JP7039952B2 - Gravure ink for laminating and its printed matter and laminate - Google Patents

Description

The present invention relates to a gravure ink for laminating, a printed matter thereof, and a laminated body.

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 for decoration or surface protection of the substrate. 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 substrate. 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 fleshed. 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.

The pattern printed with gravure ink may be used as the outermost surface of the packaging bag, or may be used as an intermediate layer when the base materials are bonded together. All are used for front printing, and the latter is used separately for laminating. This is because there is a method of use as a packaging material suitable for each case.

In the gravure ink for laminating, after the ink is printed on the base material, the base material is further bonded to the printed 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).

In recent years, attention has been paid to the use of biomass-derived materials for environmental friendliness. When a material / raw material derived from biomass is applied to the above-mentioned gravure ink for laminating, it is generally difficult to improve the characteristics as compared with the gravure ink for laminating which does not use the biomass material in many cases. In recent years, gravure inks and the like in which a polyurethane resin and a rosin resin are used in combination have been proposed (Patent Documents 4 and 5).

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. 2015-160947 JP-A-2015-160949

INDUSTRIAL APPLICABILITY The present invention has good ink stability over time even when a biomass-derived component is used. It is an object of the present invention to provide a gravure ink for laminating, which has good characteristics even in various laminated laminate configurations and further has good printability.

As a result of diligent research on the above-mentioned problems, the present inventor has found that the problem can be solved by using the gravure ink for laminating described below, and has completed the present invention.

That is, the present invention is a laminating gravure ink containing a polyurethane resin, a rosin resin and a vinyl chloride-vinyl acetate copolymer resin, which is characterized by satisfying the following (1) and (2). Regarding.
(1) The rosin resin has an acid value of 100 mgKOH / g or less and a softening point of 60 to 150 ° C.
(2) The vinyl chloride-vinyl acetate copolymer resin has a hydroxyl value of 30 to 200 mgKOH / g.

The present invention is characterized in that the mass ratio of the rosin resin to the vinyl chloride-vinyl acetate copolymer resin (rosin resin: vinyl chloride-vinyl acetate copolymer resin) is 20:80 to 90:10. Regarding gravure ink for lamination.

Further, the present invention is characterized in that the rosin resin is an ester condensed resin of a low molecular weight polyol having 2 to 4 hydroxyl groups per molecule and a number average molecular weight of less than 1000, and loginic acid. The present invention relates to the gravure ink for laminating.

The present invention also relates to the gravure ink for laminating, which further contains carnauba wax.

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

The present invention also relates to a laminated laminate having a base material 1, a printing layer made of the gravure ink for laminating, an adhesive layer, and a base material 2 in this order.

According to the present invention, the stability of the ink over time is good even when a biomass-derived component is used. It was possible to provide a gravure ink for laminating, which has good characteristics even in various laminated laminate configurations and further has good printability.

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 thereof is not exceeded. Not limited to the content.

The gravure ink for laminating of the present invention may be simply abbreviated as "gravure ink" or "ink", but they have the same meaning. Further, the layer on which the gravure ink for laminating is printed may be described as "printing layer", "ink layer" or "ink film", but they have the same meaning.

In the present invention, the polyurethane resin, the vinyl chloride-vinyl acetate copolymer resin, and the rosin resin having a certain requirement are used in combination as the binder resin to improve the laminate strength and printability. This is because the rosin resin has good substrate adhesiveness and pigment dispersibility when the acid value and the softening point are in the above ranges, and also shows improvement in printability.

<Binder resin>
The binder resin preferably contains a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, and a rosin resin in an amount of 60 to 100% by mass in the total weight of the binder resin. It is more preferably contained in an amount of 80 to 100% by mass. The binder resin is an ink binder and refers to a thermoplastic resin that is soluble in an organic solvent.

<Polyurethane resin>
The polyurethane resin preferably has a weight average molecular weight of 10,000 to 100,000, and preferably has a glass transition temperature of −60 ° C. to 0 ° C. 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 maximum value of Tan δ may be substituted for the dynamic viscoelasticity measurement.

