JP6331205B1 - Gravure ink for laminate, printed matter, and laminate - Google Patents

Abstract

The present invention provides a gravure ink for laminating that has good overprinting printability (trapping property) and that has good anti-blocking property even with respect to a substrate subjected to easy adhesion treatment.
[Solution]
A gravure ink for laminating for forming a printed layer of a laminate having a substrate 1, a printing layer, an adhesive layer, and a substrate 2 in this order, an organic pigment (A), a binder resin (B), silica A gravure ink for laminating comprising particles (C), fatty acid amide (D), and an organic solvent and satisfying the following (1), (2) and (3). (1) The binder resin (B) contains a polyurethane resin (b1), a vinyl chloride copolymer resin (b2) and / or a cellulose resin (b3). (2) 0.1 to 2% by mass of silica particles (C) is contained in 100% by mass of the gravure ink. (3) In 100% by mass of the gravure ink, 0.01 to 0.8% by mass of the fatty acid amide (D) is contained.
[Selection figure] None

Description

  The present invention relates to a gravure ink for laminating, a printed matter using the same, and a laminate.

  When a film substrate such as an OPP film, a PET film, or a NY film is used as a packaging material, printing using a printing ink is usually performed for decoration or surface protection of the substrate. The substrate subjected to printing is then sent to the laminating process through a slitting process, and finally becomes a package for food packaging, cosmetic packaging, and all other uses.

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

One of the printability problems of the gravure printing method is trapping. The trapping property is a printing defect in overprinting, and is caused by insufficient wetting and spreading of the overlapping ink. Such print defects are handled as defective lots by the print converter, causing production loss.

Various attempts have been made to improve the printability. For example, a gravure ink using a single organic solvent has also been proposed (Patent Document 1). However, it is very difficult to satisfy all printability in gravure printing only by changing the type of organic solvent, and there are methods to improve printability by changing the design of the binder resin used, but the principle is still established. It has not been. Further, if there is a defective part in the printed matter, the possibility of causing a defect also in the subsequent lamination increases.

Further, since gravure printing is a method of winding up a printed material, the printed surface is pressed against the non-printed surface of the overlapping base material. The pressure applied to the inside of the wound printed material becomes higher as the printing distance is longer, and blocking (a phenomenon in which the ink moves to the overlapped base material) occurs when an ink having a low coating property is used. For example, it is known that the anti-blocking property is improved by using a wax component in the ink for surface printing and paper (Patent Documents 2 and 3). However, in laminating applications, if the wax component is positively used, lamination hindering and poor appearance occur, so that it has been difficult to use conventionally. Further, in some laminate applications, some of the base materials are processed so that the ink can easily adhere to it, which has been a factor that further deteriorates the blocking resistance.

In laminating use, after the ink is printed on the base material, the base material is further bonded thereon with an adhesive. The methods are roughly classified into three types: an extrusion laminating method, a dry laminating method, and a non-solvent laminating method. In addition to the above problems, the laminating process is concerned about poor appearance, insufficient laminate strength, boil resistance, retort resistance, etc., and various devices have been devised to improve these (Patent Document 4, Patent Document) 5, Patent Document 6).

JP 2013-144732 A JP 2013-127038 A Japanese Patent Laying-Open No. 2015-205993 JP 2010-270216 A JP 2005-298618 A JP 2013-213109 A

An object of the present invention is to provide a gravure ink for laminating which has good overprinting printability (trapping property) and also has good blocking resistance even with respect to a substrate subjected to easy adhesion treatment.

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

That is, the present invention is a gravure ink for laminating for forming a printed layer of a laminate having a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order, comprising an organic pigment (A), a binder A gravure ink for laminating comprising a resin (B), silica particles (C), a fatty acid amide (D), and an organic solvent and satisfying the following (1), (2) and (3).
(1) The binder resin (B) contains a polyurethane resin (b1), a vinyl chloride copolymer resin (b2) and / or a cellulose resin (b3).
(2) 0.1 to 2% by mass of silica particles (C) is contained in 100% by mass of the gravure ink.
(3) In 100% by mass of the gravure ink, 0.01 to 0.8% by mass of the fatty acid amide (D) is contained.

Moreover, this invention contains 80-100 mass% in total of the said polyurethane resin (b1) and vinyl chloride copolymer resin (b2) in 100 mass% of said binder resins (B), The solid content mass ratio (b1) / (B2) is 95/5 to 40/60, and relates to the gravure ink for lamination.

In addition, the present invention relates to the gravure ink for laminating, wherein the silica particles (C) have an average particle diameter of 1 to 5 μm.

In addition, the present invention relates to the gravure ink for laminating, wherein the fatty acid amide (D) is composed of a saturated fatty acid having 10 to 20 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms. .

The present invention also relates to the gravure ink for laminating, wherein the substrate 1 is a double-sided corona discharge treatment substrate.

Moreover, this invention relates to the printed matter which has the printing layer formed on the base material 1 from the said gravure ink for lamination.

Moreover, this invention relates to the laminated body which has an adhesive bond layer and the base material 2 in order on the printing layer of the said printed matter.

According to the present invention, it is possible to provide a gravure ink for laminating that has good overprinting printability (trapping property) and good blocking resistance even for a substrate subjected to easy adhesion treatment.

