JP2021119235A - Gravure ink, and printed matter and laminate of the same - Google Patents

Abstract

To provide a gravure ink excellent in printability at gravure printing, and excellent in adhesiveness to a substrate with a wide range of a wetting index, anti-blocking property, and laminate strength.SOLUTION: A gravure ink for forming a printed layer of a laminate having a printed layer between a substrate 1 having a wetting index of 30-60 dyne/cm of a surface contacting the printed layer, and a substrate 2 contains a titanium oxide pigment, a polyurethane resin and a chlorination polyolefin resin. The gravure ink satisfies (1) and (2) as follows: (1) the titanium oxide pigment is rutile-type titanium oxide having at least a treatment layer comprising silica and/or alumina; and (2) the chlorination polyolefin resin has a chlorine content of 25-45 mass%, and contains in a range of 0.1-2 mass% in 100 mass% of the ink.SELECTED DRAWING: None

Description

The present invention relates to a gravure ink, a printed matter thereof, and a laminate.

When a film substrate such as an OPP film, PET film, NY film, or metal-deposited film is used as a packaging material, printing with a printing ink is usually performed to decorate the substrate or protect the surface. The printed base material is then sent to a laminating process through a slitting process, and finally becomes a package for food packaging, cosmetic packaging, and all other uses.

In many cases, the gravure printing method is adopted for printing on the film base material and the paper base material. The plate used in the gravure printing method has intaglio parts such as letters and patterns, soak the ink in the plate to the extent that ink enters this cell, and while rotating the plate, scrape off excess ink on the surface with a doctor blade. , The gravure ink is transferred to the base material and the meat is formed. Since this printing method can express fine shades, it is most suitable for reproducing rich gradations such as photographs, and it is suitable for mass production because it enables high-speed printing.

In gravure printing, there are a wide variety of film substrates to be printed, and most of the printed surfaces are subjected to easy-adhesion treatment or the like. However, depending on the type of ink, some inks do not adhere to the base material even though they have been subjected to an easy-adhesion treatment, while others adhere excessively and cause blocking during print winding. Such defective adhesion products and blocking products are treated as defective lots by the printing converter, resulting in production loss.

The easy-adhesion treatment includes, for example, a corona discharge treatment, a plasma treatment, a thin-film deposition treatment, an anchor coating treatment, and various other treatments. By these treatments, the wetting index of the printed surface is improved, and the adhesiveness of the ink is improved. However, the types of substrates and the wetting index vary. For example, even with the same polypropylene film, the wetting index of the printed surface differs due to differences in manufacturers and deterioration over time at high temperature and high humidity, so the same ink was printed on these films. However, in many cases, adhesiveness, blocking resistance, and laminate strength cannot be obtained in the same manner. Therefore, ensuring physical properties such as adhesion to a substrate having various wettability indexes and blocking resistance has been an issue for many years.

In the above-mentioned gravure ink for laminating, after the ink is printed on the base material, the base material is further bonded on the print layer with an adhesive. The method is roughly divided into three types: an extrusion laminating method, a dry laminating method, and a non-solvent laminating method. In addition to the above-mentioned problems, there are concerns about poor appearance, insufficient laminating strength, boil / retort resistance, etc. in the laminating process, and various measures have been taken to improve these (Patent Document 1, Patent Document). 2. Patent Document 3), for example, a printing ink containing an acrylic-modified polyolefin resin has been proposed (Patent Document 4). However, the above problems remain unsolved.

Furthermore, titanium oxide is mainly used as a pigment in gravure white ink, which is an inorganic pigment and has a high content in the ink, and is compared with the case of using an organic pigment in terms of ensuring performance such as substrate adhesion. And it's more difficult.

Japanese Unexamined Patent Publication No. 2010-270216 Japanese Unexamined Patent Publication No. 2005-298618 Japanese Unexamined Patent Publication No. 2013-213109 Japanese Unexamined Patent Publication No. 2016-132755

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

As a result of diligent research 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.

That is, the present invention is a gravure for forming a printed layer of a laminated laminate having a printed layer between a base material 1 having a wetness index of 30 to 60 dyne / cm on a surface in contact with the printed layer and the base material 2. The present invention relates to a gravure ink containing a titanium oxide pigment, a polyurethane resin and a chlorinated polyolefin resin, and satisfying the following (1) and (2).
(1) The titanium oxide pigment is rutile-type titanium oxide having a treated layer made of at least silica and / or alumina.
(2) The chlorinated polyolefin resin has a chlorine content of 25 to 45% by mass and is contained in 100% by mass of the ink in the range of 0.1 to 2% by mass.