The polyurethane resin 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 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 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 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 the polyester polyol means the structure of the polyester polyol, which is a raw material of the 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 the polyester polyol. It is a value calculated from the blending amount of.

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 50/50 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 90/10. Is more preferable.

The polyurethane resin is not particularly limited, and is appropriately produced by a known method described in, for example, Japanese Patent Application Laid-Open No. 2013-213109 and Japanese Patent Application Laid-Open No. 2005-298618. For example, it can be obtained by reacting a polyurethane resin composed of a polyol and a polyisocyanate or a urethane prepolymer having a terminal isocyanate composed of a polyol and a polyisocyanate with a polyamine. When a polyamine is used, a polyurethane resin that forms a urea bond can be obtained by reacting with an isocyanate group. Polyurethane resins containing structural units derived from polyols are 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, hydrogenated dimer diol and the like. Above all, the combined use of the polyether polyol and the polyester polyol is preferable.

As the above-mentioned polyether polyol, for example, polyethylene glycol, polytetramethylene glycol, polytrimethylene glycol, polypropylene glycol and the like are preferable, and two or more of these may be used in combination. 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 one molecule of the polyol and the hydroxyl value in 1 g of the solid content of the polyol (value converted to the amount of potassium hydroxide in the number of molar hydroxyl groups). It is obtained by (Equation 1).
(Equation 1) Number of polyols Average molecular weight = 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 acid 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. Of these, adipic acid, sebacic acid and the like are preferable.
Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octanediol. , 1,9-Nonandiol, Neopentyl Glycol, 3-Methyl-1,5-Pentanediol, 2-Methyl-1,3-Propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl- 1,5-Pentanediol, 1,12-Octadecanediol, 1,2-Alcandiol, 1,3-Alcandiol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimerdiol , Hydrophobic dimerdiol and the like.
As the diol, 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 means 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.

Known polyisocyanates can be used, and examples thereof include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.
For example, examples of the aromatic diisocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, and dialkyldiphenylmethane diisocyanate. Examples thereof include tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediocyanate, m-tetramethylxylylene diisocyanate, 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, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and 1,3-bis (isocyanatemethyl) cyclohexane. , Methylcyclohexanediisocyanate, norbornandiisocyanate, and dimerge isocyanate obtained by converting the carboxy group of dimer acid into an isocyanate group.
Of these, aromatic diisocyanates and / or alicyclic diisocyanates are preferable.
Among the above-exemplified compounds, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isocyanurates of hexamethylene diisocyanate and the like are preferable.

The polyamine refers to an amine compound having at least two amino groups. The polyamine 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 diamines and polyfunctional amines.
Diamines include ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, p-phenylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxy. Ethylpropylene diamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrropyrethylenediamine, di-2-hydroxypyrropyrethylenediamine, di-2-hydroxypropyl A diamine having a hydroxyl group such as ethylene diamine can also be used. These chain extenders can be used alone or in admixture of two or more.
As the polyfunctional amine, for example, triamine is preferable. For example, diethylenetriamine, iminobispropylamine: (IBPA, 3,3'-diaminodipropylamine), triethylenetetramine, N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6. -Iminodihexylamine, 3,7-diazanonan-1,9-diamine, N, N'-bis (3-aminopropyl) ethylenediamine are suitable.

The polyamine may contain a compound having a primary or secondary monovalent amino group. These compounds function as polymerization inhibitors aimed at stopping the excessive reaction. Preferable examples of such compounds include dialkylamines such as di-n-butylamine and amino alcohols such as 2-ethanolamine.

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin is a resin obtained by copolymerizing vinyl chloride and vinyl acetate. The hydroxyl value of the vinyl chloride-vinyl acetate copolymer resin is 30 to 200 mgKOH / g. The hydroxyl value is not particularly limited as long as it is within the above range, and the resin has excellent solvent properties. Further, by combining with a polyurethane resin and a rosin resin, it is excellent in adhesion to a base material, film physical characteristics, laminating strength and the like. More preferably, it is 50 to 150 mgKOH / g.