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

The present invention is a gravure ink for laminating for forming a printed layer of a laminate having a substrate 1, a printing layer, an adhesive layer, and a substrate 2 in this order, and includes an organic pigment (A), a binder resin ( B), silica particles (C), fatty acid amide (D), and an organic solvent are included, and the following (1), (2), and (3) are satisfied.
(1) The binder resin (B) contains a polyurethane resin (b1), a vinyl chloride copolymer resin (b2) and / or a cellulose resin (b3).
(2) 0.1 to 2% by mass of silica particles (C) is contained in 100% by mass of the gravure ink.
(3) In 100% by mass of the gravure ink, 0.01 to 0.8% by mass of the fatty acid amide (D) is contained.

In the present invention, the silica particles (C) form irregularities on the surface of the printing layer at the above-mentioned use amount, improve the wettability of the ink that is overprinted, and improve the printability (trapping property) of overprinting. . Moreover, it is guessed that there exists an effect which improves blocking resistance by reducing the contact area with the base material with which the unevenness | corrugation overlapped. Furthermore, by using the binder resin (B) and the fatty acid amide (D) in the above ranges, the trapping property and the blocking resistance are drastically improved, and the laminate suitability (adhesiveness, appearance, etc.) and the resistance are improved. It is possible to achieve both contradictory properties such as blocking properties.

<Organic pigment (A)>
In the present invention, the organic pigment (A) is used. Inks composed of organic pigments are difficult to overprint (trapping) in gravure printing, and are particularly difficult to overlay different hues. However, the trapping property is greatly improved by the silica particles (C) in the gravure ink for laminating of the present invention. The organic pigment (A) is not limited to the following examples, but is soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, ansanthrone, dianthraquinonyl, anthra Pyrimidine, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, carbon black And pigments of the type. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance Long blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, and the like.

Specific examples of preferable organic pigments (A) are shown below by generic names of color indexes. At least one or two or more selected from the group consisting of the following black pigments, indigo pigments, green pigments, red pigments, purple pigments, yellow pigments, orange pigments and brown pigments are preferred. Furthermore, at least one or more selected from the group consisting of black pigments, indigo pigments, red pigments, and yellow pigments are preferred. In particular, the use of indigo pigments and red pigments improves the printing effect (trapping property) of overprinting, and their use is particularly preferred.

<Black pigment>
Specifically, C.I. I. Of the black pigments of CI Pigment Black 1 to 34, a black pigment that is an organic compound or an organometallic complex is preferable. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7, C.I. I. Pigment black 9, C.I. I. Pigment black 20 and the like.
<Indigo pigment>
Specifically, C.I. I. Among the indigo pigments of CI Pigment Blue 1 to 80, indigo pigments that are organic compounds or organometallic complexes are preferable. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 5, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 22, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 25, C.I. I. Pigment blue 26, C.I. I. Pigment blue 60, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62, C.I. I. Pigment blue 63, C.I. I. Pigment blue 64, C.I. I. Pigment blue 75, C.I. I. Pigment blue 79, C.I. I. And CI Pigment Blue 80.
<Green pigment>
Specifically, C.I. I. Among the green pigments of CI Pigment Green 1 to 50, a green pigment that is an organic compound or an organometallic complex is preferable. I. Pigment green 1, C.I. I. Pigment green 4, C.I. I. Pigment green 7, C.I. I. Pigment green 8, C.I. I. Pigment green 10, C.I. I. And CI Pigment Green 36.
<Red pigment>
Specifically, C.I. I. Of the red pigments of CI Pigment Red 1 to 279, red pigments that are organic compounds or organometallic complexes are preferable. I. Pigment Red 1 to C.I. I. Pigment red 12, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 20, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 38, C.I. I. Pigment red 41, C.I. I. Pigment red 43, C.I. I. Pigment red 46, C.I. I. Pigment red 48, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 48: 6, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 53: 2, C.I. I. Pigment red 53: 3, C.I. I. Pigment red 54, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 68, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 89, C.I. I. Pigment red 95, C.I. I. Pigment red 112, C.I. I. Pigment red 114, C.I. I. Pigment red 119, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 136, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 147, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 164, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 169, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 181, C.I. I. Pigment red 182, C.I. I. Pigment red 183, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 192, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 200, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 210, C.I. I. Pigment red 211, C.I. I. Pigment red 213, C.I. I. Pigment red 214, C.I. I. Pigment red 216, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 237, C.I. I. Pigment red 238, C.I. I. Pigment red 239, C.I. I. Pigment red 240, C.I. I. Pigment red 242, C.I. I. Pigment red 245, C.I. I. Pigment red 247, C.I. I. Pigment red 248, C.I. I. Pigment red 251, C.I. I. Pigment red 253, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 256, C.I. I. Pigment red 257, C.I. I. Pigment red 258, C.I. I. Pigment red 260, C.I. I. Pigment red 262, C.I. I. Pigment red 263, C.I. I. Pigment red 264, C.I. I. Pigment red 266, C.I. I. Pigment red 268, C.I. I. Pigment red 269, C.I. I. Pigment red 270, C.I. I. Pigment red 271, C.I. I. Pigment red 272, C.I. I. Pigment red 279, and the like.
<Purple pigment>
Specifically, C.I. I. Among the purple pigments of CI Pigment Violet 1 to 50, a purple pigment that is an organic compound or an organometallic complex is preferable. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 5: 1, C.I. I. Pigment violet 13, C.I. I. Pigment violet 19 (γ type, β type), C.I. I. Pigment violet 23, C.I. I. Pigment violet 25, C.I. I. Pigment violet 27, C.I. I. Pigment violet 29, C.I. I. Pigment violet 31, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 37, C.I. I. Pigment violet 38, C.I. I. Pigment violet 42, C.I. I. Pigment violet 50, and the like.
<Yellow pigment>
Specifically, C.I. I. Of the yellow pigments of CI Pigment Yellow 1 to 219, yellow pigments that are organic compounds or organometallic complexes are preferable. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, pigment yellow 17, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 42, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 120, pigment yellow 125, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 137, C.I. I. Pigment, yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185 and C.I. I. And CI Pigment Yellow 213.
<Orange pigment>
Specifically, C.I. I. Of the orange pigments of CI Pigment Orange 1 to 81, an orange pigment that is an organic compound or an organometallic complex is preferable. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 16, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 37, C.I. I. Pigment o orange 38, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment range 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, or C.I. I. And CI Pigment Orange 74.
<Brown pigment>
C. I. Pigment brown 23, C.I. I. Pigment brown 25, or C.I. I. And CI Pigment Brown 26.

