyl chloride copolymer resin, a cellulosic resin, or an organic solvent. Among the gravure inks, it is known that when a polyurethane urea resin having a urea binding unit derived from polyamine is used as a binder resin as a polyurethane resin, the adhesion to a film substrate and the lamination strength are improved (Patent Document 1). ).

In the above ink for laminating, it is often used as a laminate for food packaging, for example, the ink is printed on a base material, and further, the ink is printed on the printed layer via an adhesive / anchoring agent. Another base material can be bonded. Lamination strength is required for such a laminate. The polyurethane resin used requires a urea bond from the viewpoint of blocking resistance and laminate strength, and it is said that a polyamine-derived urea bond is required for the design of the polyurethane resin.

Attempts have been made to recover and reuse the organic solvent used for gravure ink from the viewpoint of resource reuse, but in general, when a polyurethane urea resin is used as a binder resin, the solubility of the polyurethane urea resin In order to secure it, it is necessary to use a certain amount of alcohol-based organic solvent, and to mix and use multiple types of organic solvents such as ester-based organic solvent and glycol-based organic solvent, which complicates the solvent composition. There is a problem that it is difficult to collect and reuse the solvent (Patent Document 2). Further, in order to maintain printability, it is necessary to devise a method for not changing the composition of the organic solvent in the ink (Patent Document 3).

In order to achieve good printability, it is necessary to print while maintaining the above-mentioned compounding composition (also referred to as mixed composition) of the organic solvent. For example, in the external environment, the temperature and humidity are particularly severe. It has been pointed out that under such conditions, differences in the volatilization rates of various solvents occur, the solvent composition in the gravure ink changes, and printability deteriorates.

Therefore, the problem of developing a gravure ink suitable for solvent recovery and reuse while ensuring stable printability and laminate strength for industrial use has not yet been solved.

JP-A-2017-199991 Japanese Unexamined Patent Publication No. 2008-266370 Japanese Unexamined Patent Publication No. 2016-094548

An object of the present invention is to provide a gravure ink which is excellent in printability, substrate adhesion and lamination strength, and which facilitates solvent recovery and reuse.

As a result of diligent studies in view of the above problems, the present inventors have found that the problem can be solved by using the gravure ink for lamination described below, and have come to the present invention.

The present invention is a binder resin containing a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulosic resin, and a gravure ink for lamination containing an organic solvent.
60% by mass or more of the polyurethane resin (A) having no urea bond derived from polyamine is contained in the total mass of the polyurethane resin.
When the organic solvent contains an ester-based organic solvent and the total mass of the organic solvent contains 50% by mass or more of the ester-based organic solvent, or when the organic solvent contains an aromatic organic solvent, the total mass of the organic solvent is ester-based. The present invention relates to a gravure ink for laminating in which the total amount of the organic solvent and the aromatic organic solvent is 50% by mass or more.

Further, in the present invention, the total mass of the organic solvent contains 70% by mass or more of the ester-based organic solvent, or when the total mass of the organic solvent contains an aromatic organic solvent, the total mass of the organic solvent contains the ester-based organic solvent and the aromatic. The present invention relates to the above-mentioned gravure ink for laminating, which has a total of 70% by mass or more with the organic solvent.

The present invention also relates to the above-mentioned gravure ink for laminating, wherein the polyurethane resin (A) contains a constituent unit derived from a polyester polyol and / or a polyether polyol.

The present invention also relates to the above-mentioned gravure ink for lamination, wherein at least one terminal group of the polyurethane resin (A) is an alkyl group and / or a hydroxyl group.

The present invention further relates to the above-mentioned gravure ink for lamination, which contains a chlorinated polyolefin resin.

The present invention also relates to a printed matter having a printed layer formed from the above-mentioned gravure ink for laminating on a base material 1.

The present invention also relates to a laminate having an adhesive layer and a base material 2 in this order on the printed layer of the printed matter.

INDUSTRIAL APPLICABILITY According to the present invention, the present invention has made it possible to provide a gravure ink which is excellent in printability, substrate adhesion and lamination strength, and which facilitates solvent recovery and reuse.

The embodiments of the present invention will be described in detail below with reference to examples, but the matters described below are examples or representative examples of the embodiments of the present invention, and the present invention includes these contents as long as the gist thereof is not exceeded. Not limited.

In the following description, the gravure ink for laminating may be simply referred to as "ink" or "gravure ink", but they are synonymous with each other. Further, the print layer formed by the gravure ink for laminating may be referred to as "ink film", which is synonymous.

The present invention is a gravure ink containing a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulose-based resin, and an organic solvent. “The polyurethane resin is a polyurethane resin (A) that does not have a urea bond derived from polyamine. ) Is contained in an amount of 60% or more ”,“ ester-based organic solvent and aromatic organic solvent ”, or“ ester-based organic solvent ”is used as the main component (50% by mass or more) to dilute with the same organic solvent. -Provides a gravure ink that can adjust the viscosity and does not use a complicated mixed solvent, so that there is no significant change in the solvent composition and stable printability is exhibited.

(Binder resin)
The gravure ink for lamination of the present invention contains a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulosic resin as a binder resin. The binder resin refers to the binder resin in the gravure ink of the present invention, and is preferably a thermoplastic resin soluble in an organic solvent.
As the binder resin, it is preferable to use a polyurethane resin having a glass transition temperature of −100 ° C. or higher and 0 ° C. or lower, and a vinyl chloride copolymer resin and / or a cellulosic resin having a glass transition temperature of 40 ° C. or higher and 200 ° C. or lower in combination. .. Further, it is preferable to use a polyurethane resin having a glass transition temperature of −80 ° C. to −10 ° C. and a vinyl chloride copolymer resin and / or a cellulosic resin having a glass transition temperature of 50 ° C. to 190 ° C. in combination. In the present specification, the glass transition temperature is a measured value by a differential scanning calorimeter (DSC).