Further, the present invention further contains a vinyl chloride copolymer resin and / or a cellulosic resin, and contains a polyurethane resin, a vinyl chloride copolymer resin and a cellulosic resin in a mass ratio of 95/5 to 40/60. The present invention relates to the gravure ink.

The present invention also relates to the gravure ink, which is a polyurethane resin having at least a structural unit derived from a polyester polyol.

Further, the present invention is characterized in that the polyurethane resin 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. Regarding.

The present invention also relates to the gravure ink, which is characterized in that the polyurethane resin has a structure represented by the following general formula (1).
General formula (1)
-COO-CH ₂ CR ¹ R ² CH ₂ -OCO-
(In the formula, R ¹ represents an alkyl group and R ² represents a hydrogen atom or an alkyl group.)

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

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

The present invention also relates to a laminated laminate having at least a printing layer made of the gravure ink between the base material 1 and the base material 2.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a gravure ink which has good printability during gravure printing and has good adhesion, blocking resistance, and lamination strength to a substrate having a wide wetness index.

Hereinafter, embodiments of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described as long as the gist of the present invention is not exceeded. Not limited to the content.

The present invention is a gravure ink for forming a printed layer of a laminated laminate having a printed layer between a base material 1 having a wetness index of 30 to 60 din / cm on a surface in contact with the printed layer and the base material 2. It is a gravure ink containing a titanium oxide pigment, a polyurethane resin and a chlorinated polyolefin resin, and satisfying the following (1) and (2).
(1) The titanium oxide pigment is rutile-type titanium oxide having a treated layer made of at least silica and / or alumina.
(2) The chlorinated polyolefin resin has a chlorine content of 25 to 45% by mass and is contained in 100% by mass of the ink in the range of 0.1 to 2% by mass.

The gravure ink of the present invention is a gravure ink containing the titanium oxide as a pigment. It contains polyurethane resin as a binder resin, chlorinated polyolefin resin as an adhesive aid in the above range, and has good adhesion, blocking resistance, and lamination strength in a substrate having a printing substrate of 30 to 60 dyne / cm. Performance can be obtained. It is considered that this effect is a synergistic effect of the binder performance and pigment dispersibility of the polyurethane resin and the substrate adhesion of the chlorinated polyolefin resin.

Further, the gravure ink of the present invention preferably contains the total amount of the vinyl chloride copolymer resin and the cellulose resin in a mass ratio of 95/5 to 40/60 in addition to the polyurethane resin. More preferably, it is 90/10 to 50/50. This is because the vinyl chloride copolymer resin and the cellulose resin have a high glass transition temperature (hereinafter sometimes referred to as Tg), so that the film of the printing layer becomes strong and the blocking resistance is improved.

The binder resin refers to a resin component for binding a pigment containing a titanium oxide pigment. The binder resin is preferably contained in an amount of 3 to 40%, more preferably 5 to 25%, as a total mass% in the gravure ink. It is preferable that the binder resin contains the polyurethane resin, the vinyl chloride copolymer resin and / or the cellulosic resin in a total of 70 to 100% by mass in 100% by mass of the binder resin. More preferably, it is 85 to 100% by mass.

Further, it is preferable that the polyurethane resin and the vinyl chloride copolymer resin are contained in a total of 70 to 100% by mass in 100% by mass of the binder resin, and the solid content mass ratio / is 95/5 to 40/60, 90. It is more preferably / 5 to 50/50. Within this range, printability, substrate adhesion, coating film physical properties, and laminate strength are good.

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

The polyurethane resin preferably has an amine value 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 may have a urea bond, may not have a urea bond, and may be used in combination of two or more.

The polyurethane resin preferably contains a structural unit derived from a polyester polyol, and the content thereof is preferably 30 to 75% by mass, more preferably 40 to 75% by mass, based on 100% by mass of the polyurethane resin solid content. Yes, more preferably 45-70% by mass.
In the present specification, the structural unit derived from polyester polyol means the structure of polyester polyol, which is a raw material of polyurethane resin, from the oxygen atom of the hydroxyl group at one end to the oxygen atom of the hydroxyl group at the other end, and is a polyester polyol. It is a value calculated from the blending amount of.

