JP6391035B1 - Gravure ink and printed matter and laminate - Google Patents

Abstract

The present invention provides a gravure ink that has good printability during gravure printing and has good adhesion, blocking resistance, and laminate strength to a substrate with a wide wetting index.
[Solution]
A gravure ink for forming a printed layer of a laminate having a printed layer between a substrate 1 and a substrate 2, comprising a binder resin (A), a chlorinated polyolefin resin (B), an organic solvent, and water A gravure ink comprising the following (1) and (2):
(1) The binder resin (A) is a polyurethane resin (a1), a vinyl chloride copolymer resin (a2), a cellulose resin (a3), and at least one resin selected from the group consisting of a rosin resin (a4), In a mass ratio of 95/5 to 40/60.
(2) The chlorinated polyolefin resin (B) has a chlorine content of 25 to 45% by mass and is contained in the range of 0.1 to 2% by mass in 100% by mass of the ink.
[Selection figure] None

Description

The present invention relates to a gravure ink, a printed material thereof, and a laminate. More specifically, the present invention relates to an organic solvent type gravure ink for forming a printing layer between the substrate 1 and the substrate 2.

  When a film substrate such as a polyolefin film, a polyester film, a nylon film, or a metal vapor-deposited film is used as a packaging material, printing using a printing ink is usually applied to give a decoration or a pattern. The printed film substrate is then subjected to a laminating process for bonding to another substrate through a slitting process. Lamination is often performed by applying an adhesive onto a printing layer made of printing ink, and there are three types of lamination methods: an extrusion lamination method, a dry lamination method, and a non-solvent lamination method. The laminated body obtained by the laminating process is further processed into a predetermined shape, and finally becomes a package for food packaging, cosmetic packaging and other uses.

In many cases, printing ink is printed on the film substrate, a gravure printing method is employed. The plate used for the gravure printing method is an intaglio plate with characters and patterns. Soak the ink in the plate to the extent that ink enters this cell, and rotate the plate while scraping off excess ink with a doctor blade. The gravure ink is transferred to the film substrate and printed. Since this printing method can express fine shades, it is optimal for reproducing rich gradations such as photographs and is suitable for mass production because high-speed printing is possible.

There are a wide variety of film substrates to be printed, and the surface to be printed is often subjected to easy adhesion treatment or the like. The easy adhesion treatment includes, for example, corona discharge treatment, plasma treatment, vapor deposition treatment, anchor coating treatment, and others. These treatments should improve the wetting index of the printed surface and improve the adhesion between the printed layer and the film substrate. However, the value of the wetting index varies depending on the type and state of the substrate. For example, even the same polypropylene film is printed on the film substrate due to differences in manufacturer and production lot, deterioration over time after storage at high temperature and high humidity, etc. Often the wetting index of the surface is different. For this reason, even when the same ink is printed on these film substrates, there are many cases where the adhesion, blocking resistance, and laminate strength, which are industrially available levels, cannot be obtained uniformly.

  In addition, even if gravure ink can maintain physical properties such as adhesion to film bases with different wetting indices as described above, it may be inferior because it cannot maintain printing suitability such as plate fog and plate clogging properties. Many. For this reason, it is difficult to achieve both printability in addition to ensuring adhesion to substrates with various wetting indices, blocking resistance, and other physical properties, which has been a long-standing problem.

Various ideas have been made to improve the adhesion of the substrate. For example, Patent Document 1 discloses a printing ink using a polypropylene-containing polyurethane resin and a vinyl chloride-vinyl acetate polymer as a binder resin, and Patent Document 2 proposes a printing ink containing an acrylic-modified polyolefin resin. However, there is no mention of the wetting index of the substrate, and further, the printability in the art is unknown, so the above problem remains unsolved.

JP 2005-298618 A JP 2006-132755 A

An object of the present invention is to provide a gravure ink that has good printability during gravure printing, and has good adhesion, blocking resistance, and laminate strength to a substrate having a wide wetting index.

  As a result of intensive studies on the above problems, the present inventor has found that the problem can be solved by using the gravure ink described below, and has reached the present invention.

The present invention is a gravure ink for forming a printed layer of a laminate having a printed layer between a substrate 1 and a substrate 2, and includes a binder resin (A), a chlorinated polyolefin resin (B), an organic solvent A gravure ink comprising water and an organic solvent and water in a total of 100% by mass of 0.1 to 10% by mass and satisfying the following (1) and (2):
(1) The binder resin (A) has an amine value of 1 to 20 mgKOH / g and / or a hydroxyl value of 1 to 20 mgKOH / g, and is derived from a polyester polyol which is a condensate of a dibasic acid and a diol having an alkyl group. And a rosin resin (a4 ) having a softening point of 60 to 180 ° C. and a weight average molecular weight of 500 to 2000 in a mass ratio of 95/5 to 40/60. To do.
(2) The chlorinated polyolefin resin (B) has a chlorine content of 25 to 45% by mass and is contained in the range of 0.1 to 2% by mass in 100% by mass of the ink.

The present invention relates to the gravure ink according to claim 1 , wherein the binder resin (A) contains a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl value of 20 to 200 mgKOH / g.

In the present invention, the polyurethane resin (a1) contains a structural unit derived from a polyester polyol and a structural unit derived from a polyether polyol in a mass ratio of 55/45 to 99/1. About.

The present invention relates to the gravure ink, wherein the polyurethane resin (a1) has a structure represented by the following general formula (1).
General formula (1)

^{_{-COO-CH 2 CR 1 R 2}} CH 2 -OCO-

(Wherein R ¹ represents an alkyl group, and R ² represents a hydrogen atom or an alkyl group.)

The present invention relates to the gravure ink, wherein the chlorinated polyolefin resin (B) is a chlorinated polypropylene resin.

The present invention relates to a printed matter having a printed layer made of the gravure ink on a substrate 1.