The polyurethane resin preferably contains a total of 30 to 95% by mass of the polyurethane resin in the total amount of the binder resin. This is because the adhesiveness to the base material is good. The binder resin further contains a vinyl chloride copolymer resin and / or a cellulosic resin. In this case, the blocking resistance and the laminating strength are good.

Further, the total amount of the polyurethane resin, the vinyl chloride copolymer resin, and the cellulosic resin is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, in 100% by mass of the binder resin.
Further, the polyurethane resin / vinyl chloride copolymer resin and the polyurethane resin / cellulose-based resin represented by the mass ratio are preferably 95/5 to 30/70 in mass ratio, respectively. More preferably, the mass ratio is 90/10 to 40/60. This is because the blocking resistance and the laminating strength are good at this compounding ratio and combination.

<Polyurethane resin (A) that does not have a urea bond derived from polyamine>
The polyurethane resin contains 60% by mass or more of the polyurethane resin (A) having no urea bond derived from polyamine in 100% by mass of the polyurethane resin. The polyurethane resin (A) is preferably contained in an amount of 70% by mass, more preferably 80% by mass or more, and further preferably 90% by mass or more in 100% by mass of the polyurethane resin. By using the polyurethane resin (A) having no urea bond derived from polyamine, the resolubility is improved, the printability is improved, and the lamination strength is also improved.
The weight average molecular weight of the polyurethane resin (A) is preferably 10,000 to 100,000, and the glass transition temperature of the polyurethane resin (A) is preferably 0 ° C. or lower. It is still more preferably −100 ° C. to 0 ° C., and even more preferably −80 ° C. to −10 ° C. This is because the laminate strength is improved when used in combination with a vinyl chloride copolymer resin and / or a cellulosic resin.
"No polyamine-derived urea bond" is defined as having no urea bond due to the reaction of diamine, triamine or other polyamine with isocyanate, and the diamine is ethylenediamine, hexamethylenediamine or isophoronediamine. Examples of the triamine include iminobispropylamine and iminobisethylamine. However, the polyurethane resin (A) may contain a urea bond as a constituent unit derived from the reaction of monoamine and isocyanate.

The method for producing the polyurethane resin (A) is not particularly limited and is appropriately produced by a known method, but any polyurethane resin may be used as long as it is formed from at least a constituent unit derived from a polyol and a constituent unit derived from polyisocyanate. Above all, in order to improve the affinity with the mixed solvent composed of the ester-based organic solvent and the aromatic organic solvent or the ester-based organic solvent, and to improve the printability, the terminal group of the polyurethane resin is used. Is preferably a hydroxyl group and / or an alkyl group. Further, a monoamine may be used as long as it does not interfere with the affinity with the solvent. Examples of the production method include the methods described in JP-A-2017-19991.

(Polyol)
Preferable examples of the polyol include polyester polyol, polyether polyol, polylactone polyol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimer diol, hydrogenated dimer diol and the like. More preferably, it is a polyether polyol and / or a polyester polyol.

Examples of the polyether polyol include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, polytrimethylene glycol, and a polyether polyol which is a copolymer selected from these. The polyether polyol preferably has a number average molecular weight of 200 to 5,000. The number average molecular weight is calculated from the hydroxyl value with the terminal as a hydroxyl group, and is obtained by (Equation 1).
(Equation 1) Number of polyols Average molecular weight = 1000 x 56.1 x hydroxyl valence / hydroxyl value

Examples of the polyester polyol include a condensate obtained by an esterification reaction of a polybasic acid and a diol.
The polybasic acid is preferably a dibasic acid, and the dibasic acid is adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, and pimerin. Examples thereof include acids, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1,4-cyclohexyldicarboxylic acid, dimer acid, hydrogenated dimer acid and the like.
Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octanediol. , 1,9-Nonandiol, Neopentyl glycol, 3-Methyl-1,5-Pentanediol, 2-Methyl-1,3-Propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl- 1,5-Pentanediol, 1,12-Octadecanediol, 1,2-Alkanediol, 1,3-Alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimerdiol , Hydrophobic dimerdiol and the like.

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

The number average molecular weight of the polyester polyol is preferably 200 to 5,000. The number average molecular weight can be obtained by the above formula (Equation 1).

(Polyisocyanate)
Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates generally used in the production of polyurethane resins. These may be trimers and have an isocyanurate ring structure.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, and tetraalkyl. Examples thereof include diphenylmethane diisocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, and tolylene diisocyanate.
Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexanediisocyanate, and norbornan diisocyanate. , M-Tetramethylxylylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, dimerized isocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group, and the like.
Among them, preferably at least one selected from a trimer of 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, and hexamethylene diisocyanate. is there. These polyisocyanates can be used alone or in admixture of two or more.

(Alkyl group as terminal group, hydroxyl group)
The terminal group in the polyurethane resin (A) is, for example, if the structure of the polyurethane resin (A) is a linear structure, both ends of the linear structure are referred to as terminal groups, and the structure of the polyurethane resin (A) is a branched structure. If so, the end part including the end of the branch is also called the terminal group.
The terminal group is preferably an alkyl group and / or a hydroxyl group, and when it has a hydroxyl group, the hydroxyl value of the polyurethane resin (A) is preferably 0.1 to 35 mgKOH / g, and 0.5 to 20 mgKOH / g. It is still more preferable to be g. When it has an alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Preferable examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group and the like.