Of the above, preferably C.I. I. Pigment red 57: 1, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 146, C.I. I. Pigment red 242, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 14, C.I. I. Pigment orange 38, C.I. I. Pigment orange 13, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 139, C.I. I. Pigment red 185, C.I. I. Pigment red 122, C.I. I. Pigment red 178, C.I. I. Pigment red 149, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment orange 34, C.I. I. Pigment orange 64, C.I. I. Pigment black 7 and the like, and it is preferable to use at least one selected from these groups or two or more.

The pigment is an amount sufficient to ensure the concentration and coloring power of the laminating ink composition, that is, 1 to 50% by mass with respect to the total mass of the ink composition, and the solid content mass ratio in the ink composition is 10%. It is preferably contained at a ratio of ˜90 mass%. These pigments can be used alone or in combination of two or more.

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

<Binder resin (B)>
The binder resin (B) used in the present invention contains a polyurethane resin (b1), a vinyl chloride copolymer resin (b2) and / or a cellulose resin (b3). Other resins may be used in combination, and examples thereof include acrylic resins, polyester resins, styrene resins, styrene-maleic acid resins, rosin resins, rosin-modified maleic acid resins, maleic acid resins, and polyamide resins. The binder resin (B) preferably contains 70 to 100% by mass of the above (b1) to (b3) in 100% by mass of the binder resin. More preferably, it is 85-100 mass%.
In addition, the binder resin (B) is preferably contained in an amount of 3 to 20%, and more preferably 5 to 15%, in the ink.

Further, in 100% by mass of the binder resin (B), the polyurethane resin (b1) and the vinyl chloride copolymer resin (b2) are included in a total amount of 80 to 100% by mass, and the solid content mass ratio (b1) / (b2) Is preferably 95/5 to 40/60, more preferably 95/5 to 50/50. Within this range, printability, substrate adhesion, coating film properties, and laminate strength are good.

<Polyurethane resin (b1)>
The polyurethane resin (b1) preferably has a weight average molecular weight of 10,000 to 100,000, preferably has a glass transition temperature of −60 ° C. to 0 ° C., and further at 40 ° C. in dynamic viscoelasticity measurement. Those having a storage elastic modulus of 1 to 100 MPa are preferred. In the present invention, the glass transition temperature is measured by a differential scanning calorimeter (DSC) and represents the midpoint of the temperature range where the glass transition occurs.

The polyurethane resin (b1) preferably has an amine value or a hydroxyl value, and the amine value is preferably 1.0 to 20.0 mgKOH / g. Moreover, it is preferable that a hydroxyl value is 1.0-20.0 mgKOH / g.

The polyurethane resin (b1) preferably contains a structural unit derived from a polyether polyol, and the content thereof is preferably 5 to 80% by mass, more preferably 100% by mass of the solid content of the polyurethane resin (b1). Is 10-50 mass%.

The polyurethane resin (b1) preferably contains a structural unit derived from a polyester polyol, and the content thereof is preferably 5 to 80% by mass, more preferably 100% by mass, solid content of the polyurethane resin (b1). It is 10-70 mass%, More preferably, it is 30-70 mass%.

The polyurethane resin (b1) is not particularly limited, and is appropriately produced by a known method. For example, a polyurethane resin composed of a polyol and a polyisocyanate, a polyurethane resin obtained by reacting a urethane prepolymer of a terminal isocyanate composed of a polyol and a polyisocyanate, and an amine chain extender 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, and hydrogenated dimer diol. Of these, polyether polyol and polyester polyol are preferred.

Examples of the polyether polyol include polymer or copolymer polyether polyols such as ethylene oxide, propylene oxide, and tetrahydrofuran. Among them, 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 is calculated from the hydroxyl value with the terminal being a hydroxyl group, and is obtained from (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × Hydroxyl number / Hydroxyl value

Examples of the polyester polyol include condensates obtained by esterification reaction of dibasic acid and 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, 1,8-octanediol. 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl- 1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer diol , Hydrogenated dimer diol, etc. It is below.
Of these, a diol having a branched structure is preferable. The branched structure means a diol having an alkyl side chain in which at least one hydrogen atom of an alkylene group contained in the diol is substituted with an alkyl group, and includes propylene glycol, 1,3-butanediol, 2-methyl-1 , 3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4- Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, And 2,2,4-trimethyl-1,6-hexanediol and the like. These are particularly preferable for improving printability, printing effect, and laminate strength.
These polyester polyols can be used alone or in admixture of two or more. The dibasic acid is particularly preferably sebacic acid or adipic acid. Also, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups can be used in combination.