The weight average molecular weight of the vinyl chloride-vinyl acetate copolymer resin is preferably 5,000 to 100,000, more preferably 20,000 to 70,000. The structure derived from the vinyl acetate monomer in 100% by mass of the solid content 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. .. This is because the adhesiveness to the substrate, the physical characteristics of the film, the laminating strength and the like are improved by using the polyurethane resin and the rosin resin described later in combination. Further, vinyl chloride and vinyl acetate preferably have a glass transition temperature of 50 ° C to 90 ° C.

<Rosin resin>
The rosin resin used in the present invention has a structural unit derived from logoic acid (avietic acid, neo-avietic acid, palastolic acid, pimaric acid, isopimaric acid, dehydroabietic acid, etc.) as a main component (50% by mass or more). To say. The loginic acid or rosin resin may be hydrogenated. The acid value of the rosin resin is 100 mgKOH / g or less, and the softening point is 60 to 150 ° C. This is because the physical characteristics of the laminate are improved by using the vinyl chloride-vinyl acetate copolymer resin and the polyurethane resin in combination, and the stability of the gravure ink for laminating is improved to improve the printability. Rosin resin is a biomass material derived from pine fat and contributes to the improvement of the biomass component in the solid content of the ink.
Examples of the type of rosin resin include rosin-modified phenolic resin, rosin ester, rosin-modified maleic acid resin, polymerized rosin resin, and the like, and at least one rosin resin selected from these is preferable. The acid value is preferably 80 mgKOH / g or less, and more preferably 50 mgKOH / g or less. Further, the softening point is preferably 70 to 130 ° C. This is because the laminate strength is improved.

The above-mentioned softening point is a measured value by the ring-and-ball method. For example, the measurement method described in JIS K2207 can be mentioned.

(Rosin ester)
The rosin resin is preferably a rosin ester, which is an ester condensation resin of a low molecular weight polyol having a molecular weight of less than 1000 and a rosin acid. The small molecule polyol preferably has 2 to 4 hydroxyl groups (sometimes abbreviated as 2 to 4 functional). Further, it is more preferable that the small molecule polyol has a molecular weight of 50 to 500.
Examples of the low molecular weight polyol include bifunctional low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,10-decanediol, and trifunctional low molecular weight polyols such as glycerin and trimethylolpropane. , Erythritol, pentaerythritol and other tetrafunctional low molecular weight polyols are suitable. Of these, trifunctional small molecule polyols are preferred.
The weight average molecular weight of the rosin ester is preferably 500 to 2000. It is more preferably 500 to 1500.

The mass ratio of the rosin resin to the vinyl chloride-vinyl acetate copolymer resin (rosin resin: vinyl chloride-vinyl acetate copolymer resin) is preferably 20:80 to 90:10. It is more preferable that the ratio is 30:70 to 90:10.
The mass ratio of the polyurethane resin to the vinyl chloride-vinyl acetate copolymer resin (polyurethane resin: vinyl chloride-vinyl acetate copolymer resin) is preferably 95: 5 to 30:70. It is more preferable that the ratio is 90:10 to 40:60.
The polyurethane resin, vinyl chloride-vinyl acetate copolymer resin and rosin resin are preferably contained in a total amount of 3 to 20% by mass, preferably 5 to 15% by mass, in 100% by mass of the gravure ink of the present invention.

<Other binder resin>
As the above-mentioned binder resin, a resin other than the above may be used in combination as long as the effect of the present invention is not impaired. For example, a polyolefin resin, a chlorinated polyolefin resin, an ethylene-vinyl acetate copolymer resin, and a polyester resin may be used in combination. , Acrylic resin, polyamide resin, cellulose 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 , Polyvinyl chloride resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, rubber chloride, butyral, silicone resin and modified resins thereof are suitable. These resins can be used alone or in admixture of two or more, and the content thereof is preferably 0 to 40% by mass, preferably 0 to 20% by mass, based on 100% by mass of the solid content of the binder resin. % Is more preferable.