In order to introduce a hydroxyl group or an alkyl group as the terminal group of the polyurethane resin (A), a method of reacting the polyol with a polyisocyanate and then using a hydroxyl group or a polymerization terminator having an alkyl group can be mentioned. For example, a polyol and a polyisocyanate are reacted at a temperature of 50 ° C. to 150 ° C. using a solvent inert to the isocyanate group as needed, and further using a urethanization catalyst if necessary (urethaneization reaction), and the terminals are terminally prepared. A prepolymer having an isocyanate group is produced in, and then a polymerization terminator having a hydroxyl group and an alkyl group is reacted with the prepolymer in one step to obtain a polyurethane resin (A) by a known method such as a one-shot method. Can be done.
In order to introduce a hydroxyl group as a terminal group, for example, a diol such as ethylene glycol, propylene glycol, 1,3-propanediol or 1,4-butanediol, or a primary or secondary amino group such as 2-ethanolamine. A method of using a monoalcohol amine compound having a hydroxyl group as a polymerization terminator having a hydroxyl group, or a method of obtaining a polyurethane resin (A) having a hydroxyl group at the terminal by carrying out the urethanization reaction in excess of the hydroxyl value of the polyol is preferably mentioned. Be done.
In order to introduce an alkyl group as a terminal group, a monohydric alcohol such as ethanol, propanol or isopropanol is used as a polymerization terminator having an alkyl group, or a compound having a monovalent amino group such as di-n-butylamine is used. The method to be used is preferably mentioned.

In producing the urethane prepolymer having an isocyanate group at the terminal, the amount of the polyol and the polyisocyanate is the ratio of the number of moles of the isocyanate group of the polyisocyanate to the number of moles of the total hydroxyl group of the high molecular weight polyol, NCO /. It is preferable that the OH ratio is in the range of 1.05 to 3.0. More preferably, the NCO / OH ratio is 1.1 to 2.0.

Further, it is preferable to use an organic solvent for the synthesis of the prepolymer from the viewpoint of reaction control. An organic solvent having a composition similar to that of the organic solvent used as the ink is preferable. A mixed solvent composed of an ester-based organic solvent and an aromatic organic solvent, an ester-based organic solvent, or the like is preferable. As another organic solvent that can be used, an organic solvent that is inactive in reacting with an isocyanate group is preferable. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatics such as toluene and xylene. Group hydrocarbons; Examples thereof include esters such as ethyl acetate and butyl acetate. These can be used alone or in combination of two or more as a mixed solvent.

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

<Vinyl chloride copolymer resin>
The vinyl chloride copolymer resin is not particularly limited as long as it contains a structural unit derived from vinyl chloride and a structural unit derived from other monomers. Of these, vinyl chloride-vinyl acetate copolymer resin and vinyl chloride-acrylic copolymer resin are preferable.

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin is a copolymer of vinyl chloride and vinyl acetate, and the molecular weight is preferably 5,000 to 100,000 with a weight average molecular weight of 20,000 to 70,000. Is more preferable. The structure derived from the vinyl acetate monomer in 100% by mass of the solid content of the vinyl chloride-vinyl acetate copolymer is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. .. In this case, the solubility in an organic solvent is improved, and the adhesion to the substrate, the physical characteristics of the film, the lamination strength and the like are improved.
Further, in order to improve the solubility in an organic solvent, those containing a hydroxyl group derived from vinyl alcohol by a saponification reaction or copolymerization are more preferable, and the hydroxyl value is preferably 20 to 200 mgKOH / g. The glass transition temperature is preferably 50 ° C to 90 ° C.

<Vinyl chloride-acrylic copolymer resin>
The vinyl chloride-acrylic copolymer resin is mainly composed of a copolymer resin of a vinyl chloride monomer and an acrylic monomer, and the acrylic monomer has improved adhesiveness to a base material and solubility in an organic solvent (meth). ) It is preferable to contain an acrylic acid hydroxyalkyl ester. The acrylic monomer may be blocked or randomly incorporated into the main chain of polyvinyl chloride, or may be graft-polymerized on the side chain of polyvinyl chloride. The vinyl chloride-acrylic copolymer resin preferably has a weight average molecular weight of 10,000 to 100,000, and more preferably 30,000 to 70,000. The hydroxyl value is preferably 20 to 200 mgKOH / g, and the glass transition temperature is preferably 50 ° C to 90 ° C.

The structure derived from the vinyl chloride monomer in the vinyl chloride-acrylic copolymer resin is preferably 70 to 95% by mass based on 100% by mass of the vinyl chloride-acrylic copolymer resin solid content. In this case, the solubility in an organic solvent is improved, and the adhesion to the substrate, the physical characteristics of the film, the lamination strength and the like are improved.

In the following description, (meth) acrylic or (meth) acrylate means methacrylic and acrylic, methacrylate and acrylate, respectively.

The acrylic monomer preferably has a hydroxyl group, and examples thereof include 2-hydroxyethyl (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, 3-hydroxypropyl (meth) acrylic acid, and 2 (meth) acrylic acid. -Hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate and other (meth) acrylic acids Glycol mono (meth) acrylates such as hydroxyalkyl esters, polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, 1,4-cyclohexanedimethanol mono (meth) acrylates, caprolactone-modified (meth) acrylates, hydroxy Examples include ethyl acrylamide. Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are more preferable because they improve the solubility in a solvent. These can be used alone or in combination of two or more. Acrylic monomers other than the above may be contained at any time.

<Cellulose resin>
Examples of the cellulose-based resin include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose and the like, and the above alkyl groups include, for example, methyl group, ethyl group, propyl group and isopropyl group. Examples thereof include a butyl group, an isobutyl group, a pentyl group, a hexyl group and the like, and an alkyl group may further have a substituent. Of these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable. The molecular weight preferably has a weight average molecular weight of 5,000 to 1,000,000, and more preferably 10,000 to 200,000. Further, it is preferable that the glass transition temperature is 100 ° C. to 160 ° C.

(Nitrocellulose)
Nitrocellulose is preferably obtained as a nitrate ester obtained by reacting natural cellulose with nitric acid and substituting three hydroxyl groups in the 6-membered ring of the anhydrous glucopyranose group in the natural cellulose with a nitric acid group, and the weight average is sufficient. The molecular weight is preferably 10,000 to 100,000, and even more preferably 10,000 to 80,000. This is preferable because the strength of the ink film is improved, the solubility in a solvent, the low temperature stability of the ink, and the compatibility with the combined resin are improved. The nitrogen content is preferably 10.5-12.5% by mass.