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

Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate Nate, dimethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis Examples include -chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. These may be trimers to form an isocyanurate ring structure. These polyisocyanates can be used alone or in admixture of two or more. Of these, isocyanurate of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate is preferable.

The amine 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, such as ethylenediamine, propylenediamine, hexamethylenediamine, and pentamethylene. In addition to diamine chain extenders such as diamine, isophorone diamine, dicyclohexylmethane-4,4′-diamine, p-phenylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di- 2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2 Diamine chain extender having a hydroxyl group such as hydroxypropyl ethylenediamine can also be used. These chain extenders can be used alone or in admixture of two or more. If necessary, a polyfunctional amine chain extender having three or more functions can also be used. Specifically, 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. Of these, isophoronediamine, hexamethylenediamine, and iminobispropylamine are preferable.

Moreover, a monovalent active hydrogen compound can also be used as a polymerization terminator for the purpose of terminating excess reaction. Such a compound is not particularly limited as long as it is a monoamine compound having a primary or secondary amino group, and examples thereof include dialkylamines such as di-n-butylamine and aminoalcohols such as 2-ethanolamine. . Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, particularly when it is desired to introduce a carboxyl group into the polyurethane resin. When using a polymerization terminator, the chain terminator and chain extender may be used together to carry out the chain extension reaction, and after the chain extension reaction has been performed to some extent with the chain extender, the end terminator is added alone. Thus, an end termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

In the method of synthesizing the polyurethane resin (b1), it is preferable to react the polyol with polyisocyanate and then react with an amine chain extender and, if necessary, a polymerization terminator to form a polyurethane resin. For example, a polyol and a polyisocyanate are reacted with an inert solvent for an isocyanate group as necessary, and further, if necessary, reacted at a temperature of 50 ° C. to 150 ° C. using a urethanization catalyst (urethanization reaction). And a prepolymer method in which a polyurethane resin is obtained by reacting this prepolymer with an amine chain extender, or a polymer polyol, a polyisocyanate, an amine chain extender and ( And a polymerization stopper) can be produced by a known method such as a one-shot method in which a polyurethane resin (b1) is obtained by reacting in one step. The amine chain extender can also be used in a urethanization reaction with polyisocyanate together with a polymer polyol.

In producing the prepolymer, the amount of polyol and polyisocyanate is the ratio of the number of moles of isocyanate groups in the polyisocyanate to the number of moles of hydroxyl groups in the total of the polymer polyol. NCO / OH ratio = 1.1-3. It is preferable to be in the range of 0.0. More preferably, the NCO / OH ratio is 1.3 to 2.5.

In addition, it is preferable in terms of reaction control to use an organic solvent for the synthesis of the prepolymer. The organic solvent that can be used is preferably an organic solvent that is inactive with an isocyanate group, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene. And the like; esters such as ethyl acetate and butyl acetate; and halogenated hydrocarbons such as chlorobenzene and perchlene. These may be used alone or in combination as a mixed solvent.

Furthermore, a catalyst can also be used for the synthesis reaction of this prepolymer. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal 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-obtained prepolymer having an isocyanate group at the terminal is reacted with diamine, triamine or the like which is an amine chain extender at 10 to 60 ° C., and a high molecular weight polyurethane resin containing an active hydrogen group at the terminal (b1 ) Is obtained.

The ratio of the total number of moles of amino groups of the amine chain extender to the number of moles of isocyanate groups in the prepolymer is 1.01 to 2.00, preferably 1.03 to 1.06. It is preferable to make it react.

<Vinyl chloride copolymer resin (b2)>
The vinyl chloride copolymer resin is not particularly limited as long as it contains a structural unit derived from vinyl chloride and a structural unit derived from other monomers. Of these, vinyl chloride-vinyl acetate copolymer resin and vinyl chloride-acrylic copolymer resin are preferable.

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin is a copolymer of vinyl chloride and vinyl acetate, and the molecular weight is preferably 5,000 to 100,000 in terms of weight average molecular weight, and 20,000 to 70,000. Is more preferable. The structure derived from the vinyl acetate monomer in the solid content of 100% by mass of the vinyl chloride-vinyl acetate copolymer resin is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. . In this case, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, laminate strength, and the like are improved.
Moreover, since the solubility to an organic solvent improves, what contains the hydroxyl group derived from vinyl alcohol by a saponification reaction or copolymerization is still more preferable, and it is preferable that it is 20-200 mgKOH / g as a hydroxyl value. The glass transition temperature is preferably 50 ° C to 90 ° C.

<Vinyl chloride-acrylic copolymer resin>
Vinyl chloride-acrylic copolymer resin is mainly composed of a copolymer resin of vinyl chloride monomer and acrylic monomer, and the acrylic monomer has improved adhesion to substrates and solubility in organic solvents (meth) It is preferable to contain a hydroxyalkyl ester of acrylic acid. The acrylic monomer may be incorporated into the main chain of the polyvinyl chloride in a block or randomly, or may be grafted to the side chain of the polyvinyl chloride. The vinyl chloride-acrylic copolymer resin preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 30,000 to 70,000.

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

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

The acrylic monomer is preferably a (meth) acrylic acid alkyl ester, and the alkyl group preferably has 1 to 20 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) acrylic acid Examples include octadecyl. Furthermore, the alkyl group may further have a benzene ring structure. These can be used alone or in combination of two or more.