<Pigment>
In the present invention, the pigment can be either an inorganic pigment or an organic pigment, and although not particularly limited, good substrate adhesion can be obtained by using the organic pigment. The organic pigment is not limited to the following examples, but is not limited to soluble azo type, insoluble azo type, azo type, phthalocyanine type, halogenated phthalocyanine type, anthraquinone type, anthanthrone type, dianslaquinonyl type, anthrapyrimidine type, Perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindoline-based, quinophthalone-based, azomethine-azo-based, flavanthrone-based, diketopyrrolopyrrole-based, isoindoline-based, indancelon-based, carbon black-based, etc. Pigments can be mentioned. Also, for example, Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolon Orange, Carmin FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance. Examples thereof include lonblue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigment.

Hereinafter, as the organic pigment, at least one or more selected from the group consisting of black pigment, indigo pigment, green pigment, red pigment, purple pigment, yellow pigment, orange pigment and brown pigment is preferable. It should be noted that C.I. I. Pigments can be used as appropriate.

On the other hand, examples of the inorganic pigment include white inorganic pigments such as titanium oxide and zinc oxide. Among the inorganic pigments, the use of titanium oxide is particularly preferable. Titanium oxide exhibits a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance, and from the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina.

Examples of inorganic pigments other than white include aluminum particles, mica (mica), bronze powder, chrome vermillion, chrome yellow, cadmium yellow, cadmium red, ultramarine, navy blue, red iron oxide, yellow iron oxide, iron black, zinc oxide and the like. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and may be 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 pigment is preferably contained in an amount sufficient to secure the concentration and coloring power of the gravure ink, that is, 1 to 50% by mass in 100% by mass of the total mass of the gravure ink, and 2 to 45% by mass. It is more preferable to do so. In addition, these pigments can be used alone or in combination of two or more.

The hue in the gravure ink of the present invention is an ink composition of other hues (a total of 5 colors of yellow, red, indigo, ink, and white as basic colors, red (orange) as an outer color of process gamut, and grass, if necessary. It may be mixed with (green), three colors of purple, and transparent yellow, peony, vermilion, brown, and pearl).

<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, 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. , Known organic solvents such as ester-based organic solvents, methanol, ethanol, n-propanol, isopropanol, n-butanol, and other alcohol-based 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, an organic solvent containing no aromatic organic solvent and / or a ketone organic solvent such as methyl ethyl ketone (hereinafter referred to as “MEK”) is more preferable. In particular, those containing an ester-based organic solvent and an alcohol-based organic solvent as main components are preferable.

<Additives>
The gravure ink composition of the present invention may appropriately contain known additives, and in the production of ink compositions, known additives such as pigment derivatives, dispersants, wetting agents, and adhesive aids are used as necessary. Agents, leveling agents, defoaming agents, antistatic agents, trapping agents, anti-blocking agents, wax components, isocyanate-based curing agents, silane coupling agents and the like can be used. In addition, it is preferable to contain 0.01 to 3% by mass of carnauba wax as a wax component in order to improve blocking resistance.

(Carnauba wax)
The carnauba wax is preferably derived from coconut oil. Carnauba wax preferably has a melting point of 60 to 110 ° C. Further, it is preferably 70 to 100 ° C.

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

<Manufacturing of gravure ink>
The gravure ink of the present invention can be produced by dissolving and / or dispersing a pigment, a binder resin, or the like in an organic solvent. Specifically, for example, an organic pigment, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin and the above rosin resin are mixed to produce a pigment dispersion dispersed in an organic solvent, and the obtained pigment dispersion is further added. A gravure ink can be produced by blending a resin component such as a polyurethane resin and, if necessary, another resin or an additive. Further, the particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the crushed media of the disperser, the filling rate of the crushed media, the dispersion treatment time, the discharge rate 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 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 in Zahn Cup # 4 corresponds to about 9 to 40 seconds. The viscosity of the gravure ink 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 mixed. After printing with the gravure ink composition of the present invention on the substrate 1, a printed layer can be formed by removing volatile components to obtain a printed matter.