<Other binder resins>
As the binder resin, a resin other than the polyurethane resin containing the polyurethane resin (A), the vinyl chloride copolymer resin, and the cellulose-based resin may be used in combination as long as it has binder performance. For example, a polyolefin resin and chlorine may be used in combination. Polyolefin resin, ethylene-vinyl acetate copolymer resin, polyester resin, acrylic resin, polyamide resin, urethane-acrylic resin, styrene resin, styrene-acrylic acid resin, styrene-maleic acid resin, maleic anhydride resin, maleic acid resin, Vinyl acetate resin, rosin resin, rosin-modified maleic acid resin, cycloolefin resin, alkyd resin, polyvinyl chloride resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, rubber chloride, butyral, petroleum resin, silicone resin And these modified resins and the like. These resins can be used alone or in combination of two or more, and the content thereof is preferably 0 to 30% by mass, preferably 0 to 15% by mass, based on 100% by mass of the solid content of the binder resin. % Is more preferable. The binder resin does not contain a chlorinated polyolefin resin.

<Chlorinated polyolefin resin>
The ink in the present invention preferably contains a chlorinated olefin resin. The chlorinated olefin resin preferably has a chlorine content of 25 to 45% by mass, more preferably 26 to 40% by mass, because the adhesiveness to the easy-adhesion-treated substrate and the lamination strength are improved. Here, the chlorine content in the present invention means the content mass% of chlorine atoms in 100% by mass of the chlorinated polyolefin resin. Further, from the viewpoint of solubility in a mixed solvent such as an ester solvent / alcohol solvent, the weight average molecular weight of the chlorinated polyolefin in the present invention is preferably 5,000 to 80,000, preferably 10,000 to 80,000. It is still more preferable to be 50,000. Further, from the viewpoint of the balance with the blocking resistance, the chlorinated olefin resin is preferably contained in an amount of 0.05 to 2% by mass in 100% by mass of the ink. More preferably, it is 0.1 to 1.0% by mass.
In the present invention, the chlorinated polyolefin resin has a structure in which hydrogen of the polymer of α-olefin represented by the following general formula (2) is substituted with chlorine.
General formula (2)

CH ₂ = CH-R ³

(In the formula, R ³ is an alkyl group having 1 or more carbon atoms.)
Since the chlorinated polyolefin resin has a flexible alkyl group as a branched structure, it is in a viscous state even at a low temperature, and the substrate adhesiveness is improved by the above use. The polyolefin structure of the chlorinated polyolefin resin is not particularly limited. For example, resins containing homopolymers or copolymers of α-olefin unsaturated hydrocarbons such as polypropylene, poly-1-butene, and poly-4-methyl-1-pentene are preferable. Among them, those containing a polypropylene structure (that is, a chlorinated polypropylene structure) are particularly preferable. When the chlorinated polyolefin resin is used in combination with a polyurethane resin that does not have a polyurea-derived structural unit, excellent substrate adhesion and lamination strength can be obtained.

<Organic solvent>
The gravure ink of the present invention contains an organic solvent, and 50% by mass of either a mixed solvent composed of an ester-based organic solvent and an aromatic organic solvent or an ester-based organic solvent is contained in 100% by mass of the organic solvent. Contains the above. The content of the organic solvent in 100% by mass is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. As the aromatic organic solvent, toluene, xylene and the like are preferable, and as the ester organic solvent, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate and the like are preferable. In consideration of the environment, it is preferable to use an ester-based organic solvent in order to obtain a non-toluene-based organic solvent that does not contain an aromatic organic solvent.

"50% by mass or more of either the ester-based organic solvent and the aromatic organic solvent or the ester-based organic solvent" means "50% by mass of the mixed solvent of the ester-based organic solvent and the aromatic organic solvent". It means either "% or more" or "50% by mass or more of ester-based organic solvent", and the former requires that both ester-based organic solvent and aromatic organic solvent are contained, in which case. Is treated as "a mixed solvent of an ester-based organic solvent and an aromatic organic solvent". On the other hand, the latter "50% by mass or more of the ester-based organic solvent" does not include the case where the aromatic organic solvent is contained.

(Mixed solvent composed of ester-based organic solvent and aromatic-based organic solvent)
The mixed mass ratio of the ester-based organic solvent and the aromatic-based organic solvent (ester-based organic solvent: aromatic-based organic solvent) is preferably 10:90 to 90:10, preferably 20:80 to 80:20. It is still more preferable, and more preferably 30:70 to 70:30.

(Ester-based organic solvent)
As the ester-based organic solvent, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate and the like are preferable, and ethyl acetate and / or n-propyl acetate is more preferable.

(Other organic solvents)
The organic solvent may contain a mixed solvent composed of an ester-based organic solvent and an aromatic organic solvent, or an organic solvent other than the ester-based organic solvent. For example, a ketone-based organic solvent such as methyl ethyl ketone or methyl isobutyl ketone, or methanol may be contained. , Ethanol, n-propanol, isopropanol, n-butanol and other alcohol-based organic solvents (excluding the glycol ether-based organic solvents described below), ethylene glycol monopropyl ether, propylene glycol monomethyl ether and other glycol ether-based organic solvents, etc. A known organic solvent can be used. In order to improve printability, it is preferable to contain a glycol ether-based organic solvent in an amount of 30% by mass or less in 100% by mass of the organic solvent. Further, in 100% by mass of the organic solvent, the alcohol-based organic solvent (excluding the glycol ether-based organic solvent) is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less. Is more preferable.
The gravure ink of the present invention may contain water as a liquid medium, but the content thereof is preferably 0.1 to 5% by mass in 100% by mass of the liquid medium.