The polyurethane resin preferably contains a structural unit derived from a polyether polyol, and the content thereof is preferably 0.5 to 30% by mass, more preferably 1 to 25, based on 100% by mass of the polyurethane resin solid content. It is mass%.
In the present specification, the structural unit derived from the polyether polyol indicates the structure of the polyether polyol, which is a raw material of the polyurethane resin, from the oxygen atom of the hydroxyl group at one terminal to the oxygen atom of the hydroxyl group at the other end. It is a value calculated from the blending amount of the polyether polyol.

The polyurethane resin preferably contains both a structural unit derived from a polyester polyol and a structural unit derived from a polyether polyol, and has a mass of a structural unit derived from a polyester polyol and a structural unit derived from a polyether polyol (polyester / polyether). It is preferably contained in a ratio of 55/45 to 99/1, more preferably in a mass ratio of 60/40 to 90/10, and to be contained in a mass ratio of 70/30 to 85/15. Is more preferable. When the amount of the structural unit derived from the polyester polyol increases, the adhesion to the substrate is improved by the synergistic effect of the combined use with the chlorinated polyolefin resin described later. In total, the structural unit derived from the polyester polyol and the structural unit derived from the polyether polyol are preferably contained in an amount of 30 to 75% by mass, more preferably 45 to 75% by mass, based on 100% by mass of the polyurethane resin.

The polyurethane resin is not particularly limited, and is appropriately produced by a known method. For example, it can be obtained by reacting a polyurethane resin composed of a polyol and a polyisocyanate, a urethane prepolymer having a terminal isocyanate composed of a polyol and a polyisocyanate, and an amine compound further containing an amine-based chain extender. Therefore, a polyurethane resin containing a polyol structural unit derived from a polyol is preferable.

Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone diol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimerdiol, hydrogenated dimerdiol and the like. Above all, the combined use of the polyether polyol and the polyester polyol is preferable.

Examples of the above-mentioned polyether polyols include homopolymers such as ethylene oxide, propylene oxide and tetrahydrofuran, and polyether polyols of copolymers composed of a combination of two or more kinds. Of these, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are preferable, and the number average molecular weight is preferably 500 to 10,000. The number average molecular weight of the polyol described in the present specification is calculated from the valence of the hydroxyl group of the polyol single molecular chain and the hydroxyl value in 1 g of the polyol solid content (converted value of the number of molar hydroxyl groups in potassium hydroxide). It is obtained by (Equation 1).
(Equation 1) Number average molecular weight of polyol = 1000 × 56.1 × valence of hydroxyl group / hydroxyl value

Examples of the polyester polyol include a condensate obtained by an esterification reaction between a dibasic acid and a diol. 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-octane. Diol, 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 Examples thereof include diols and hydrogenated dimer diols.

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 of the hydrogen atoms of the alkylene group contained in the diol is substituted with an alkyl group, and is propylene glycol, 1,3-butanediol, or 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 adhesiveness to substrates having various wettability indices, which will be described later.
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 polyvalent carboxylic acid having 3 or more carboxyl groups can also be used in combination.

The polyurethane resin preferably contains a structure represented by the following general formula (1) as a structure derived from the diol constituting the polyester polyol.
General formula (1)
-COO-CH ₂ CR ¹ R ² CH ₂ -OCO-
(In the formula, R ¹ represents an alkyl group and R ² represents a hydrogen atom or an alkyl group.)
Examples of the diol constituting the above structure include neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol and the like.

When a polyurethane resin containing the above structure is used, the laminate strength is significantly improved when used in combination with a chlorinated polyolefin resin described later. The structure of the general formula (1) preferably contains 25 to 80% by mass, more preferably 35 to 75% by mass, in 100% by mass of the polyurethane resin.

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 (Equation 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 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, diisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group, and the like.
Of these, at least one selected from trimers of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, and hexamethylene diisocyanate is preferable. These polyisocyanates can be used alone or in combination of two or more.

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

The amine compound may contain a compound having a primary or secondary monovalent amino group. These compounds function as polymerization inhibitors aimed at terminating excessive reactions. Examples of such compounds include dialkylamines such as di-n-butylamine and aminoalcohols such as 2-ethanolamine. Further, especially when it is desired to introduce a carboxyl group into a polyurethane resin, amino acids such as glycine and L-alanine can be used as a polymerization inhibitor. When a polymerization inhibitor is used, the chain extension reaction may be carried out by using the polymerization terminator and the chain extender together, or the polymerization terminator is added alone after the chain extension reaction is carried out to some extent by the chain extender. Then, the polymerization termination reaction may be carried out. On the other hand, the molecular weight can be controlled without using a polymerization terminator, but in this case, a method of adding the prepolymer to the solution containing the chain extender is preferable in terms of reaction control.