Further, the acrylic monomer may have a hydroxyl group. Examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 2. (Meth) acrylic acid such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate Hydroxyalkyl esters, glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified (meth) acrelane And hydroxyethyl acrylamide. Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are more preferable because they improve solubility in solvents. These can be used alone or in combination of two or more.

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

<Cellulose-based resin (b3)>
Examples of the cellulose resin (b3) include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose and the like, and the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, An isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and the like can be given. Further, the alkyl group may have a substituent. Among these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable. The molecular weight is preferably 5,000 to 1,000,000 in terms of weight average molecular weight, more preferably 10,000 to 200,000. Moreover, the thing whose glass transition temperature is 120 to 180 degreeC is preferable.

<Silica particles (C)>
Examples of the silica (C) include natural products, synthetic products, crystalline, non-crystalline, hydrophobic, and hydrophilic ones. There are dry and wet methods for synthesizing silica. Combustion method, arc method and wet method are known as dry methods, and sedimentation method and gel method are known. Silica (C) may be hydrophilic silica having a hydrophilic functional group on the surface, or may be hydrophobic silica that is hydrophobized by modifying the hydrophilic functional group with alkylsilane or the like. Preferably, the ink containing hydrophilic silica particles promotes the wetting and spreading of the ink during overprinting, improves the overprinting effect (hereinafter sometimes referred to as “trapping property”), and has anti-blocking properties due to the unevenness of the printed surface. Has the effect of improving the performance. As addition amount of a silica particle (C), it contains 0.1-2.0 mass% in 100 mass% of gravure inks for lamination of this invention. The content is preferably 0.1 to 1.0% by mass.

The silica particles (C) used in the present invention preferably have an average particle diameter of 1 to 5 μm in order to create irregularities on the surface of the ink layer. In addition, the average particle diameter of a silica particle means the particle diameter in the integrated value 50% (D50) in a particle size distribution, and can be calculated | required by the Coulter counter method.
The silica particles (C) preferably have a specific surface area of 50 to 600 m ² / g by the BET method. More preferably, it is 100 m-450 m < ² > / g. The silica particles (C) used in the gravure ink for lamination of the present invention can be used in combination with those having different average particle diameters or BET specific surface areas.

<Fatty acid amide (D)>
The fatty acid amide (D) used in the gravure ink for lamination of the present invention is not particularly limited as long as it has a fatty acid residue and an amide group. Fatty acid amide (D) is dissolved or dispersed in the gravure ink for laminating, but after printing, it is oriented on the surface of the printed film and exhibits slipperiness, improving the blocking resistance against the overlapping substrates. It is thought to let you. The description is based on technical considerations and does not limit the invention.

Examples of the fatty acid amide (D) include a monoamide (D1), a substituted amide (D2), a bisamide (D3), a methylolamide, and an ester amide. Since the blocking resistance is improved, the monoamide (D1), It is preferably at least one selected from the group consisting of substituted amide (D2) and bisamide (D3). Content of fatty acid amide (D) is 0.01-0.8 mass% in 100 mass% of gravure inks. When the content is 0.8% by mass or less, the laminate appearance and laminate strength are improved, and the laminate is not hindered. Moreover, if content is 0.01 mass% or more, blocking resistance will become favorable. The content is more preferably 0.02 to 0.5% by mass.

<Monoamide (D1)>
Monoamide (D1) is represented by the following general formula (1).
General formula (1)
R ¹ -CONH ₂
(In the formula, R ¹ represents a residue obtained by removing COOH from a fatty acid.)
Examples of the monoamide (D1) include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide, oleic acid amide, erucic acid amide and the like.

<Substituted amide (D2)>
The substituted amide (D2) is represented by the following general formula (2).
General formula (2)
R ² —CONH—R ³
(In the formula, R ² and R ³ represent a residue obtained by removing COOH from a fatty acid, and may be the same or different.)
Examples of the substituted amide (D2) include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.

<Bisamide (D3)>
Bisamide (D3) is represented by the following general formula (3) or general formula (4).
General formula (3)
R ⁴ —CONH—R ⁵ —HNCO—R ⁶
General formula (4)
^{R 7 -NHCO-R 8 -CONH-} R 9
(Wherein R ⁴ , R ⁶ , R ⁷ , and R ⁹ represent a residue obtained by removing COOH from a fatty acid, which may be the same or different, and R ⁵ and R ⁸ are alkylene groups having 1 to 10 carbon atoms. Or represents an arylene group.)
Examples of the bisamide (D3) include methylene bis stearic acid amide, ethylene bis capric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, and hexamethylene bis stearic acid. Amides, hexamethylene bisbehenic acid amides, hexamethylene hydroxystearic acid amides, ethylene bisoleic acid amides, ethylene biserucic acid amides, hexamethylene bisoleic acid amides, N, N′-distearyl adipic acid amides, N, N ′ -Distearyl sebacic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide and the like can be mentioned.

The arylene group is preferably at least one selected from a phenylene group, a toluylene group, and an m-xylylene group.