(Pigment)
The gravure ink of the present invention preferably contains a pigment, and preferably contains 0.2 to 60% by mass based on 100% by mass of the gravure ink. The pigment can be any of an organic pigment, an inorganic pigment, and an extender pigment, but the inorganic pigment contains titanium oxide, and the extender pigment includes silica, barium sulfate, kaolin, clay, calcium carbonate, and carbon dioxide. Magnesium and the like are preferred. As the organic pigment, it is preferable to use one composed of an organic compound and an organic metal complex.

(Organic pigment)
The organic pigments are not limited to the following examples, but are soluble azo type, insoluble azo type, azo type, phthalocyanine type, halogenated phthalocyanine type, anthraquinone type, anthraquinone type, dianslaquinonyl type, and anthrapyrimidine type. , Perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethinazo, flavanthron, diketopyrrolopyrrole, isoindoline, indanslon, carbon black, etc. Pigments can be mentioned.

As the hue of the organic pigment, at least one selected from the group consisting of black pigment, indigo pigment, green pigment, red pigment, purple pigment, yellow pigment, orange pigment and brown pigment is preferable. Furthermore, at least one or more selected from the group consisting of black pigments, indigo pigments, red pigments, and yellow pigments is preferable. Specific examples of organic pigments include C.I. of Color Index International (abbreviated as CI). I. Shown by number.
Preferably C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 146, C.I. I. Pigment Red 242, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 14, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 13, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 139, C.I. I. Pigment Red 185, C.I. I. Pigment Red 122, C.I. I. Pigment Red 178, C.I. I. Pigment Red 149, C.I. I. Pigment Red 144, C.I. I. Pigment Red 166, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 37, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Green 7, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 64, C.I. I. Pigment Black 7, preferably one or more.

Inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, aluminum particles, mica (mica), bronze powder, chromium vermilion, chrome yellow, cadmium yellow, cadmium red, and ultramarine. , Navy blue, red iron oxide, yellow iron oxide, iron black, etc., and aluminum has a leafing type or a non-leaving type, but the non-leaving type is preferable.

<Titanium oxide pigment>
In the present invention, the titanium oxide pigment may have a crystal structure of any of anatase type, rutile type and brookite type. Of these, rutile-type titanium oxide is preferably used because it has good pigment dispersibility. In the industrial production of titanium oxide, rutile ore or ilmenite ore (FeTIO3) is used as a raw material. There are two main manufacturing methods, the chlorine method and the sulfuric acid method, and any manufacturing method may be used.
Further, the titanium oxide pigment is preferably surface-treated in order to improve printability in gravure printing. In particular, those surface-treated with at least one metal selected from Si, Al, Zn, Zr and their oxides are preferable.

Further, the oil absorption amount according to the measurement method specified in JIS K5101 is preferably 14 to 35 ml / 100 g, and more preferably 17 to 32 ml / 100 g. Further, the average particle size (median particle size) measured by a transmission electron microscope is preferably 0.2 to 0.3 μm. The total content of the titanium oxide pigment is preferably 10 to 60% by weight, more preferably 10 to 45% by weight, based on 100% by weight of the ink. Further, a plurality of types of titanium oxide pigments may be used in combination.
In the gravure ink of the present invention, in addition to the titanium oxide pigment, other inorganic pigments and organic pigments can be further used in combination.

<Additives>
The gravure ink of the present invention can appropriately contain conventionally known additives, and in the production of ink compositions, additives such as pigment derivatives, dispersants, wetting agents, adhesive aids, and leveling are required. Agents, antifoaming agents, antistatic agents, viscosity modifiers, chelate cross-linking agents, trapping agents, blocking inhibitors, wax components other than the above, isocyanate-based curing agents, silane coupling agents and the like can be used.

(Isocyanate-based curing agent)
As the isocyanate-based curing agent, polyisocyanate and modified compounds thereof can be used. Specifically, biuret, isocyanurate, and adduct bodies of polyisocyanate are preferable, and diisocyanate is preferable as the polyisocyanate, and aromatic diisocyanates such as tolylene diisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, and the like are preferable. Aliphatic diisocyanates such as alicyclic diisocyanate and hexamethylene diisocyanate, and aromatic aliphatic diisocyanates such as α, α, α', α'-tetramethylxylylene diisocyanate can be used. Specific commercially available products include 24A-100, 22A-75, TPA-100, TSA-100, TSS-100, TAE-100, TKA-100, P301-75E, E402-808, E405-70B, AE700. -100, D101, D201, A201H (Asahi Kasei), Mitec Y260A (Mitsubishi Chemical), Coronate CORONATE HX, Coronate CORONATE HL, Coronate CORONATE L (Nippon Polyurethane Industry), Desmodur N75MPA / X (Bayer) ) Etc. can be exemplified. Of these, isophorone diisocyanate and the adduct and / or isocyanurate form of isophorone diisocyanate are preferable.

(Pigment dispersant)
A pigment dispersant can also be used in combination to stably disperse the pigment. As the pigment dispersant, surfactants such as anionic, nonionic, cationic and amphoteric can be used. From the viewpoint of storage stability of the ink, the dispersant is preferably contained in the ink in an amount of 0.1 to 10.0% by mass with respect to 100% by mass of the total mass of the ink. Further, it is more preferably contained in the range of 0.1 to 3.0% by mass.

<Manufacturing of gravure ink>
The gravure ink of the present invention can be produced by dissolving and / or dispersing a polyurethane resin (A), a vinyl chloride copolymer resin and / or a cellulosic resin and a pigment in an organic solvent. Specifically, for example, an organic pigment, a polyurethane resin (A), a vinyl chloride copolymer resin, and, if necessary, the above pigment dispersant were mixed to produce a pigment dispersion dispersed in an organic solvent. A gravure ink can be produced by further adding a polyurethane resin, water, or if necessary, another resin, additives, or the like to the pigment dispersion. Further, as the particle size distribution of the pigment dispersion, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill, a gamma mill, or the like, which are generally used as a disperser, can be used. Above all, production by a bead mill disperser such as a sand mill is preferable. It can be produced by appropriately adjusting the type and size of beads of the bead mill disperser, the filling rate of beads, the dispersion treatment time, the viscosity, and the like.