The method for synthesizing the polyurethane resin is preferably a synthesis method in which a polyol is reacted with a polyisocyanate to form a polyurethane resin, or a method in which the polyol is reacted with a polyisocyanate and then reacted with an amine chain extender to form a polyurethane resin.
For example, in a method in which a polyol is reacted with a polyisocyanate and then reacted with an amine-based chain extender to form a polyurethane resin, a solvent inert to the isocyanate group is used as necessary for the polyol and the polyisocyanate, and further, if necessary. For example, a urethanization catalyst is used to react at a temperature of 50 ° C. to 150 ° C. (urethaneization reaction) to produce a prepolymer having an isocyanate group at the terminal, and then the prepolymer is reacted with an amine-based chain extender (chain). A prepolymer method for obtaining a polyurethane resin by subjecting it to an extension reaction) can be mentioned. However, the method for producing the polyurethane resin is not limited to these.

In producing the above prepolymer, 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, and the value of NCO / OH is 1.1 to 1. It is preferable that the range is 3.0. More preferably, NCO / OH = 1.3 to 2.5.

Further, it is preferable to use an organic solvent for the synthesis of the prepolymer from the viewpoint of reaction control. As the organic solvent that can be used, an organic solvent that is inactive in reacting with an isocyanate group is preferable, and examples thereof include a ketone-based organic solvent such as methyl ethyl ketone and an ester-based organic solvent such as ethyl acetate and normal propyl acetate.

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.

The above-mentioned prepolymer having an isocyanate group at the terminal is reacted with an amine-based chain extender such as diamine or triamine at 10 to 60 ° C. to obtain a high-molecular-weight polyurethane resin containing an active hydrogen group at the terminal. Be done.

The ratio (NH / residual NCO) of the total number of moles of amino groups of the amine compound to the number of moles of isocyanate groups in the prepolymer is in the range of 1.01 to 2.00, preferably 1.03 to 1.06. It is preferable to react in such a manner.

<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 base material, 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 base material, 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. An acrylic monomer 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.

<Other binder resins>
As the binder resin, a resin other than the above urethane resin, vinyl chloride copolymer resin, and cellulose resin may be used in combination as long as it has binder performance. For example, a polyolefin resin, an ethylene-vinyl acetate copolymer resin, etc. 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 modified resins thereof. These resins can be used alone or in admixture 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 chlorinated olefin resin in the present invention preferably has a chlorine content of 25 to 45% by mass, preferably 26 to 40% by mass, in order to improve the adhesiveness to the easy-adhesion-treated substrate and the lamination strength. More preferred. Here, the chlorine content in the present invention means the content mass% of chlorine atoms in 100% by mass of the chlorinated olefin 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 5000 to 30000. Further, from the viewpoint of the balance with the blocking resistance, the chlorinated olefin resin is preferably contained in an amount of 0.1 to 2% by mass in 100% by mass of the ink. More preferably, it is 0.2 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 a viscous liquid even at a low temperature, and the substrate adhesiveness is improved by the above amount. 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. In this case, excellent substrate adhesion can be obtained when used in combination with the above-mentioned polyurethane resin having a polyester structural unit composed of a diol having an alkyl substituent and a dibasic acid.

Further, the chlorinated polyolefin resin may be a copolymer resin with another monomer.
As long as it has the above chlorine content, there is no particular limitation. As the copolymerizable monomer, an acrylic monomer, an acidic monomer, a vinyl acetate monomer, a styrene monomer and the like are preferable. Examples of the acrylic monomer include the above-mentioned acrylic monomer, and examples of the acidic monomer include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, and anhydrous. Examples thereof include aconitic acid, maleic anhydride, and (meth) acrylic acid.

<Titanium oxide pigment>
The titanium oxide pigment that can be used in the present invention has a rutile-type crystal structure that is surface-treated with at least silica or alumina. Having this processing layer improves the printability of the gravure ink. Further, it may be treated with other metals, and examples thereof include elemental metals composed of elements of Si, Al, Zn and Zr, oxides of Al and Zn, and the like. The "treated" state of the titanium oxide means that the surface of the titanium oxide particles is coated.

Further, the titanium oxide has an oil absorption amount of 14 according to the measurement method specified in JIS K5101.
It is preferably ~ 35 ml / 100 g, and more preferably 17 to 32 ml / 100 g. The average particle size (median particle size) measured by a transmission electron microscope is preferably 0.15 to 0.35 μm, more 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 addition to the titanium oxide pigment, other inorganic pigments and organic pigments can be further used in the gravure ink of the present invention.