The present invention relates to a laminate having a printed layer made of the gravure ink at least between a substrate 1 and a substrate 2.

According to the present invention, it is possible to provide a gravure ink that has good printability during gravure printing and has good adhesion, blocking resistance, and laminate strength with respect to a substrate having a wide wetting index.

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

In this specification, gravure ink may be simply referred to as “ink”, but it is synonymous. In addition, the printed layer may be described as “ink layer” or “ink coating”, but it is synonymous.

The present invention is a gravure ink for forming a printed layer of a laminate having a printed layer between a substrate 1 and a substrate 2, and includes a binder resin (A), a chlorinated polyolefin resin (B), an organic solvent And a gravure ink which contains water and satisfies the following (1) and (2).
(1) The binder resin (A) is a polyurethane resin (a1), a vinyl chloride copolymer resin (a2), a cellulose resin (a3), and at least one resin selected from the group consisting of a rosin resin (a4), In a mass ratio of 95/5 to 40/60.
(2) The chlorinated polyolefin resin (B) has a chlorine content of 25 to 45% by mass and is contained in the range of 0.1 to 2% by mass in 100% by mass of the ink.
The adhesion of the substrate to the substrate 1 is improved by the composition of the binder resin, and the adhesion of the substrate is further improved by using an appropriate amount of the predetermined chlorinated polyolefin resin (B). Moreover, by including water in the organic solvent-based gravure ink having this resin composition, the printability is improved, and a uniform print layer can be obtained.

<Binder resin (A)>
In the present invention, the binder resin refers to a binder resin in ink. Binder resin (A) is a mass ratio of polyurethane resin (a1) and at least one resin selected from the group consisting of vinyl chloride copolymer resin (a2), cellulose resin (a3) and rosin resin (a4). ((A1) / (total amount of (a2) to (a4)) in a ratio of 95/5 to 40/60, preferably in a ratio of 90/10 to 50/50. In 100% by mass of the resin (A), the total content of (a1) to (a4) is preferably 70 to 100% by mass, more preferably 85 to 100% by mass, and the binder resin (A) is an ink. It is preferable to contain in 3 to 30% in the total mass% of, and it is more preferable to contain in 5 to 20%.

Moreover, in 100 mass% of the binder resin (A), the polyurethane resin (a1) and the vinyl chloride copolymer resin (a2) are included in a total of 80 to 100 mass%, and the solid content mass ratio (a1) / (a2) Is preferably 95/5 to 40/60, more preferably 90/5 to 50/50. Within this range, printability, substrate adhesion, coating film properties, and laminate strength are good. In the present specification, solid content means the total mass of nonvolatile components.

<Polyurethane resin (a1)>
The polyurethane resin (a1) preferably has a weight average molecular weight of 10,000 to 100,000, preferably has a glass transition temperature of −60 ° C. to 0 ° C., and further at 40 ° C. in dynamic viscoelasticity measurement. Those having a storage elastic modulus of 1 to 100 MPa are preferred. In the present invention, the glass transition temperature is measured by a differential scanning calorimeter (DSC) and represents the midpoint of the temperature range where the glass transition occurs.

The polyurethane resin (a1) preferably has an amine value and / or a hydroxyl value, and the amine value is preferably 1 to 20 mgKOH / g. The hydroxyl value is preferably 1 to 20 mgKOH / g. The polyurethane resin (a1) may have a urea bond or may not have a urea bond, and two or more kinds may be used in combination.

The polyurethane resin (a1) preferably contains a polyether polyol-derived structural unit, and the content thereof is preferably 0.5 to 30% by mass in 100% by mass of the solid content of the polyurethane resin (a1). More preferably, it is 1-25 mass%. In the present specification, the structural unit derived from the polyether polyol is a structure from the oxygen atom of the hydroxyl group at one end to the oxygen atom of the hydroxyl group at the other end of the polyether polyol which is a raw material of the polyurethane resin (a1). This is a value calculated from the blending amount of the polyether polyol.

The polyurethane resin (a1) preferably includes a structural unit derived from a polyester polyol, and the content thereof is preferably 30 to 75% by mass, more preferably 100% by mass, solid content of the polyurethane resin (a1). It is 40-75 mass%, More preferably, it is 45-70 mass%. In the present specification, the structural unit derived from the polyester polyol refers to the structure from the oxygen atom of the hydroxyl group at one end to the oxygen atom of the hydroxyl group at the other end of the polyester polyol that is the raw material of the polyurethane resin (a1). The value calculated from the blended amount of polyester polyol.

The polyurethane resin (a1) preferably contains both a structural unit derived from a polyester polyol and a structural unit derived from a polyether polyol, and a mass ratio of the structural unit derived from a polyester polyol and the structural unit derived from a polyether polyol (polyester). / Polyether) is preferably contained at 55/45 to 99/1, more preferably contained at a mass ratio of 60/40 to 90/10, and contained at a mass ratio of 70/30 to 85/15. More preferably. This is because the adhesion can be further improved with respect to the substrates having various wetness indexes described later. When the amount of the structural unit derived from the polyester polyol is increased, the adhesion to the substrate is improved by a synergistic effect with the chlorinated polyolefin resin (B) described later. In addition, the structural unit derived from the polyester polyol and the structural unit derived from the polyether polyol are in total, preferably 30 to 75% by mass, and preferably 45 to 75% by mass in 100% by mass of the polyurethane resin (a1). More preferred.

The polyurethane resin (a1) is not particularly limited, and is suitably produced by a known method described in, for example, JP2013-213109A or JP2005-298618A. For example, it can be obtained by subjecting a polyurethane resin comprising a polyol and a polyisocyanate, a urethane prepolymer of a terminal isocyanate comprising a polyol and a polyisocyanate, and a chain extension reaction with an amine compound. Accordingly, a polyurethane resin containing a polyol-derived structural unit is preferred.

Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone diol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimer diol, and hydrogenated dimer diol. It is preferable to use a polyester polyol, and it is more preferable to use a polyether polyol and a polyester polyol in combination.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytrimethylene glycol, and copolymer polyether polyols composed of a combination of two or more of these. Among them, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are preferable, and the number average molecular weight is preferably 500 to 10,000. In addition, the number average molecular weight of the polyol described in this specification is based on the valence (average number) of the hydroxyl group of one polyol molecule and the hydroxyl value (1 mol of hydroxyl group mole value converted to potassium hydroxide) in 1 g of polyol solids. It is calculated and is obtained by (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × hydroxyl number of hydroxyl group / hydroxyl value

As said polyester polyol, the condensate etc. which are obtained by esterification reaction of a dibasic acid and diol are mentioned, for example. Dibasic acids include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1 , 4-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-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl- 1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer diol , Hydrogenated dimer diol, etc. It is below.

As the diol constituting the polyester polyol, a diol having an alkyl group is preferable. The diol having an alkyl group means a diol having a structure in which at least one hydrogen atom of an alkylene group contained in the diol is substituted with an alkyl group, and includes propylene glycol, 1,3-butanediol, 2-methyl-1 , 3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4- Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, And 2,2,4-trimethyl-1,6-hexanediol and the like. These are particularly preferable because they exhibit strong adhesion to substrates having various wetting indices described later.
These polyester polyols can be used alone or in admixture of two or more. The dibasic acid is particularly preferably sebacic acid or adipic acid. Also, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups can be used in combination.

It is preferable that a polyurethane resin (a1) contains the structure represented by following General formula (1) as a structure derived from the diol which comprises the said polyester polyol.
General formula (1)

^{_{-COO-CH 2 CR 1 R 2}} CH 2 -OCO-

(Wherein R ¹ represents an alkyl group, and R ² represents a hydrogen atom or an alkyl group.)
The alkyl group preferably has 1 to 6 carbon atoms, and examples of the diol constituting the structure include neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3- Propanediol and the like are preferred.

When the polyurethane resin (a1) containing the above structure is used, the laminate strength is greatly improved by the combined use with the chlorinated polyolefin resin (B) described later. The structure of the general formula (1) is preferably contained in an amount of 25 to 80% by mass and more preferably 35 to 75% by mass in 100% by mass of the polyurethane resin (a1).

The number average molecular weight of the polyester polyol is preferably 500 to 10,000. The number average molecular weight is determined by the above (Formula 1). The acid value of the polyester polyol used in the present invention is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less.

Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, and 1,3-phenylene. Diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate and the like can be mentioned.
Examples of the aliphatic diisocyanate include methylene diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate,
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, Examples thereof include norbornane diisocyanate and dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group.
These may be trimers to form an isocyanurate ring structure. These polyisocyanates can be used alone or in admixture of two or more. Of these, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate and the like are preferable.

The amine compound includes at least a polyamine compound that serves as a chain extender. In one embodiment, the amine compound may include an amine compound that serves as a polymerization terminator, if necessary, in addition to the polyamine compound.
The polyamine compound that serves as a chain extender is not limited to the following, but preferably has a molecular weight of 500 or less, and examples include diamine-based and polyfunctional amine-based compounds, such as ethylenediamine, propylenediamine, hexamethylenediamine, and pentane. In addition to diamine chain extenders such as methylenediamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, p-phenylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, Di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine A diamine chain extender having a hydroxyl group such as di-2-hydroxypropylethylenediamine can also be used. These chain extenders can be used alone or in admixture of two or more. If necessary, a trifunctional or higher polyfunctional amine chain extender can also be used. Specifically, diethylenetriamine, iminobispropylamine: (IBPA, 3,3′-diaminodipropylamine), triethylenetetramine, N- (3-aminopropyl) butane-1,4-diamine: (spermidine), Examples include 6,6-iminodihexylamine, 3,7-diazanonan-1,9-diamine, and N, N′-bis (3-aminopropyl) ethylenediamine. Of these, isophoronediamine, hexamethylenediamine, and iminobispropylamine are preferable.

Examples of the amine compound that serves as a polymerization terminator include monovalent amine compounds. The monovalent amine compound may be a primary amine or a secondary amine. The monovalent amine compound functions as a polymerization terminator for the purpose of stopping the excessive reaction. Examples of such compounds include dialkylamines such as di-n-butylamine and amino alcohols such as 2-ethanolamine.

<Vinyl chloride copolymer resin (a2)>
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 in terms of weight average molecular weight, and 20,000 to 70,000. Is more preferable. The structure derived from the vinyl acetate monomer in the solid content of 100% by mass of the vinyl chloride-vinyl acetate copolymer resin is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. . In this case, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, laminate strength, and the like are improved.
Moreover, since the solubility to an organic solvent improves, what contains the hydroxyl group derived from vinyl alcohol by a saponification reaction or copolymerization is still more preferable, and it is preferable that it is 20-200 mgKOH / g as a hydroxyl value. The glass transition temperature is preferably 50 ° C to 90 ° C.

<Vinyl chloride-acrylic copolymer resin>
The vinyl chloride-acrylic copolymer resin is mainly composed of a copolymer resin of vinyl chloride monomer and acrylic monomer, and the acrylic monomer has improved adhesion to the base material and solubility in organic solvents (meth). It is preferable to contain a hydroxyalkyl ester of acrylic acid. The acrylic monomer may be incorporated into the main chain of polyvinyl chloride in a block or random manner, or may be grafted to 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, more preferably 30,000 to 70,000.

Moreover, it is preferable that the structure derived from the vinyl chloride monomer in vinyl chloride-acrylic copolymer resin is 70-95 mass% in 100 mass% of vinyl chloride-acrylic copolymer resin solid content. In this case, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, laminate strength, and the like are improved.

In the following description, (meth) acryl or (meth) acrylate means methacryl and acryl, methacrylate and acrylate, respectively.