If the ink contains air bubbles or unexpectedly coarse particles, it is preferable to remove them by filtration or the like in order to deteriorate the quality of the printed matter. As the filter, a conventionally known one can be used.

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

<Gravure printing>
(Gravure version)
In the above gravure printing, the gravure plate is a metal cylindrical one, and recesses are created in each color by engraving, corrosion, or laser. There are no restrictions on the use of engraving and laser, and it can be set arbitrarily according to the pattern. As the number of lines, those having 150 to 350 lines are appropriately used, and the larger the number of lines, the finer the printing is possible. The thickness of the print layer is preferably 0.1 μm to 100 μm.
(Printer)
In a gravure printing machine, one printing unit includes the above gravure plate and a doctor blade. There are many printing units, and printing units corresponding to organic solvent-based gravure or flexographic ink and pattern ink can be set, and each unit has an oven drying unit. Printing is performed by rotary printing, which is a take-up printing method. The type of plate and the type of doctor blade are appropriately selected, and the one according to the specifications can be selected.

<Base material 1>
The substrate 1 has a wetting index of 30 to 60 din / cm on the surface to be printed (the surface in contact with the printing layer). It is more preferably 35 to 55 dyne / cm. The wettability index is a value measured by the method described in JIS K6768 using a wettability index standard solution.
The base material 1 that can be used in the printed matter of the present invention includes, for example, polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polycarbonate, polyesters such as polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, and poly. Examples thereof include a film-like substrate made of vinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or a composite material thereof. Further, a vapor-deposited base material obtained by depositing an inorganic compound such as silica, alumina, or aluminum on a polyethylene terephthalate or nylon film can also be used, and the vapor-deposited surface may be coated with polyvinyl alcohol or the like.
The base material 1 is preferably easily adhered so that the wettability index of the surface in contact with the printing layer is within the above range. Examples of the easy-adhesion treatment include corona discharge treatment, ultraviolet / ozone treatment, plasma treatment, oxygen plasma treatment, primer treatment and the like. For example, in the corona discharge treatment, a hydroxyl group, a carboxyl group, a carbonyl group and the like are expressed on the substrate. Since hydrogen bonds can be used, it is preferable that the ink contains a compound having a functional group such as a hydroxyl group or an amino group.

<Base material 2>
Examples of the base material 2 include the same ones as the base material 1, and may be the same or different. Of these, unstretched polyethylene, unstretched polypropylene, nylon base material, aluminum foil base material, aluminum-deposited base material, and the like are preferable.

<Laminated body>
In the laminate of the present invention, a film layer is further bonded to the printed layer of the printed matter in order. The laminated body is preferably a laminated body including an adhesive layer, and is preferably a laminated body having a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order. Examples of the adhesive layer include a layer made of an anchor coating agent, a urethane-based laminated adhesive, a molten resin, and the like. Examples of the anchor coating agent (AC agent) include imine-based AC agent, isocyanate-based AC agent, polybutadiene-based AC agent, and titanium-based AC agent, and examples of urethane-based laminate adhesive include polyether urethane-based laminate adhesive and polyester-based laminate. Examples include adhesives, and there are those containing an organic solvent and those without a solvent. Further, examples of the molten resin include molten polyethylene and the like.
As a method for producing a laminate, for example, a normal extrusion laminate (extruded laminate) in which a molten polyethylene resin is laminated on a printed layer via various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium. ) Method, dry laminating method or non-solvent laminating method in which a urethane-based adhesive is applied to the printed surface and a plastic film is laminated on it, or direct laminating method in which molten polypropylene is directly pressure-bonded and laminated on the printed surface. Etc., obtained by a known laminating process.

Hereinafter, the present invention will be described in detail with reference to examples, but the following embodiments are only examples of the present invention, and the present invention is not limited to these examples. Unless otherwise specified, parts and% in the present invention represent parts by mass and% by mass.

(Acid value and hydroxyl value)
The measurement was performed according to the method described in JIS K0070.

(Weight average molecular weight)
The weight average molecular weight was determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation) and using polystyrene as a standard substance as a converted molecular weight. The measurement conditions are shown below.
Column: The following columns were connected in series and used.
TSKgel SuperAW2500 manufactured by Tosoh Corporation
TSKgel SuperAW3000 manufactured by Tosoh Corporation
TSKgel SuperAW4000 manufactured by Tosoh Corporation
TSKgel guardcolum SuperAWH manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min

[Synthesis Example 1] (Synthesis of Polyurethane Resin P1)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, polyester polyol A (3-methyl-1,3-propanediol and adipic acid condensate "MPO / AA") is used. 278.8 parts of a certain number average molecular weight 2,000 polyester polyol), 21.2 parts of tolylene diisocyanate (hereinafter abbreviated as "TDI"), and 670 parts of ethyl acetate were charged and reacted at 70 ° C. for 6 hours under a nitrogen stream. Then, 30 parts of isocyanate (hereinafter abbreviated as “IPA”) was added and cooled to obtain a polyurethane resin P1 solution having a mass average molecular weight of 30,000 and a hydroxyl value of 4 mgKOH / g and a solid content of 30.0 mass%.