The melting point of the fatty acid amide (D) is preferably 50 ° C to 150 ° C. As applicable, monoamide (D1) includes, for example, lauric acid amide (melting point 87 ° C.), palmitic acid amide (melting point 100 ° C.), stearic acid amide (melting point 101 ° C.), behenic acid amide (melting point 110 ° C.), Examples include hydroxystearic acid amide (melting point 107 ° C.), oleic acid amide (melting point 75 ° C.), erucic acid amide (melting point 81 ° C.), and the like. Examples of the substituted amide (D2) include N-oleyl palmitic acid amide (melting point 68 ° C.), N-stearyl stearic acid amide (melting point 95 ° C.), N-stearyl oleic acid amide (melting point 67 ° C.), and N-oleyl stearic acid. Examples include amide (melting point: 74 ° C.), N-stearyl erucamide (melting point: 69 ° C.), and the like. Examples of the bisamide (D3) include methylene bis stearic acid amide (melting point 142 ° C.), ethylene bis stearic acid amide (melting point 145 ° C.), ethylene bishydroxy stearic acid amide (melting point 145 ° C.), ethylene bisbehenic acid amide (melting point 142 ° C), hexamethylenebisstearic acid amide (melting point 140 ° C), hexamethylenebisbehenic acid amide (melting point 142 ° C), hexamethylene hydroxystearic acid amide (melting point 135 ° C), ethylene bisoleic acid amide (melting point 119 ° C), Ethylenebiserucamide (melting point 120 ° C.), hexamethylenebisoleic acid amide (melting point 110 ° C.), N, N′-distearyladipic acid amide (melting point 141 ° C.), N, N′-distearyl sebacic acid amide ( Melting point 136 ° C.), N, N′-diolet Ruajipin acid amide (melting point 118 ℃), N, N'- dioleyl sebacic acid amide (melting point 113 ° C.), and the like. Examples of methylolamide include methylol stearamide (melting point: 110 ° C.). Examples of ester amides include stearamide ethyl stearate (melting point: 82 ° C.). Among these, those having a molecular weight of 200 to 800 are preferable in order to maintain the laminate strength. More preferably, it is 250-700.

The fatty acid constituting the fatty acid amide is preferably a saturated fatty acid having 12 to 20 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms, and a saturated fatty acid having 16 to 18 carbon atoms and / or 18 to 22 carbon atoms. The unsaturated fatty acid is more preferable. Particularly preferred as saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, and particularly preferred unsaturated fatty acids are oleic acid and erucic acid.
Most preferred is a fatty acid amide comprising at least one fatty acid selected from the group consisting of palmitic acid, stearic acid, behenic acid, hydroxystearic acid, oleic acid, and erucic acid.

<Organic solvent>
The gravure ink for lamination of the present invention may contain an organic solvent as a liquid medium. The organic solvent used is preferably used as a mixed solvent, aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate. Well-known organic solvents such as alcohol organic solvents such as ester organic solvents, methanol, ethanol, n-propanol, isopropanol, and n-butanol can be used. Among these, an organic solvent not containing an aromatic organic solvent such as toluene and xylene (non-toluene organic solvent) is more preferable. More preferably, an organic solvent that does not contain an aromatic organic solvent and / or a ketone organic solvent such as methyl ethyl ketone (hereinafter referred to as “MEK”) is more preferable. Particularly preferred are those containing an ester organic solvent and an alcohol organic solvent as main media.
The gravure ink for laminating of the present invention may contain water as a liquid medium, but its content is 0.1 to 10% by mass in 100% by mass of the liquid medium.

<Other resins>
The gravure ink for laminating in the present invention may contain other polymer materials, such as chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, terpene resin, Phenol-modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, and modified resins thereof can be exemplified. These resins can be used alone or in admixture of two or more, and the content is preferably 0 to 30% by mass in 100% by mass of the solid content of the binder resin (B).

<Additives>
The gravure ink composition of the present invention can appropriately contain known additives as additives, and known additives such as pigment derivatives, dispersants, wetting agents, adhesion aids as necessary in the production of ink compositions. Agents, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, isocyanate curing agents, silane coupling agents, and the like can be used.

In order to disperse the pigment stably, the dispersant may be used in combination. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. From the viewpoint of the storage stability of the ink, the dispersant is preferably contained in the ink at 0.1 to 10.0% by mass with respect to 100% by mass of the total mass of the ink. Furthermore, it is more preferable that it is contained in the range of 0.1 to 3.0% by mass.

<Manufacture of ink composition>
The gravure ink for lamination of the present invention can be produced by dissolving and / or dispersing an organic pigment (A), a binder resin (B), silica particles (C), and a fatty acid amide (D) in an organic solvent. . Specifically, for example, the organic pigment (A) and the silica particles (C) are mixed with the polyurethane resin (b1), the vinyl chloride copolymer resin (b2), and, if necessary, the dispersant, and dispersed in an organic solvent. A gravure ink for lamination is prepared by blending the obtained pigment dispersion with a polyurethane resin (b1), a fatty acid amide (D), or other resins and additives as necessary. Can be manufactured. The particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

In the case where bubbles or unexpectedly large particles are included in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

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

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

<Substrate 1>
Examples of the substrate 1 that can be used in the printed matter of the present invention include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, and polychlorinated. Examples include film bases made of vinyl, polyvinylidene chloride, cellophane, paper, aluminum, etc., or composite materials of these materials, and vapor-deposited bases that deposit inorganic compounds such as silica, alumina, and aluminum on polyethylene terephthalate and nylon films. A material can also be used, and polyvinyl alcohol or the like may be coated on the vapor deposition surface of an inorganic compound or the like.
The substrate 1 may be subjected to surface treatment such as corona discharge treatment on one side or both sides. Corona discharge treatment generates functional groups such as hydroxyl groups, carboxyl groups, and carbonyl groups on the substrate, thereby improving the adhesion between the substrate surface and the printing (ink) layer. When ink is printed on the corona-treated surface of the single-sided corona-treated substrate, the printed layer is in contact with the non-corona-treated surface during winding. However, when printing is performed on a substrate that has been subjected to a double-sided corona discharge treatment, the printed layer contacts the corona discharge treatment surface during winding. Therefore, in the double-sided corona-treated substrate, the blocking resistance of the printing layer tends to be very deteriorated. However, the ink of the present invention can achieve both laminate suitability and blocking resistance even for such a substrate.