The acrylic monomer is preferably a (meth) acrylic acid alkyl ester, and the alkyl group preferably has 1 to 20 carbon atoms. 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. The alkyl group may further have a benzene ring structure. These can be used alone or in combination of two or more.

Further, the acrylic monomer preferably has a hydroxyl group, and examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic such as 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate Acid hydroxyalkyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycol mono (meth) acrylate such as 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified ) Acrylate, and hydroxyethyl acrylamide. Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are more preferable because they improve solubility in organic solvents. These can be used alone or in combination of two or more.

In addition, the acrylate ester may have a functional group other than a hydroxyl group, and examples of the functional group include a carboxyl group, an amide bond group, an amino group, and an alkyleneoxy group.

<Cellulose-based resin (a3)>
Examples of the cellulose resin (a3) include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose and the like, and the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, An isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group and the like can be mentioned, and an alkyl group may have a substituent. Among these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable. The molecular weight is preferably 5,000 to 1,000,000 in terms of weight average molecular weight, more preferably 10,000 to 200,000. Moreover, the thing whose glass transition temperature is 100 to 160 degreeC is preferable.

<Rosin resin (a4)>
The rosin resin used in the present invention has a structural unit derived from rosin acid (such as abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, dehydroabietic acid) as a main component (50% by mass or more). Say. The rosin acid or rosin resin may be hydrogenated. The acid value of the rosin resin is preferably 150 mgKOH / g or less, and the acid value is preferably 100 mgKOH / g or less, and more preferably 50 mgKOH / g or less. The softening point is preferably 60 to 180 ° C. The softening point is more preferably 70 to 150 ° C. Examples of the type of rosin resin include rosin-modified phenol resin, rosin ester, rosin-modified maleic resin, and polymerized rosin resin, and at least one rosin resin selected from these is preferable. The softening point is a value measured by the ring and ball method. The softening point can be measured by a measuring method described in JISK2207, for example.

(Rosin ester)
The rosin resin is preferably a rosin ester which is an ester condensation resin of a low molecular polyol having a molecular weight of less than 1000 and rosin acid. The low molecular polyol preferably has 2 to 4 hydroxyl groups (may be abbreviated as 2 to 4 functional groups). The low molecular polyol preferably has a molecular weight of 50 to 500. Examples of the low molecular polyol include bifunctional low molecular polyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,10-decanediol, and trifunctional low molecular polyols such as glycerin and trimethylolpropane. , Tetrafunctional low molecular polyols such as erythritol and pentaerythritol are suitable. Of these, tri- and / or tetrafunctional low molecular polyols are preferred. The weight average molecular weight of the rosin ester is preferably 500 to 2000. More preferably, it is 500-1500.

<Other binder resins>
As long as the binder resin (A) has a binding function in the ink, resins other than the above (a1) to (a4) may be used together. For example, 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, cycloolefin resin, alkyd resin, Examples thereof include polyvinyl chloride resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, silicone resin, and modified resins thereof. These resins can be used alone or in admixture of two or more. The content thereof is preferably 0 to 30% by mass with respect to 100% by mass of the solid content of the binder resin (A). -15 mass% is more preferable. In addition, binder resin (A) does not contain chlorinated polyolefin resin (B).

<Chlorinated polyolefin resin (B)>
In the chlorinated polyolefin resin (B) in the present invention, the chlorine content is preferably 25 to 45% by mass, and preferably 26 to 40% by mass in order to improve the adhesion to the easy adhesion treatment substrate and the laminate strength. More preferably. Here, the chlorine content in the present invention is the content mass% of chlorine atoms in 100 mass% of the chlorinated polyolefin resin (B). 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 resin (B) in the present invention is preferably 5,000 to 30,000. Moreover, it is preferable to contain 0.1-2 mass% of chlorinated polyolefin resin (B) in 100 mass% of ink from a viewpoint of a balance with blocking resistance. More preferably, it is 0.2-1.0 mass%.
In the present invention, the chlorinated polyolefin resin (B) has a structure in which hydrogen of an α-olefin polymer is replaced with chlorine, and the α-olefin is represented by the following general formula (2). An alkene in which the double bond is in the α position, ie at the end.
General formula (2)


CH ₂ = ^{CH-R 1}

(In the formula, R ¹ is an alkyl group having 1 or more carbon atoms.)
Since the chlorinated polyolefin resin (B) has a flexible alkyl group as a branched structure, the chlorinated polyolefin resin (B) is flexible even at a low temperature, and improves the substrate adhesion with the above-mentioned use amount. The α-olefin structure in the chlorinated polyolefin resin (B) is not particularly limited. For example, a resin containing a homopolymer or copolymer of an α-olefin unsaturated hydrocarbon such as polypropylene, poly-1-butene and poly-4-methyl-1-pentene is preferable. Among these, those containing a polypropylene structure (that is, a chlorinated polypropylene structure) are particularly preferable. In this case, excellent substrate adhesion can be obtained when the polyurethane resin (a1) having a polyester structural unit composed of the above-described diol having an alkyl group and a dibasic acid is used in combination.

Further, the chlorinated polyolefin resin (B) may be a copolymer resin with other monomers, and there is no particular limitation as long as it is the chlorine content. The copolymerizable monomer is preferably an acrylic monomer, an acidic monomer, a vinyl acetate monomer, a styrene monomer, or the like. Examples of the acrylic monomer include the acrylic monomers described above, and the acidic monomer is maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, anhydrous Examples include aconitic acid, hymic anhydride, (meth) acrylic acid, and the like.

<Pigment>
In the present invention, the pigment may be either an inorganic pigment or an organic pigment, and is not particularly limited, but good substrate adhesion can be obtained by using an organic pigment. Examples of organic pigments include, but are not limited to, soluble azo series, insoluble azo series, azo series, phthalocyanine series, halogenated phthalocyanine series, anthraquinone series, ansanthrone series, dianthraquinonyl series, anthrapyrimidine series, Perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, carbon black, etc. Pigments are preferred.