[Synthesis Examples 2 to 7] (Synthesis of Polyurethane Resins P2 to P7)
Polyurethane resins P2 to P6 were obtained in the same manner as in Synthesis Example 1 except that the raw materials and usage ratios shown in Table 1 were used. The abbreviations in Table 1 are as follows.
PPG: Polypropylene Glycol MDI: 4,4'-Diphenylmethane Diisocyanate IPDI: Isophorone Diisocyanate 2EtAm: 2-Ethanolamine DEAE: 2-Diethylaminoethanol

[Comparative Synthesis Example 1] (Synthesis of Polyurethane Resin PP1)
213 parts of MPO / AA with a number average molecular weight of 2000, 22.3 parts of PPG with a number of molecular weight of 400, 53.4 parts of MDI, ethyl acetate in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube. 180 parts were charged and reacted at 90 ° C. for 4 hours under a nitrogen stream to obtain a solution of the terminal isocyanate prepolymer. Next, a mixture of 9.8 parts of isophorone diamine (hereinafter also abbreviated as "IPDA"), 0.2 parts of 2-hydroxyethylethylenediamine (hereinafter also abbreviated as "AEA"), 1.3 parts of 2EtAm, 245 parts of ethyl acetate and 275 parts of IPA. The obtained solution of the terminal isocyanate prepolymer was gradually added at room temperature, and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin PP1 solution having a mass average molecular weight of 36,000 and a solid content of 30.0% by mass. It was.

[Comparative Synthesis Example 2] (Synthesis of Polyurethane Resin PP2)
Polyurethane resin PP2 was obtained in the same manner as in Comparative Synthesis Example 1 except that the raw materials and usage ratios shown in Table 1 were used. The abbreviations in Table 1 are as follows.
PPA: Polyester polyol, a condensate of adipic acid and 1,2-propanediol

[Example 1] (Manufacturing of gravure ink I1)
10 parts of phthalocyanine indigo pigment (Lionol blue FG-7358-G CI Pigment Blue 15: 4 manufactured by Toyo Color Co., Ltd.), vinyl chloride vinyl acetate copolymer resin (solvine ALLP: vinyl chloride manufactured by Nissin Chemical Industry Co., Ltd.) / Vinyl acetate / Vinyl alcohol = 92/1/7 (mass ratio) copolymer resin, solid content 25% ethyl acetate solution) 17.2 parts, ethyl acetate 20.3 parts, chlorinated polypropylene resin (Nippon Paper Co., Ltd.) Supercron 370M Chlorine content 29% by mass, weight average molecular weight 30,000 solid content 50%) 0.6 parts are stirred and mixed, pigment-dispersed with a bead mill (using zirconia beads), and then polyurethane resin solution PU1 (solid). 30 parts) and 22 parts of ethyl acetate were stirred and mixed to obtain gravure ink I1.

[Examples 2 to 17] (Production of inks I2 to I17)
Gravure inks I2 to I17 were obtained in the same manner as in Example 1 except that the raw materials and usage ratios shown in Table 2 were used. The numerical values in the table represent the total value of each component, and the names in the table represent the following.
DLX5-8: Nitrocellulose resin ICI Novell enterprises Nitrogen content 12.0% (solid content 30% isopropanol solution)
JR403: Titanium oxide Lionol Red 6B FG4306G manufactured by TAYCA Corporation: Soluble azo pigment C.I. I. Pigment Red 57: 1

[Comparative Examples 1 to 6] (Manufacturing of inks T1 to T6)
Gravure inks T1 to T6 were obtained in the same manner as in Example 1 except that the raw materials and usage ratios shown in Table 2 were used.

[Creation of printed matter using ink I1]
The viscosity of the gravure ink I1 was adjusted by diluting the viscosity of Zahn Cup # 3 (manufactured by Rigo Co., Ltd.) with ethyl acetate to 16.0 seconds (at 25 ° C.), and the gravure calibrator equipped with a plate depth of 30 μm gravure plate Printed matter was printed on the corona discharge-treated surfaces of FOR-BT # 20 and E5100 # 15, which are plastic substrates, and dried at 40 to 50 ° C. to obtain printed matter using gravure ink I1.
The base materials FOR-BT # 20 and E5100 # 15 represent the following.
-FOR-BT # 20: Double-sided corona discharge-treated polypropylene (OPP) film manufactured by Futamura Chemical Co., Ltd. Film thickness 20 μm
E-5100 # 15: Single-sided corona discharge-treated polyester (PET) film manufactured by Toyobo Co., Ltd. Film thickness 15 μm

[Creation of printed matter using gravure inks I2 to I17 and gravure inks T1 to T6]
Gravure inks I2 to I17 (Examples) and gravure inks T1 to T6 (Comparative examples) are applied in the same manner as in the example of printed matter using ink I1 except that gravure inks I2 to I17 and gravure inks T1 to T6 are used. The printed matter used was obtained respectively.

[Creation of laminate using gravure ink I1]
For printed matter using ink I1, further add a polyether urethane-based laminate adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.) as an ethyl acetate solution having a solid content of 25% by weight and 10% by weight so as to be 1.5 g / m2. The printed surface was coated and dried, and laminated with aluminum-deposited unstretched polypropylene (VMCP2203, film thickness 25 μm, manufactured by Toray Film Processing Co., Ltd.) for dry laminating.

[Preparation of laminate using gravure inks I2 to I17 and laminate using gravure inks T1 to T6]
Gravure inks I2 to I17 (Examples) and gravure inks T1 to T6 (Comparative examples) in the same manner as in the example of the laminate using the ink I1 except that the gravure inks I2 to I17 and the gravure inks T1 to T4 were used. Each of the laminates using the above was obtained.

[Characteristic evaluation]
The characteristics of the gravure inks I1 to I17 (Examples) and the gravure inks T1 to T6 (Comparative Examples) obtained in the above Examples and Comparative Examples, and the printed matter and laminate using them were evaluated as described below. The evaluation results are shown in Table 3. In the table, "* Ink condition is inferior" means that the ink gelled or significantly thickened and the condition was poor, and evaluation was impossible.