Examples of the substrate subjected to corona treatment on one side include polypropylene films (FOR, FOS) manufactured by Futamura Chemical Co., Ltd., polyester films (E5100) manufactured by Toyobo Co., Ltd., nylon films manufactured by Unitika (ON-RT), and the like. Examples of the substrate subjected to corona treatment on both surfaces include polypropylene film (FOR-BT) manufactured by Futamura Chemical Co., Ltd., polyester film (E5200) manufactured by Toyobo Co., Ltd., and nylon film (ONMB-RT) manufactured by Unitika.

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

<Laminate>
The laminate of the present invention is obtained by sequentially bonding an adhesive layer and a film layer to the printed layer of the printed matter. For example, the usual extrusion laminating (extrusion laminating) method in which a molten polyethylene resin is laminated on the printing layer through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium, and urethane on the printing surface It is obtained by a known laminating process such as a dry laminating method in which a plastic film is applied and a non-solvent laminating method, or a direct laminating method in which a molten polypropylene is directly pressed and laminated on the printing surface. It is done.

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

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

(Weight average molecular weight)
The weight average molecular weight was determined as a converted molecular weight using polystyrene as a standard substance by measuring a molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation). The measurement conditions are shown below.
Column: The following columns were used in series.
TSKgel SuperAW2500 manufactured by Tosoh Corporation
TSKgel SuperAW3000 manufactured by Tosoh Corporation
TSKgel SuperAW4000 made by Tosoh Corporation
TSKgel guardcolumn 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]
140 parts of a polyester polyol (hereinafter “NPG / AA”) obtained from neopentyl glycol 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, and isophorone diisocyanate (hereinafter “IPDI”). ) 60.7 parts and 65.2 parts of ethyl acetate were reacted at 80 ° C. for 4 hours under a nitrogen stream to obtain a solvent solution of a terminal isocyanate prepolymer. Next, 25.2 parts of isophorone diamine (hereinafter “IPDA”), 2.0 parts of iminobispropylamine (hereinafter “IBPA”), 1.0 part of 2-ethanolamine (hereinafter “2EtAm”), ethyl acetate / isopropanol (hereinafter referred to as “below”) “IPA”) = 50/50 mixed solvent mixed with 608.9 parts, the obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C. and then reacted at 80 ° C. for 1 hour to obtain a solid content. A polyurethane resin solution PU1 having 30%, an amine value of 11.1 mgKOH / g, a hydroxyl value of 3.2 mgKOH / g, and a weight average molecular weight of 45,000 was obtained.

(Synthesis example 2) [Polyurethane resin PU2]
A polyurethane resin solution PU2 was obtained in the same manner as in Synthesis Example 1 using the raw materials shown in Table 1. Abbreviations in Table 1 are as follows.
MPO / AA: Polyester polyol which is a condensate of 3-methyl-1,3-propanediol and adipic acid PEG: Polyethylene glycol TDI: Tolylene diisocyanate (methyl-1,3-phenylene diisocyanate)

(Synthesis Example 3) [Vinyl chloride-acrylic copolymer resin]
In a 1.0 L autoclave, 1.0 g of potassium peroxodisulfate (K ₂ S ₂ O ₈ ) was dissolved in 500 g of ion-exchanged water and deaerated. After raising the temperature to 60 ° C., 425 g of a mixture comprising 357 g of vinyl chloride, 63 g of 2-hydroxypropyl acrylate, and 5.0 g of sodium di-2-ethylhexylsulfosuccinate (product name: Aerosol OT) was placed in the autoclave. The mixture was added and reacted at 60 ° C. and 6.5 atm. The polymerization reaction was continued until the autoclave reached 2.5 atm. The resulting emulsion was precipitated with sodium chloride, filtered, washed and dried to obtain a vinyl chloride-acrylic copolymer resin. Furthermore, vinyl chloride-acrylic copolymer resin was dissolved in ethyl acetate to obtain a varnish (PVAc1) having a solid content of 30%. In addition, the content rate of 2-hydroxypropyl acrylate in the obtained resin was 14.0%, the weight average molecular weight 50000, and the glass transition temperature 70 degreeC.

(Example 1) [Preparation of gravure ink S1 for laminating]
40 parts of polyurethane resin solution PU1 (solid content 30%), vinyl chloride-vinyl acetate copolymer resin (Solvain TAO: manufactured by Nissin Chemical Industry Co., Ltd. Vinyl chloride: vinyl acetate: vinyl alcohol = 91: 2: 7 (solid content 30 % Ethyl acetate solution)) 5.0 parts, 0.5 part of silica particles 1 listed in Table 2, 0.2 part of palmitic acid amide, C.I. I. 10 parts of Pigment Blue 15: 3 and 44.3 parts of a solution of N propyl acetate / IPA = 70/30 were mixed and dispersed for 20 minutes with an Eiger mill to obtain a gravure ink S1 for laminating.