The organic pigment is C.I. I. The pigment can be used at any time. Of these, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 146, C.I. I. Pigment red 242, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 14, C.I. I. Pigment orange 38, C.I. I. Pigment orange 13, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 139, C.I. I. Pigment red 185, C.I. I. Pigment red 122, C.I. I. Pigment red 178, C.I. I. Pigment red 149, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment orange 34, C.I. I. Pigment orange 64, C.I. I. Pigment black 7 and the like.

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

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

Among inorganic pigments, extender pigments can also be used. As extender pigments, barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate, silica and the like are preferable.

The pigment is preferably contained in an amount sufficient to ensure the concentration and coloring power of the gravure ink, that is, 1 to 45% by mass in the total mass of gravure ink of 100% by mass, and contained at 2 to 35% by mass. More preferably. These pigments can be used alone or in combination of two or more.

The hue in the gravure ink of the present invention may be selected from ink compositions of other hues as necessary (a total of five colors of yellow, red, indigo, black, and white as basic colors, red (orange) as grass color outside process gamut, grass (Green), purple (three colors), transparent yellow, peony, vermilion, brown, and pearl) may be used in combination.

<Organic solvent>
The gravure ink of the present invention contains an organic solvent as a liquid medium. The organic solvent used is preferably used as a mixed solvent, aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate. Well-known organic solvents such as alcohol organic solvents such as ester organic solvents, methanol, ethanol, n-propanol, isopropanol, and n-butanol can be used. Among these, an organic solvent not containing an aromatic organic solvent such as toluene and xylene (non-toluene organic solvent) is more preferable. More preferably, an organic solvent that does not contain an aromatic organic solvent and / or a ketone organic solvent such as methyl ethyl ketone (hereinafter referred to as “MEK”) is more preferable. Moreover, since printability improves, it is preferable that it is a mixed solvent of an ester organic solvent and an alcohol organic solvent. A preferable mass ratio of the ester organic solvent and the alcohol organic solvent (ester organic solvent / alcohol organic solvent) is 40/60 to 90/10.

Furthermore, the gravure ink of the present invention contains water as a liquid medium. The content is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 8% by mass, in 100% by mass of the liquid medium. More preferably, it is 0.3-6 mass%. This content improves the printing aptitude such as the plate, that is, the plate covering property and the like.

<Additives>
The gravure ink of the present invention can appropriately include known additives as additives, and known additives such as pigment derivatives, dispersants, wetting agents, adhesion aids, as necessary in the production of ink compositions, Leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, isocyanate curing agents, silane coupling agents, and the like can be used. In addition, since blocking resistance improves, it is preferable to contain 0.01-2 mass% of fatty acid amide and / or hydrocarbon wax as a wax component.

As the fatty acid amide, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide, oleic acid amide, erucic acid amide and the like are preferable. The hydrocarbon wax is preferably polyethylene wax or Fischer-Tropsch wax having a softening point of 85 to 120 ° C.

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

<Manufacture of gravure ink>
The gravure ink of the present invention can be produced by dissolving and / or dispersing a pigment, a binder resin (A), and a chlorinated polyolefin resin (B) in an organic solvent. Specifically, for example, an organic pigment, a polyurethane resin (a1), a vinyl chloride copolymer resin (a2), and, if necessary, the above dispersant are mixed to produce a pigment dispersion dispersed in an organic solvent. A gravure ink can be produced by further blending the obtained pigment dispersion with a polyurethane resin (a1), a chlorinated poly-α-olefin resin, water, or other resin or additive as required. The particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

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

<Printed matter>
The gravure ink of the present invention can be printed by a gravure printing method. For example, it is diluted with an organic solvent to a viscosity and concentration suitable for gravure printing, and supplied alone or mixed to each printing unit. After printing on the base material 1 using the gravure ink of the present invention, a volatile component is dried and removed to form a printed layer, thereby obtaining a printed matter.

<Substrate 1>
Examples of the substrate 1 that can be used in the printed matter of the present invention include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, and polychlorinated. Examples thereof include vinyl, polyvinylidene chloride, cellophane, paper, aluminum and the like, or a film-like substrate made of a composite material thereof. Further, a vapor deposition substrate obtained by vapor-depositing an inorganic compound such as silica, alumina or aluminum on polyethylene terephthalate or nylon film can be used, and the vapor-deposited surface may be coated with polyvinyl alcohol or the like.
The substrate 1 is preferably subjected to easy adhesion treatment on the surface to be printed (surface in contact with the printing layer). Examples of the easy adhesion treatment include corona discharge treatment, ultraviolet / ozone treatment, plasma treatment, and oxygen plasma treatment. , Primer treatment and the like. For example, in the corona discharge treatment, a hydroxyl group, a carboxyl group, a carbonyl group, etc. are expressed on the substrate. Since hydrogen bonds can be used, the ink preferably contains a compound having a functional group such as a hydroxyl group or an amino group.
Moreover, as for the base material 1, it is more preferable that the wetting index of the surface to be printed is 34-60 dyne / cm, and it is still more preferable that it is 35-55 dyne / cm. The wetting index is a value measured by the method described in JISK6768 using a wetting index standard solution.

<Substrate 2>
Examples of the substrate 2 include those similar to the substrate 1, and may be the same or different. Among these, unstretched polyethylene, unstretched polypropylene, nylon base material, aluminum foil base material, aluminum vapor deposition base material and the like are preferable.