<Adhesion>
Printed matter using gravure inks I1 to I17 and gravure inks T1 to T6 were left at 25 ° C. for 1 day, and then an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) with a width of 12 mm was attached to the printed surface, and this was applied to the base material surface. The state of the appearance of the printed surface when the printed surface was rapidly peeled off in the 90 ° direction was visually determined. The judgment criteria were as follows.
[Evaluation criteria]
5. The ink film on the printed surface does not peel off at all (good)
4. The peeled area of the ink film is 1% or more and less than 5% (practical)
3. 3. The peeled area of the ink film is 5% or more and less than 20% (slightly defective)
2. The peeled area of the ink film is 20% or more and less than 50% (defective)
1. 1. Ink film peels off by 50% or more (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

<Laminate strength>
For the laminate using gravure inks I1 to I17 and the laminate using gravure inks T1 to T6, the printed portion is cut to a width of 15 mm and peeled off on the ink surface and the base material surface, and then the peel strength (laminate strength). ) Was measured with a 2.01 universal tensile tester manufactured by Intesco.
[Evaluation criteria]
5. Tensile strength is 1.0N / 15mm or more (good)
4. Tensile strength is less than 0.6N / 15mm and 1.0N / 15mm (practical)
3. 3. Tensile strength is less than 0.4N / 15mm and 0.6N / 15mm (slightly defective)
2. Tensile strength is less than 0.2N / 15mm and 0.4N / 15mm (defective)
1. 1. Tensile strength is less than 0.2N / 15mm (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

<Printability (meatability)>
With respect to the printed matter using the gravure inks I1 to I17 and the gravure inks T1 to T6, the inking property was evaluated by the retention rate% of the transferred area of the ink in the gradation 5% portion. The retention rate% is a value represented by "transition area at the end of printing x 100 / transition area at the start of printing", and the printability test is performed at an ambient temperature of 30 ° C., a printing speed of 200 m / min, and a printing time of 60 minutes. It was done in.
[Evaluation criteria]
5. Ink transfer retention rate is 100% (good)
4. Ink transfer retention rate is 80% or more and less than 100% (practical)
3. 3. Ink transfer retention rate is 60% or more and less than 80% (slightly defective)
2. Ink transfer retention rate is 30% or more and less than 60% (defective)
1. 1. Ink transfer retention rate is less than 30% (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

<Printability (plate fogability)>
The plate fogability was evaluated for the gravure inks I1 to I17 and the gravure inks T1 to T6. The diluting solvent was ethyl acetate, the viscosity was set to 16 seconds (25 ° C) with Zahn Cup # 3, the environmental temperature was 30 ° C, the printing speed was 200 m / min, and the plate cover portion was 90 minutes after the plate was idled in the printing machine. The area of the above was visually judged and evaluated.
[Evaluation criteria]
5. Plate covering area is 0% or more and less than 5% (good)
4. The plate covering area is 5% or more and less than 10% (practical)
3. 3. Plate covering area is 10% or more and less than 15% (slightly defective)
2. Plate covering area is 15% or more and less than 30% (defective)
1. 1. The plate cover area is 30% or more (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

<Ink stability>
Gravure inks I1 to I17 and gravure inks T1 to T6 were stored at 50 ° C. for 10 days. Then, the viscosity was measured to evaluate the change in viscosity from that before storage. The viscosity was measured at 25 ° C. It was performed in 4 outflow seconds.
[Evaluation criteria]
5. Viscosity change less than 2 seconds (good)
4. Viscosity difference is 2 seconds or more and less than 5 seconds (practical)
3. 3. Viscosity difference is 5 seconds or more and less than 10 seconds (slightly defective)
2. Viscosity difference is 10 seconds or more and less than 15 seconds (defective)
1. 1. Viscosity difference is 15 seconds or more (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

From the above results, the problem could be achieved by using the gravure or flexo ink of the present invention. When the polyurethane resin (A) having no urea bond derived from polyamine is contained and the organic solvent contains either a mixed solvent of an ester-based organic solvent and an aromatic organic solvent or an ester-based organic solvent. Special effects are obtained in printability and laminate strength, whereas either property is achieved when the polyurethane urea resin has a polyamine-derived urea bond, which is a comparative example, or when the polyurethane resin is not contained. It was not possible and it was shown that the invention described in the present application satisfies the characteristics. Further, since the composition of the organic solvent contained in the gravure ink of the present invention is not complicated, it is advantageous for recovering and reusing the organic solvent.

Claims (7)

A binder resin containing a polyurethane resin, a vinyl chloride copolymer resin and / or a cellulosic resin, and a gravure ink for laminating containing an organic solvent.
60% by mass or more of the polyurethane resin (A) having no urea bond derived from polyamine is contained in the total mass of the polyurethane resin.
When the organic solvent contains an ester-based organic solvent and the total mass of the organic solvent contains 50% by mass or more of the ester-based organic solvent, or when the organic solvent contains an aromatic organic solvent, the total mass of the organic solvent is ester-based. A gravure ink for laminating in which the total amount of the organic solvent and the aromatic organic solvent is 50% by mass or more. If the total mass of the organic solvent contains 70% by mass or more of the ester-based organic solvent, or if the total mass of the organic solvent contains an aromatic organic solvent, the total of the ester-based organic solvent and the aromatic organic solvent is included in the total mass of the organic solvent. The gravure ink for laminating according to claim 1, wherein the content is 70% by mass or more. The gravure ink for lamination according to claim 1 or 2, wherein the polyurethane resin (A) contains a constituent unit derived from a polyester polyol and / or a polyether polyol. The gravure ink for lamination according to any one of claims 1 to 3, wherein at least one terminal group of the polyurethane resin (A) is an alkyl group and / or a hydroxyl group. The gravure ink for lamination according to any one of claims 1 to 4, further comprising a chlorinated polyolefin resin. A printed matter having a printed layer formed from the gravure ink for laminating according to any one of claims 1 to 5 on a base material 1. A laminate having an adhesive layer and a base material 2 in this order on the printed layer of the printed matter according to claim 6.