The solid content weight ratio of titanium oxide and the binder resin is preferably 15: 10 to 50:10, more preferably 20: 10 to 45:10.

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, dianthraquinone type, anthrapyrimidine type, and perylene type. , Perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethinazo, flavanthron, diketopyrrolopyrrole, isoindoline, indanslon, carbon black and other pigments Can be mentioned. Also, for example, Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmin FB, Chromophtal Yellow, Chromophtal Red, Phtalocyanin Blue, Phthalocyanin Green, Dioxazine Violet, Quinacridone Magenta, Kinacridone Red, Indance. Ron blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, etc. Can be used together at any time.

Examples of the inorganic pigments include 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 may be either a leaving type or a non-leaving type.

Among the inorganic pigments, the extender pigment is not limited to the following, but barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate, silica and the like are preferable.

The titanium oxide pigment is preferably contained in an amount sufficient to secure the concentration and coloring power of the gravure ink, that is, 1 to 45% by mass in 100% by mass of the total mass of the gravure ink, and 2 to 35% by mass. It is more preferable to contain it.

<Organic solvent>
The gravure ink of the present invention preferably contains an organic solvent as a liquid medium. The organic solvent used is preferably used as a mixed solvent, such as 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. , Ester-based organic solvents, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and other known organic solvents can be used. Of these, an organic solvent (non-toluene-based organic solvent) that does not contain an aromatic organic solvent such as toluene or xylene is more preferable. More preferably, it is an organic solvent that does not contain an aromatic organic solvent and / or a ketone-based organic solvent such as methyl ethyl ketone (hereinafter referred to as "MEK"), and the ester-based organic solvent is the main component (50% or more) in the organic solvent. ) Is preferably contained. In particular, those containing an ester-based organic solvent and an alcohol-based organic solvent are preferable.
Further, the gravure ink of the present invention preferably contains water as a liquid medium. The content thereof is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, based on 100% by mass of the liquid medium. This content improves printability such as plate clogging, plate fog, and the like.

<Additives>
The gravure ink composition of the present invention can appropriately contain known additives, and in the production of the ink composition, known additives such as pigment derivatives, pigment dispersants, wetting agents, and adhesives are used as necessary. Auxiliary agents, leveling agents, defoaming agents, antistatic agents, trapping agents, blocking inhibitors, wax components, isocyanate-based curing agents, silane coupling agents and the like can be used. In addition, in order to improve blocking resistance, it is preferable to contain fatty acid amide and hydrocarbon wax in an amount of 0.01 to 2% by mass as a wax component.

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

<Manufacturing of gravure ink>
The gravure ink of the present invention can be produced by dissolving and / or dispersing a titanium oxide pigment, a binder resin, and a chlorinated polyolefin in an organic solvent. Specifically, for example, a titanium oxide pigment, a polyurethane resin, a vinyl chloride copolymer resin, and, if necessary, the above pigment dispersant are mixed to produce a pigment dispersion dispersed in an organic solvent, and the obtained pigment dispersion is produced. The gravure ink can be produced by further adding a polyurethane resin, water, or if necessary, another resin, an additive, or the like to the body. 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.

The viscosity of the laminating gravure ink produced by the above method is 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) by the gravure printing method. Is preferable. More preferably, it is 50 to 400 cps. In this viscosity range, the viscosity of Zahn Cup # 4 corresponds to about 9 to 40 seconds. The viscosity of the gravure ink composition can be adjusted by appropriately selecting the type and amount of the raw material 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.

<Printed matter>
The gravure ink of the present invention can be printed by a gravure printing method. For example, it is diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing and supplied to each printing unit alone or in combination. After printing with the gravure ink composition of the present invention on a substrate, a printed layer can be formed by removing volatile components to obtain a printed matter.

<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 K 6768 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 polyethylene terephthalate or a 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 present invention is not limited to these examples. Unless otherwise specified, parts and% in the present invention represent parts by weight and% by weight.

(Hydroxy group value)
Obtained according to JIS K0070.
(Acid value)
Obtained according to JIS K0070.
(Amine value)
The amine value was determined according to the following method according to JIS K0070 with the same amount of potassium hydroxide as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin.
The sample was precisely weighed in an amount of 0.5 to 2 g (sample solid content: Sg). To the 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 to the obtained solution as an indicator, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). With the point where the color of the solution changed from green to yellow as the end point, the amine titer was determined by the following (Equation 2) using the titration amount (AmL) at this time.
(Formula 2) Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

(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

(Wetting index of base material)
It was determined according to the method described in JIS K 6768 using a wetness index standard solution.