<Laminate>
In the laminate of the present invention, the substrate 2 is further bonded in this order to the printed layer of the printed matter. In addition, the laminated body containing an adhesive bond layer is preferable, and the laminated body which has the base material 1, the printing layer, the adhesive bond layer, and the base material 2 in order is preferable. Examples of the adhesive layer include a layer made of an anchor coat agent, a urethane-based laminate adhesive, a molten resin, and the like. Examples of anchor coating agents (AC agents) include imine AC agents, isocyanate AC agents, polybutadiene AC agents, and titanium AC agents. Urethane laminate adhesives include polyether urethane laminate adhesives and polyester laminates. Examples thereof include an adhesive and the like, and those containing an organic solvent and those without a solvent. Moreover, molten polyethylene etc. are mentioned as molten resin.
As a method for producing a laminate, for example, a normal extrusion laminate (extrusion laminate) in which a molten polyethylene resin is laminated on a printed layer through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium. ) Method, a dry laminating method or non-solvent laminating method in which an adhesive such as urethane is applied to the printing surface and a plastic film is laminated thereon, or a direct laminating method in which molten polypropylene is directly pressed and laminated on the printing surface. It can be obtained by a known laminating process.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the present invention, parts and% represent parts by weight and% by weight unless otherwise noted.

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

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

(Base material wetting index)
It calculated | required in accordance with the method of JISK6768 using the wetting index standard solution.

(Synthesis example 1) [Polyurethane resin PU1]
40 parts of a polyester polyol (hereinafter “MPD / AA”) having a number average molecular weight of 2000, which is a condensate of 3-methyl-1,5-pentanediol and adipic acid, and polypropylene glycol (hereinafter “PPG”) having a number average molecular weight of 1,000. Part, 37.3 parts of isophorone diisocyanate (hereinafter “IPDI”) and 34.3 parts of ethyl acetate were reacted at 80 ° C. for 4 hours under a nitrogen stream to obtain a solvent solution of a terminal isocyanate urethane prepolymer. Next, 15.1 parts of isophorone diamine (hereinafter “IPDA”), 2.0 parts of iminobispropylamine (hereinafter “IBPA”), 1.0 part of 2-ethanolamine (hereinafter “2EtAm”), ethyl acetate / isopropanol (hereinafter referred to as “below”) "IPA") = To the mixture of 328.4 parts of a 50/50 mixed solvent, the obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C and then reacted at 80 ° C for 1 hour to obtain a solid content. A polyurethane resin solution PU1 having 30%, an amine value of 4.5 mgKOH / g, a hydroxyl value of 5.9 mgKOH / g, and a weight average molecular weight of 48,000 was obtained.

(Synthesis Examples 2 to 4) [Polyurethane resins PU2 to PU4]
Using the raw materials shown in Table 1, polyurethane resin solutions PU2 to PU4 were obtained in the same manner as in Synthesis Example 1. Abbreviations in Table 1 are as follows.
NPG / AA: Polyester polyol which is a condensate of neopentyl glycol and adipic acid MPO / AA: Polyester polyol which is a condensate of 2-methyl-1,3-propanediol and adipic acid PEG: Polyethylene glycol TDI : Tolylene diisocyanate (methyl-1,3-phenylene diisocyanate)

(Synthesis Example 5) [Vinyl chloride-acrylic copolymer resin (PVAc1)]
In a 1.0 L autoclave, 1.0 g of potassium peroxodisulfate (K ₂ S ₂ O ₈ ) was dissolved in 500 g of ion-exchanged water and deaerated. After raising the temperature to 60 ° C., 425 g of a mixture consisting of 357 g of vinyl chloride, 63 g of 2-hydroxypropyl acrylate, and 5.0 g of sodium di-2-ethylhexylsulfosuccinate (product name: Aerosol OT) was placed in an autoclave. Addition and reaction were carried out at 6.5 ° C. at 0 ° C. The polymerization reaction was continued until the autoclave reached 2.5 atm. The resulting emulsion was precipitated with sodium chloride, filtered, washed and dried to obtain a vinyl chloride-acrylic copolymer resin. Furthermore, vinyl chloride-acrylic copolymer resin was dissolved in ethyl acetate to obtain a varnish (PVAc1) having a solid content of 30%. In addition, the content rate of 2-hydroxypropyl acrylate in the obtained resin was 14.0%, the weight average molecular weight 50000, and the glass transition temperature 70 degreeC.

In this specification, Examples 20 to 23, and printed materials and laminates using the same are reference examples.
(Example 1) [Preparation of gravure ink S1]
40 parts of polyurethane resin solution PU1 (solid content 30%), vinyl chloride-vinyl acetate copolymer resin (Solvine TA5R: manufactured by Nissin Chemical Industry Co., Ltd. Vinyl chloride: vinyl acetate: vinyl alcohol = 88: 1: 11 (solid content 30 % Ethyl acetate solution))) 5 parts C.I. I. 10 parts of Pigment Blue 15: 3 (product name: Lionol Blue FG7330, manufactured by Toyokara Co., Ltd.), 43.5 parts of a solution of propyl acetate / IPA = 70/30, and 2.5 parts of water were mixed, and 20 parts by Eiger Mill. After dispersing for 5 minutes, 0.5 part of oleic acid amide and 1.0 part of chlorinated polypropylene resin (product name: 370M chlorine content 30% solid content 50%) manufactured by Nippon Paper Industries Co., Ltd. were added to the dispersion. The mixture was stirred and mixed for 10 minutes to obtain gravure ink S1.