<Base material 1>
The base material that can be used in the printed matter of the present invention is, for example, polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resin such as polystyrene, AS resin and ABS resin, nylon, polyamide and polyvinyl chloride. , Polyvinylidene chloride, cellophane, paper, aluminum, etc., or a film-like substrate made of a composite material thereof. Further, a vapor-deposited base material obtained by depositing an inorganic compound such as silica, alumina, or aluminum on a polyethylene terephthalate or a nylon film can also be used, and the vapor-deposited surface may be coated with polyvinyl alcohol or the like.
It is preferable that the surface to be printed (the surface in contact with the print layer) of the substrate is easily adhered, and the easy adhesion treatment includes, for example, corona discharge treatment, ultraviolet / ozone treatment, plasma treatment, oxygen plasma treatment, and the like. Primer treatment and the like can be mentioned. 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>
The base material 2 may be the same as or different from the base material 1, and may be further laminated with different types of base materials 2 to form a laminated body. Of these, an unstretched polyolefin base material is preferable, and an unstretched polyethylene base material and an unstretched polypropylene base material are preferable.

<Laminated body>
In the laminate of the present invention, a film layer made of the base material 2 is further bonded to the printed matter 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, a printing layer, an adhesive layer, and a film layer in this order. The film layer may be the same as or different from the base material.
Examples of the adhesive layer include a layer made of an anchor coat 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 the 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 manufacturing 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 plastic film is laminated on the printed surface by applying an adhesive such as urethane, 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. The parts and% in the present invention represent parts by weight and% by weight unless otherwise specified.

(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 finely 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). The amine value was determined by the following (formula 2) using the titration amount (AmL) at this point, with the point where the color of the solution changed from green to yellow as the end point.
(Equation 2) Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

(Softening point)
It was measured according to the ring ball method (JISK2207).

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

(Synthesis Example 1) [Polyurethane Resin PU1]
80 parts of a polyester polyol which is a condensate of 3-methyl-1,5-pentanediol (hereinafter "MPD") and adipic acid (hereinafter "AA") having a number average molecular weight of 2000, and polypropylene glycol having a number average molecular weight of 2000. 20 parts (hereinafter "PPG"), 1.5 parts of 1,3-propanediol, 31 parts of isophorone diisocyanate (hereinafter "IPDI"), and 33.1 parts of ethyl acetate are reacted at 80 ° C. for 5 hours under a nitrogen stream. A solvent solution of the terminal isocyanate urethane prepolymer was obtained.
Next, 11 parts of isophorone diamine (hereinafter "IPDA"), 1.5 parts of iminobispropylamine (hereinafter "IBPA"), 0.8 parts of 2-ethanolamine (hereinafter "2EtAm"), ethyl acetate / isopropanol (hereinafter "IPA"). A mixture of 307.1 parts of a mixed solvent of 60/40 was gradually added with the obtained terminal isocyanate prepolymer solution at 40 ° C., and then reacted at 80 ° C. for 1 hour to have a solid content of 30%. , A polyurethane resin solution PU1 having an amine value of 4.2 mgKOH / g, a hydroxyl value of 5.0 mgKOH / g, and a weight average molecular weight of 50,000 was obtained.

(Synthesis Example 2) [Polyurethane Resin PU2]
70 parts of polyester polyol which is a condensate of neopentyl glycol (hereinafter "NPG") and sebacic acid (hereinafter "SA") having a number average molecular weight of 2000, 30 parts of PPG having a number average molecular weight of 1000, IPDI 28.9 parts, and ethyl acetate. 32.2 parts were reacted under a nitrogen stream at 80 ° C. for 5 hours to obtain a solvent solution of the terminal isocyanate urethane prepolymer.
Next, the obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C. to a mixture of 11.5 parts of IPDA, 2.0 parts of 2EtAm, and 300 parts of a mixed solvent of ethyl acetate / IPA = 60/40, and then 80. The reaction was carried out at ° C. for 1 hour to obtain a polyurethane resin solution PU2 having a solid content of 30%, an amine value of 8.9 mgKOH / g, a hydroxyl value of 12.9 mgKOH / g and a weight average molecular weight of 40,000. Sebacic acid is derived from castor oil.