(Synthesis Example 1) [Polyurethane Resin PU1]
40 parts of polyester polyol (hereinafter "MPD / AA") which is a condensate of methylpentanediol having a number average molecular weight of 2000 and adipic acid, 60 parts of polypropylene glycol (hereinafter "PPG") having a number average molecular weight of 1000, isophorone diisocyanate (hereinafter "" IPDI ") 37.3 parts 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 the terminal isocyanate urethane prepolymer. Then, 15.1 parts of isocyanate diamine (hereinafter "IPDA"), 2.0 parts of iminobispropylamine (hereinafter "IBPA"), 1.0 part of 2- (2-aminoethylamino) ethanol (hereinafter "2AEA"), To a mixture of 328.4 parts of a mixed solvent of ethyl acetate / isopropanol (hereinafter “IPA”) = 50/50, the obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C., and then 1 at 80 ° C. The reaction was carried out for a time to obtain a polyurethane resin solution PU1 having a solid content of 30%, an amine value of 4.0 mgKOH / g, a hydroxyl value of 3.5 mgKOH / g, and a weight average molecular weight of 38,000.

(Synthesis Examples 2 to 4) [Polyurethane Resin PU2 to PU4]
Using the raw materials shown in Table 1, polyurethane resin solutions PU2 to PU4 were obtained by the same method as in Synthesis Example 1. The 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-phenylenediisocyanate)

(Synthetic Example 5) [Vinyl chloride-acrylic copolymer resin (PVAc1)]
In a 1.0 L autoclave, _{1.0 g of potassium persulfate (K 2} S ₂ O ₈ ) was dissolved in 500 g of ion-exchanged water and degassed. After heating 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-ethylhexyl sulfosuccinate (product name: aerosol OT) was placed in an autoclave at 60 g. It was added and reacted at ° C. and 6.5 atm. The polymerization reaction was carried out 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. Further, a vinyl chloride-acrylic copolymer resin was dissolved in ethyl acetate to obtain a varnish (PVAc1) having a solid content of 30%. The content of 2-hydroxypropyl acrylate in the obtained resin was 14.0%, the weight average molecular weight was 50,000, and the glass transition temperature was 70 ° C.

(Example 1) [Preparation of gravure ink S1]
30 parts of polyurethane resin solution PU1 (solid content 30%), vinyl chloride-vinyl acetate copolymer resin (solvine TA5R: manufactured by Nisshin Kagaku Kogyo Co., Ltd. Vinyl chloride: vinyl acetate: vinyl alcohol = 88: 1: 11 (solid content 30) % Ethyl acetate solution)) 5 parts, JR-806 (Titanium rutyl oxide crystal structure manufactured by Teika Co., Ltd. Surface treatment with silica and alumina, average particle size 0.27 μm, oil absorption 21 (ml / 100 g))
30 parts and 34 parts of a solution of propyl acetate / IPA = 70/30 were mixed and dispersed with an Eiger mill for 20 minutes. Product name: 370M Chlorine content 30% Solid content 50%) 0.5 parts was added and then stirred and mixed for 10 minutes to obtain gravure ink S1.

(Examples 2 to 19) [Preparation of gravure inks S2 to S19]
Gravure inks S2 to S19 were obtained by the same method as in Example 1 except that the raw materials shown in Table 2 were used. The abbreviations in Table 2 represent the following.
CR-57: Titanium rutile crystal structure manufactured by Ishihara Sangyo Co., Ltd. Surface treatment with alumina, zirconia and organic substances Average particle size 0.24 μm Oil absorption 17 (ml / 100 g)
CR-85: Titanium rutile oxide crystal structure manufactured by Ishihara Sangyo Co., Ltd. Silica and alumina surface treatment Average particle size 0.25 μm Oil absorption 30 (ml / 100 g)
DLX5-8: Nitrocellulose manufactured by ICI Novel enterprises
Nitrogen content 12.0% (solid content 30% isopropanol solution)
814B: Chlorinated polypropylene resin manufactured by Nippon Paper Industries, Ltd. Chlorine content 41%
2027MB: Chlorinated polypropylene resin manufactured by Nippon Paper Industries, Ltd. Chlorine content 27%
803LT: Chlorinated polyolefin resin manufactured by Nippon Paper Industries, Ltd. Chlorine content 26.5%
3228S: Acid-modified chlorinated polyolefin resin manufactured by Nippon Paper Industries, Ltd. Chlorine content 28%
In Table 2, the weight of the solvent solution is shown for the binder resin, and the weight of the resin solid content is shown for the chlorinated polyolefin.