(Examples 2 to 23) [Creation of gravure inks S2 to S23]
Gravure inks S2 to S23 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 2 were used.
In addition, the abbreviation in Table 2 represents the following.
DLX5-8: Nitrocellulose manufactured by ICI Novelenterprises, nitrogen content 12.0% (solid content 30% isopropanol solution)
Harrier Star P: rosin-modified pentaerythritol ester manufactured by Harima Chemicals Co., Ltd. Softening point 100 ° C. Acid value 10 mg KOH / g Weight average molecular weight 1500 (solid content 30% ethyl acetate solution)
814B: Nippon Paper Industries Co., Ltd. Chlorinated polypropylene resin Chlorine content 41%
・ 2027MB: Nippon Paper Industries Co., Ltd. Chlorinated polypropylene resin Chlorine content 27%
・ 803LT: Chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd. Chlorine content 26.5%
・ 3228S: Nippon Paper Industries' acid-modified chlorinated polyolefin resin Chlorine content 28%
・ Titanium oxide: JR403 manufactured by Teika

(Comparative Examples 1 to 7) [Creation of gravure inks SS1 to SS7]
Gravure inks SS1 to SS7 were obtained by the same method as that described in Example 1 except that the raw materials shown in Table 3 were used. In addition, the abbreviation in Table 3 shows the following.
A-124GP: Takamatsu Yushi Co., Ltd. Polyester resin Solid 25% solution 851L: Nippon Paper Industries acid modified chlorinated polyolefin resin Chlorine content 19%

(Example 24)
<Printing gravure ink>
The gravure ink S1 obtained above was mixed with a mixed solvent (methyl ethyl ketone “MEK”: N propyl acetate “NPAC”: isopropanol “IPA” = 40: 40: 20) with a viscosity of 16 seconds (25 ° C., Zahn Cup No. 1). 3) Dilute to become 3), and print on the corona discharge treatment surface or alumina vapor deposition surface of the plastic substrate shown below at a printing speed of 100 m / min with a Helio 175 line solid plate (plate-type compressed, 100% solid pattern). Printed materials J1, K1, L1, and M1 were obtained using the following base materials (1) to (4), respectively. The printing conditions were a temperature of 25 ° C. and a humidity of 60%.

-Base material used for J1 printing (1): Biaxially stretched polypropylene (OPP) base material manufactured by Toyobo Co., Ltd. P2261 Thickness of 20 μm Corona discharge treated surface wetting index 35 dyne / cm
Base material (2) used for K1 printing: Biaxially stretched polypropylene (OPP) base material manufactured by Toyobo Co., Ltd. P2261 Thickness of 20 μm Corona discharge treated surface wetting index 40 dyne / cm
-Base material (3) used for printing of L1: Biaxially stretched polyester (PET) base material manufactured by Unitika PTM film thickness 12 μm Wetting index 45 dyne / cm of corona discharge treated surface
-Substrate (4) used for M1 printing: Mitsui Chemicals Tosero Co., Ltd. Alumina-deposited biaxially stretched polyester (alumina-deposited PET) substrate TL-PETH Wetting index 55 dyne / cm on the deposition surface
In addition, the base material (1) used for the printing of J1 described above was intentionally corona discharge treated surface by leaving the base material (2) used for the printing of K1 at 40 ° C.-80% RH for 5 days. The wetting index is reduced.

<Extrusion laminating>
A solid content of 1% (weight ratio, methanol / water = diluted) obtained by diluting a polyethyleneimine anchor coating agent (EL420 manufactured by Toyo Morton Co., Ltd.) with a solvent consisting of methanol: water = 70: 30 (mass ratio) on the printed layer of the printed matter J1. 70/30) solution is applied, and a low-density polyethylene (Novatech LC600, manufactured by Nippon Polychem) melted at 315 ° C. is superimposed on the coated surface, and at the same time, unstretched polypropylene (FCMN, membrane) By laminating 40 μm thick, manufactured by Tosero Co., Ltd., an extrusion laminate process was performed to obtain a laminate.

<Dry laminating>
A polyester urethane-based laminate adhesive (TM250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) with an ethyl acetate solution having a solid content of 20% is applied to the printed surface of the printed matter L1, and the adhesive layer after drying is 2.0 g / m ^2. After coating and drying to obtain a laminate, unbonded polypropylene (CPP) having a thickness of 80 μm was bonded to the adhesive layer, and dry lamination was performed to obtain a laminate.

(Examples 25-46)
Printed materials J2 to J23, K2 to K23, L2 to L23, and M2 to M23 were obtained in the same manner as in Example 24 except that the inks listed in Table 2 were used in the combinations described in Table 4. Further, extrusion lamination was performed on the printed surfaces of the printed materials J2 to J23 by the same method as described above to obtain a laminate. Moreover, the dry lamination process was performed to the printing surface of the printed matter of printed matter L2-L23 by the method similar to the above, and the laminated body was obtained. Evaluation was performed after the laminate was held at 40 ° C. for 48 hours.

(Comparative Examples 8-14)
Printed materials JJ1 to JJ7, KK1 to KK7, LL1 to LL7, and MM1 to MM7 were obtained in the same manner as in Example 24 except that the inks shown in Table 3 were used in the combinations shown in Table 5. Further, extrusion lamination was performed on the printed surfaces of the printed materials JJ1 to JJ7 in the same manner as described above to obtain a laminate. Moreover, the dry lamination process was performed by the method similar to the above to the printing surface of the printed matter of printed matter LL1-LL7, and the laminated body was obtained. Evaluation was performed after the laminate was held at 40 ° C. for 48 hours.

<Evaluation>
The following evaluation was performed on the gravure inks, printed materials, and laminates of Examples and Comparative Examples. Tables 4 and 5 show the results.

<Adhesion>
Printed materials J1 to J23, K1 to K23, L1 to L23 and M1 to M23, and JJ1 to JJ7, KK1 to KK7, LL1 to LL7 and MM1 to MM7 are each left at 25 ° C. for 1 day, and then have a 12 mm wide adhesive on the printed surface. A tape (cellophane tape manufactured by Nichiban Co., Ltd.) was applied, and the appearance of the printed surface was visually determined when it was rapidly peeled in the direction of 90 ° with respect to the substrate surface. The criteria for determination were as follows.
(Evaluation criteria)
5. The ink film on the printing surface does not peel off at all (good)
4). The peeled area of the ink coating is 1% or more and less than 5% (practical)
3. Ink film peeling area of 5% or more and less than 20% (slightly poor)
2. Ink film peeling area of 20% or more and less than 50% (defect)
1. The ink film is peeled off by 50% or more (very bad)
In addition, 5 and 4 are ranges in which there is no practical problem.