(Synthesis Example 3) [Polyurethane Resin PU3]
50 parts of polyester polyol which is a condensate of MPD and SA with a number average molecular weight of 2000, 50 parts of castor oil polyol (URIC manufactured by Itoh Oil Chemicals Co., Ltd.) with a number average molecular weight of 2500, IPDI 28.9 parts, and 39.7 parts of ethyl acetate are nitrogen. The reaction was carried out at 80 ° C. for 5 hours under an air stream to obtain a solvent solution of the terminal isocyanate urethane prepolymer.
Next, the obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C. to a mixture of 11 parts of IPDA, 0.5 part of 2EtAm, and 357.9 parts of a mixed solvent of ethyl acetate / IPA = 60/40, and then 80. The reaction was carried out at ° C. for 1 hour to obtain a polyurethane resin solution PU3 having a solid content of 30%, an amine value of 5.0 mgKOH / g, a hydroxyl value of 2.7 mgKOH / g and a weight average molecular weight of 60,000. The castor oil polyol is derived from castor oil.

(Example 1) [Creation of gravure ink S1]
30 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 (hydroxyl value 140 mgKOH) / G Solid content 30% ethyl acetate solution)) 6 parts, 9 parts of the following rosin resin 1 and C.I. I. 10 parts of Pigment Blue 15: 4 (product name: Lionol Blue FG7330 manufactured by Toyokara Co., Ltd.) and 45 parts of a solution of propyl acetate / IPA = 70/30 were mixed and dispersed in an Eiger mill for 20 minutes to gravure ink S1. Got

(Examples 2 to 16) [Preparation of gravure inks S2 to S16]
Gravure inks S2 to S19 were obtained by the same method as in Example 1 except that the raw materials shown in Table 1 were used.
The abbreviations in Table 1 represent the following.
-Solvine AL: Vinyl chloride-vinyl acetate copolymer resin manufactured by Nissin Chemical Industry Co., Ltd. hydroxyl value 63 mgKOH / g Ethyl acetate solution with solid content of 30% -Titanium oxide: Silica / alumina-treated rutile-type titanium oxide JR701 manufactured by TAYCA Corporation
-Rosin resin 1: Rosin ester, which is an ester condensate of rosin acid and glycerin Acid value 10 mgKOH / g, weight average molecular weight 500-1500, softening point 87 ° C. Solid content 30% ethyl acetate solution-Rosin resin 2: rosin acid and penta Rosin ester, an ester condensate of erythritol Acid value 25 mgKOH / g, weight average molecular weight 1000-2000, softening point 120 ° C. Solid content 30% rosin acetate solution / rosin resin 3: Rosin hydride and polyol with molecular weight less than 500 Ester condensate Acid value 5 mgKOH / g, softening point 70 ° C. Solid content 30% ethyl acetate solution / rosin resin 4: Rosin-modified maleic acid resin Acid value 50 mgKOH / g, softening point 145 ° C. Solid content 30% ethyl acetate solution Rosin resin 1 to 4 contain 50% by mass or more of rosin (pine fat) -derived components.
・ Carnauba wax: Carnauba wax manufactured by Toa Kasei Co., Ltd. Melting point 70-90 ° C

(Comparative Examples 1 to 8) [Creation of Gravure Inks SS1 to SS8]
Gravure inks SS1 to SS8 were obtained by the same method as described in Examples 1 to 19 except that the raw materials shown in Table 2 were used. The abbreviations in Table 2 are as follows.
・ Solvine C: Vinyl chloride-vinyl acetate copolymer resin manufactured by Nisshin Kagaku Kogyo Co., Ltd. hydroxyl value 0 mgKOH / g Solid content 30% ethyl acetate solution ・ Hariester MSR-4: Harima Chemicals Co., Ltd. ・ Rodin resin acid value 140 mgKOH / g solid 30% ethyl acetate solution