(Comparative Examples 1 to 5) [Preparation of Gravure Inks SS1 to SS5]
Gravure inks SS1 to SS5 were obtained by the same method as described in Examples 1 to 19 except that the raw materials shown in Table 3 were used. The abbreviations in Table 3 are as follows.
-JA-3: Titanium oxide anatase type crystal structure manufactured by TAYCA Corporation No surface treatment Average particle size 0.18 μm Oil absorption 23 (ml / 100 g)
・ A-124GP: Polyester resin made by Takamatsu Oil & Fat Co., Ltd. 25% solid content solution ・ 851L: Acid-modified chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd. Chlorine content 19%

(Example 20)
<Printing of gravure ink>
The gravure ink S1 obtained above is subjected to a viscosity of 16 seconds (25 ° C., Zahn cup No.) by a mixed solvent (methyl ethyl ketone "MEK": Npropyl acetate "NPAC": isopropanol "IPA" = 30: 40: 30). 3. Dilute to 3) and print with Helio 175-line solid plate (plate type compressed, 100% solid pattern) on the corona discharge-treated surface or alumina-deposited surface of the plastic substrate shown below at a printing speed of 100 m / min. Then, printed matter 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 printing J1 (1): Biaxially stretched polypropylene (OPP) base material manufactured by Toyobo Co., Ltd. P2261 Thickness 20 μm Wetting index of corona discharge treated surface 34 dyne / cm
-Base material used for printing K1 (2): Biaxially stretched polypropylene (OPP) base material manufactured by Toyobo Co., Ltd. P2261 Thickness 20 μm Wetting index of corona discharge treated surface 40 dyne / cm
-Base material used for printing L1 (3): Unitika's biaxially stretched polyester (PET) base material PTM film thickness 12 μm Wetting index of corona discharge treated surface 45 dyne / cm
-Base material used for printing M1 (4): Alumina-deposited biaxially stretched polyester (alumina-deposited PET) base material manufactured by Mitsui Chemicals Tohcello Co., Ltd.
As for the base material (1) used for printing J1, the base material (2) used for printing K1 was allowed to stand at 40 ° C.-80% RH for 6 days to intentionally treat the corona discharge surface. It is the one that lowered the wettability index of.

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

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

(Examples 21 to 38)
Printed matter J2 to J19, K2 to K19, L2 to L19, and M2 to M19 were obtained in the same manner as in Example 20 except that the inks shown in Table 2 were used in the combinations shown in Table 4. Further, the printed surface of the printed matter J2 to J19 was subjected to an extrusion laminating process in the same manner as described above to obtain a laminated body. Further, the printed matter of the printed matter L2 to L19 was dry-laminated in the same manner as described above to obtain a laminated body. The evaluation was performed after holding the laminate at 40 ° C. for 48 hours.

(Comparative Examples 6 to 10)
Printed matter JJ1 to JJ5, KK1 to KK5, LL1 to LL5, and MM1 to MM5 were obtained in the same manner as in Example 20 except that the inks shown in Table 3 were used in the combinations shown in Table 5. Further, the printed surfaces of the printed matter JJ1 to JJ5 were subjected to an extrusion laminating process in the same manner as described above to obtain a laminated body. Further, the printed matter of the printed matter LL1 to LL5 was dry-laminated in the same manner as described above to obtain a laminated body. The evaluation was performed after holding the laminate at 40 ° C. for 48 hours.

<Evaluation>
The following evaluations were performed on the gravure inks, printed matter, and laminates of Examples and Comparative Examples. The results are shown in Tables 4 and 5.

<Adhesion>
Printed matter J1 to J19, K1 to K19, L1 to L19 and M1 to M19 and JJ1 to JJ5, KK1 to KK5, LL1 to LL5 and MM1 to MM5 are each left at 25 ° C. for 1 day and then adhered to the printed surface with a width of 12 mm. A tape (cellophane tape manufactured by Nichiban Co., Ltd.) was attached, and the appearance of the printed surface when the tape (cellophane tape manufactured by Nichiban Co., Ltd.) was rapidly peeled off in the 90 ° direction with respect to the substrate surface was visually judged. The judgment criteria were as follows.
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.