<Blocking resistance>
About printed matter J1-J23, K1-K23 and JJ1-JJ7, KK1-KK7, blocking resistance was evaluated on condition of the following.
(Sample and pressure)
Printed layer of OPP printed matter / OPP substrate non-corona treated surface 10 kg / cm ²
(Standing condition) 40 ° C.-80% RH 48 hours (Evaluation method) The printed surface and the substrate are peeled off, and the degree of peeling of the ink film from the printed surface is visually determined.
(Evaluation criteria)
5. The ink film on the printing surface does not peel off at all, and the peel resistance is low (good)
4). An ink film with a peel area of 1% or more and less than 5% and a low peel resistance (practical)
3. Ink film peeling area of 5% or more and less than 20% (slightly poor)
2. Ink film peeling area of 20% or more and less than 50% (defect)
1. The ink film peels 50% or more (very bad)
In addition, 5 and 4 are ranges in which there is no practical problem.

<Lamination strength>
For a laminate using printed materials J1 to J23 and L1 to L23, and a laminate using JJ1 to JJ7 and LL1 to LL7, the printed part is cut at a width of 15 mm, and then peeled off at the ink surface and the substrate surface. The strength (laminate strength) was measured with a 2011 universal tensile tester manufactured by Intesco.
(Evaluation criteria)
5. Tensile strength is 1.0N / 15mm or more (good)
4). Tensile strength is 0.6N / 15mm or more and less than 1.0N / 15mm (practical)
3. Tensile strength is 0.4N / 15mm or more and less than 0.6N / 15mm (slightly poor)
2. Tensile strength is 0.2N / 15mm or more and less than 0.4N / 15mm (defect)
1. Tensile strength is less than 0.2N / 15mm (very bad)
In addition, 5 and 4 are ranges in which there is no practical problem.

<Printability (plate fog)>
Plate fogging evaluation was performed on the gravure inks S1 to S23 and SS1 to SS7. The dilution solvent is MEK: NPAC: IPA = 40: 40: 20, the viscosity is 16 seconds (25 ° C.) with Zahn cup # 3, and the area of the plate covering part after 90 minutes of idling of the plate in the printing press is Visual evaluation and evaluation were performed.
(Evaluation criteria)
5. Plate cover area is 0% or more and less than 5% (good)
4). Plate cover area is 5% or more and less than 10% (practical)
3. Plate cover area is 10% or more and less than 15% (slightly poor)
2. Plate cover area is 15% or more and less than 30% (defect)
1. Plate cover area is 30% or more (very bad)
In addition, 5 and 4 are ranges in which there is no practical problem.

<Appearance>
About the laminated body using printed matter J1-J23 and the laminated body using JJ1-JJ7, it cut out to the test piece of 200 mm x 200 mm size, and evaluated the external appearance in the following five steps. In the following description, unevenness refers to a shaded portion of a printed portion, and a defect refers to a pinhole or repellency in the printed portion.
(Evaluation criteria)
1. Unevenness or defects in the laminate cannot be confirmed visually (good)
2. One layer of unevenness or defect can be visually confirmed (practical)
3. It is possible to visually check 2 to 5 irregularities or defects in the laminate (slightly defective).
4). Unevenness or defects can be visually confirmed in the laminate by 6 to 10 (defective)
5. Eleven or more irregularities or defects can be visually confirmed on the laminate (very bad).
In addition, 5 and 4 are ranges in which there is no practical problem.

From the evaluation results, it is shown that the gravure ink of the present invention is a gravure ink having good printability at the time of gravure printing and having good adhesion, blocking resistance and laminate strength to a substrate having a wide range of wetness index. It was done. Furthermore, it has been shown that it has an excellent effect of reducing unevenness and defects (pinholes and repellency) in the printed layer of the laminate.

Claims (7)

A gravure ink for forming a printed layer of a laminate having a printed layer between a substrate 1 and a substrate 2, comprising a binder resin (A), a chlorinated polyolefin resin (B), an organic solvent, and water A gravure ink comprising: an organic solvent and water in a total content of 100% by mass of water of 0.1 to 10% by mass and satisfying the following (1) and (2):
(1) The binder resin (A) has an amine value of 1 to 20 mgKOH / g and / or a hydroxyl value of 1 to 20 mgKOH / g, and is derived from a polyester polyol which is a condensate of a dibasic acid and a diol having an alkyl group. And a rosin resin (a4 ) having a softening point of 60 to 180 ° C. and a weight average molecular weight of 500 to 2000 in a mass ratio of 95/5 to 40/60. To do.
(2) The chlorinated polyolefin resin (B) has a chlorine content of 25 to 45% by mass and is contained in the range of 0.1 to 2% by mass in 100% by mass of the ink. The gravure ink according to claim 1, wherein the binder resin (A) contains a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl value of 20 to 200 mgKOH / g. The polyurethane resin (a1) contains a structural unit derived from a polyester polyol and a structural unit derived from a polyether polyol in a mass ratio of 55/45 to 99/1. Gravure ink. The gravure ink according to any one of claims 1 to 3, wherein the polyurethane resin (a1) has a structure represented by the following general formula (1).
General formula (1)

^{_{-COO-CH 2 CR 1 R 2}} CH 2 -OCO-

(Wherein R ¹ represents an alkyl group, and R ² represents a hydrogen atom or an alkyl group.) The gravure ink according to any one of claims 1 to 4, wherein the chlorinated polyolefin resin (B) is a chlorinated polypropylene resin. The printed matter which has the printing layer which consists of the gravure ink in any one of Claims 1-5 on the base material 1. FIG. A laminate comprising at least a printed layer made of the gravure ink according to any one of claims 1 to 5 between the substrate 1 and the substrate 2.