(Example 17)
<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" = 40: 40: 20). 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 vapor-deposited surface of the plastic substrate shown below at a printing speed of 100 m / min. Then, printed matter J1 and K1 were obtained, respectively. The printing conditions were a temperature of 25 ° C. and a humidity of 60%.
-Base material used for printing J1: Biaxially stretched polypropylene (OPP) base material manufactured by Toyobo Co., Ltd. P2161 Film thickness 20 μm
-Base material used for printing K1: Mitsui Chemicals Tocello Co., Ltd. Alumina-deposited biaxially stretched polyester (alumina-deposited PET) base material TL-PET HS

<Dry laminating 1>
A urethane-based laminated adhesive (TM320L / curing agent manufactured by Toyo Morton Co., Ltd.) is applied to the printed surface of the printed matter J1 with an ethyl acetate solution having a solid content of 20% so that the adhesive layer after drying becomes 2.0 g / m ² . After coating and drying, a 40 μm-thick aluminum vapor-deposited polypropylene film (VMCPP) (ML-WS film thickness 40 μm manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was bonded to the adhesive layer and dry-laminated to obtain a laminate. ..
<Dry laminating 2>
A urethane-based laminated adhesive (TM320L / curing agent manufactured by Toyo Morton Co., Ltd.) is applied to the printed surface of the printed matter K1 with an ethyl acetate solution having a solid content of 20% so that the adhesive layer after drying becomes 2.0 g / m ² . After coating and drying, an unstretched polypropylene film (CPP) having a thickness of 40 μm (TUXFCS film thickness 40 μm manufactured by Mitsui Chemicals Tocello Co., Ltd.) was bonded to the adhesive layer and dry-laminated to obtain a laminate.

(Examples 18 to 32)
Printed matter J2 to J16 and K2 to K16 were obtained in the same manner as in Example 17 except that the inks shown in Table 1 were used in the combinations shown in Table 3. Further, the ink-coated surface of each of the obtained printed matter was laminated by the same method as in the dry laminating process 1 and the dry laminating process 2, to obtain a laminated body. The evaluation described below was performed after holding the laminate at 40 ° C. for 48 hours.

(Comparative Examples 9 to 16)
Printed matter JJ1 to JJ8 and KK1 to KK8 were obtained in the same manner as in Example 17 except that the inks shown in Table 2 were used in the combinations shown in Table 4. Further, the ink-coated surface of each of the obtained printed matter was laminated by the same method as in the dry laminating process 1 and the dry laminating process 2, to obtain a laminated body. The evaluation described below was performed after holding the laminate at 40 ° C. for 48 hours.

<Evaluation>
The following evaluations were made using the gravure inks, printed matter and laminates of Examples and Comparative Examples. The results are shown in Tables 3 and 4.

<Ink stability over time>
Using the gravure inks S1 to S16 of the example and the gravure inks SS1 to SS8 of the comparative example, the ink was left at 40 ° C. for 7 days, and the viscosity measurement data based on the elapsed time was measured with a Zahn cup # 4 manufactured by Rigosha. The storage stability of the ink was evaluated from the difference in viscosity immediately after finishing and after the elapsed time. In each ink, the number of seconds (viscosity) measured by Zahn Cup # 4 before the time-lapse test was in the range of 10 seconds to 30 seconds.
[criterion]
5. The change in viscosity over time is less than 1.2 times that immediately after finishing. (Good)
4. The change in viscosity over time is 1.2 to 1.5 times immediately after finishing. (Practical)
3. 3. The change in viscosity over time is 1.5 to 2 times immediately after finishing. (Slightly bad)
2. 2. Viscosity change over time is more than double that immediately after finishing. (Defective)
1. 1. Those that have separated, settled, or separated. (Extremely bad)
The evaluation that does not hinder practical use is 5 or 4.