<Blocking resistance>
The blocking resistance of printed matter J1 to J19, K1 to K19, JJ1 to JJ5, and KK1 to KK5 was evaluated under the following conditions.
(Sample and pressure)
Printed surface of OPP printed matter / Non-corona treated surface of OPP base material 10 kg / cm ²
(Standing condition) 40 ° C-80% RH 48 hours (Evaluation method) The printed surface and the base material are peeled off, and the degree of peeling of the ink film from the printed surface is visually judged.
Judgment criteria 5. The ink film on the printed surface does not peel off at all, and the peeling resistance is low (good)
4. 2. The peeling area of the ink film is 1% or more and less than 5%, and the peeling resistance is small (practical). 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 a laminate using printed matter J1 to J19 and L1 to L19, and a laminate using JJ1 to JJ5 and LL1 to LL5, the printed portion is cut to a width of 15 mm, peeled off on the ink surface and the base material surface, and then peeled off. The strength (laminate strength) was measured with a 2.01 universal tensile tester manufactured by Intesco.
Judgment 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. 3. Tensile strength is 0.4N / 15mm or more and less than 0.6N / 15mm (slightly defective)
2. Tensile strength is 0.2N / 15mm or more and less than 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 (plate fogability)>
The plate castability of the gravure inks S1 to S18 and SS1 to SS5 was evaluated. The diluting solvent was MEK: NPAC: IPA = 30:40:30, the viscosity was set to 16 seconds (25 ° C) with Zahn Cup # 3, and the area of the plate cover portion 90 minutes after the plate slipped on the printing machine was set. A visual judgment was made and an evaluation was performed.
Judgment 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.

(Comparative Example 11)
The gravure ink S1 prepared in Example 1 is printed on a polypropylene base material (product name N10 wetness index 28dyne / cm manufactured by Toray Industries, Inc.) in the same manner as in Example 20 and subjected to extrusion lamination to obtain a laminate. rice field. When the adhesion and the laminate strength of the obtained printed matter and the laminate were evaluated, all the ink coatings were peeled off in the adhesion evaluation, and the laminate strength was 0.1 N / 15 mm.

(Comparative Example 12)
The gravure ink S1 prepared in Example 1 is printed on an aluminum-deposited polyester base material (product name H-27 wetness index 63dyne / cm manufactured by Reiko Co., Ltd.) in the same manner as in Example 20, and extrusion laminating is performed. , A laminate was obtained. When the adhesion and the laminate strength of the obtained printed matter and the laminate were evaluated, all the ink coatings were peeled off in the adhesion evaluation, and the laminate strength was 0.1 N / 15 mm.

From the evaluation results, it was found that the gravure ink of the present invention has good printability during gravure printing, and has good adhesion, blocking resistance, and lamination strength to a substrate having a wide wetness index. rice field.

Claims (8)

A gravure ink for forming a printed layer of a laminated laminate having a printed layer between a base material 1 having a wetness index of 30 to 60 dyne / cm on a surface in contact with the printed layer and the base material 2, and being oxidized. A gravure ink containing a titanium pigment, a polyurethane resin and a chlorinated polyolefin resin and satisfying the following (1) and (2).
(1) The titanium oxide pigment is rutile-type titanium oxide having a treated layer made of at least silica and / or alumina.
(2) The chlorinated polyolefin resin has a chlorine content of 25 to 45% by mass and is contained in 100% by mass of the ink in the range of 0.1 to 2% by mass. The first aspect of claim 1, further comprising a vinyl chloride copolymer resin and / or a cellulosic resin, and containing a polyurethane resin, a vinyl chloride copolymer resin and a cellulosic resin in a mass ratio of 95/5 to 40/60. Gravure ink. The gravure ink according to claim 1 or 2, wherein the polyurethane resin is a polyurethane resin having at least a structural unit derived from a polyester polyol. The polyurethane resin according to any one of claims 1 to 3, wherein the polyurethane resin 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 4, wherein the polyurethane resin has a structure represented by the following general formula (1).
General formula (1)
-COO-CH ₂ CR ¹ R ² CH ₂ -OCO-
(In the formula, 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 5, wherein the chlorinated polyolefin resin is a chlorinated polypropylene resin. A printed matter having a printed layer made of the gravure ink according to any one of claims 1 to 6 on the base material 1. A laminated laminate having at least a printing layer made of the gravure ink according to any one of claims 1 to 6 between the base material 1 and the base material 2.