<Printability (plate fogability)>
Plate fogability was evaluated using the gravure inks S1 to S16 of the examples and the gravure inks SS1 to SS8 of the comparative examples. The diluting solvent was MEK: NPAC: IPA = 40: 40: 20, the viscosity was 16 seconds (25 ° C.) with Zahn Cup # 3, and the area of the plate cover portion after 90 minutes of idling of the plate in the printing machine was set. A visual judgment was made and an evaluation was performed.
[criterion]
5. The plate cover area is 0% or more and less than 5% (good)
4. The plate cover area is 5% or more and less than 10% (practical)
3. 3. The plate cover area is 10% or more and less than 15% (slightly defective)
2. 2. The plate cover 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.

<Blocking resistance>
The blocking resistance of the printed matter J1 to J16 (Example) and the printed matter JJ1 to JJ8 (Comparative Example) was evaluated under the following conditions.
(Sample and pressure)
Printed matter of OPP printed matter / OPP base material non-corona treated surface 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.
[criterion]
5. The ink film on the printed surface does not peel off at all, and the peeling resistance is low (good).
4. The peeling area of the ink film is 1% or more and less than 5%, and the peeling resistance is small (practical).
3. 3. The peeled area of the ink film is 5% or more and less than 20% (slightly defective)
2. 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>
The printed portion of the laminate using the printed matter J1 to J16 (Example) and the printed matter JJ1 to JJ8 (Comparative Example) and the laminated matter using the K1 to K16 (Example) and the printed matter KK1 to KK8 (Comparative Example) is widened. After cutting at 15 mm and peeling off on the ink surface and the substrate surface, the peel strength (laminate strength) was measured with a 2.01 universal tensile tester manufactured by Intesco.
[criterion]
(In the case of a laminated body using printed matter J1 to J16 and printed matter JJ1 to JJ8)
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. 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.
[criterion]
(In the case of a laminated body using printed matter K1 to K16 and printed matter KK1 to KK8)
5. Tensile strength is 1.5N / 15mm or more (good)
4. Tensile strength is 1.0N / 15mm or more and less than 1.5N / 15mm (practical)
3. 3. Tensile strength is 0.8N / 15mm or more and less than 1.0N / 15mm (slightly defective)
2. 2. Tensile strength is 0.4N / 15mm or more and less than 0.8N / 15mm (defective)
1. 1. Tensile strength is less than 0.4N / 15mm (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a gravure ink for laminating, which has good stability over time of the ink even when a biomass-derived component is used, has good characteristics even in various laminated laminated body configurations, and has good printability. We were able to.

It was further satisfied that the blocking resistance was good, and it was shown that it is useful as an environment-friendly laminating gravure ink for forming a laminated laminate used as a packaging material.

Claims (2)

A method for producing a laminated laminate, which comprises a step of printing a gravure ink for laminating on a base material 1 to form a print layer, and a step of sequentially laminating an adhesive layer and a base material 2 on the print layer.
The laminating gravure ink contains a polyurethane resin, a rosin resin which is a rosin ester, and a vinyl chloride-vinyl acetate copolymer resin.
The mass ratio of the rosin resin to the vinyl chloride-vinyl acetate copolymer resin (rosin resin: vinyl chloride-vinyl acetate copolymer resin) is 30:70 to 90:10.
The acid value of the rosin resin is 100 mgKOH / g or less, and the softening point of the rosin resin is 60 to 150 ° C.
The rosin ester is an ester condensate of rosin acid and at least one selected from the group consisting of glycerin, trimethylolpropane, erythritol and pentaerythritol.
The hydroxyl value of the vinyl chloride-vinyl acetate copolymer resin is 30 to 200 mgKOH / g.
A method for manufacturing a laminated laminate , wherein the adhesive layer is a urethane-based laminated adhesive . The method for producing a laminated laminate according to claim 1 , further comprising carnauba wax .