(Examples 2 to 21) [Production of gravure inks S2 to S21 for laminating]
Laminate gravure inks S2 to S21 were obtained in the same manner as in Example 1 except that the silica particles shown in Table 2, the fatty acid amide shown in Table 3, and the raw materials shown in Table 4 were used.
In addition, the abbreviation in Table 4 represents the following.
DLX5-8: Nitrocellulose manufactured by ICI Novel enterprises Nitrogen content: 12.0% (solid content: 30% isopropanol solution)

The average particle diameter of silica particles 1 to 4 in Table 2 is the median diameter (D50) determined by the Coulter counter method, and the specific surface area is a value measured by the BET method. The surface tension is a measured value of the du Nouy method (ring method, ring method) and represents static surface tension.
The melting point of the fatty acid amide in Table 3 was determined by DSC (differential scanning calorimetry measurement). The measuring machine used was DSC8231 manufactured by Rigaku Corporation, and the measurement temperature range was 25 to 180 ° C., the heating rate was 10 ° C./min, and the endothermic peak temperature was the melting point. Saturation / unsaturation was defined as “saturated” when the fatty acid-derived structure did not have a carbon-carbon double bond, and “unsaturated” when the fatty acid-derived structure had a carbon-carbon double bond.

(Comparative Examples 1 to 13) [Preparation of gravure ink compositions T1 to T7]
Except for using the raw materials shown in Table 5, gravure inks T1 to T7 were obtained in the same manner as in Examples 1 to 21 above.

(Example 22)
<Printing of gravure ink for laminating>
The gravure inks S1 (blue ink) and S21 (red ink) obtained as described above were mixed with a mixed solvent (methyl ethyl ketone “MEK”: N propyl acetate “NPAC”: isopropanol “IPA” = 40: 40: 20). Dilute so that the viscosity is 16 seconds (25 ° C., Zaan Cup No. 3), S1 is a Helio 175 line solid plate (plate type Elon gate, 90% solid pattern), S21 is a Helio 175 line solid plate (plate type plate) Presto, 90% solid pattern) on the corona discharge-treated surface of FOR-BT # 20 and E5100 # 15, which are plastic substrates, at a printing speed of 100 m / min. GG1 was obtained respectively. The printing conditions were a printing distance of 400 m at a temperature of 25 ° C. and a humidity of 60%.
The base materials FOR-BT # 20 and E5100 # 15 represent the following.
FOR-BT # 20: manufactured by Futamura Chemical Co., Ltd. Double-sided corona discharge-treated polypropylene (OPP) film thickness 20 μm
E-5100 # 15: manufactured by Toyobo Co., Ltd., single-sided corona discharge treated polyester (PET) film, film thickness: 15 μm

About the obtained printed matter GG1, a polyether urethane-based laminate adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.) as an ethyl acetate solution having a solid content of 25% by weight and 10% by weight is 1.5 g / m ² . It was coated and dried on the printed surface, and was laminated with aluminum-deposited unstretched polypropylene (VMCP2203, film thickness 25 μm, manufactured by Toray Film Processing Co., Ltd.) to perform dry lamination.

(Examples 23 to 42)
Printed matter G2 to G21 (OPP) and printed matter GG2 to GG21 (PET) were obtained in the same manner as in Example 22 except that the inks listed in Table 4 were used in combinations described in Table 6-1. Further, dry lamination was performed on the printed surfaces of the printed materials GG2 to GG21 by the same method as described above. Evaluation was performed after the laminate was kept at 40 ° C. for 48 hours.

(Comparative Examples 9-16)
Printed materials H1 to H8 (OPP) and printed materials HH1 to HH8 (PET) were obtained in the same manner as in Example 22, except that the inks listed in Table 5 were used in combinations described in Table 6-2. Further, dry lamination was performed on the printed surfaces of the printed materials HH1 to HH8 in the same manner as in Examples 22 to 42 to obtain a laminate. Evaluation was performed after the laminate was held at 40 ° C. for 48 hours.

<Evaluation>
Gravure inks S1 to S21 (Examples), T1 to T8 (Comparative Examples) and printed materials G1 to G21 (OPP), GG1 to GG21 (PET), printed materials H1 to H8 (OPP), HH1 to HH8 (PET), and The following evaluation was performed on a laminate using GG1 to GG21 and HH1 to HH8. The results are shown in Tables 6-1 and 6-2.

<Blocking resistance>
The printed materials G1 to G21 (OPP), GG1 to GG21 (PET), printed materials H1 to H8 (OPP), and HH1 to HH8 (PET) were evaluated for blocking resistance under the following conditions.
(Sample and pressure)
Printing surface of OPP printed material / OPP substrate corona-treated surface 10 kg / cm ²
Printing surface of PET printed material / Non-corona-treated surface of PET substrate 10 kg / cm ²
(Standing conditions) 40 ° C.-80% RH 12 hours 24 hours 72 hours (Evaluation method) The printed surface and various substrates are peeled off, and the degree of removal (peeling) of the ink film from the printed surface is visually determined.
Criterion 5: The ink film on the printed surface does not peel at all, and the peel resistance is low (good)
4 ... The peeled area of the ink film is 1% or more and less than 5%, and the peel resistance is small (practical)
3 .. The peeled area of the ink coating is 5% or more and less than 20% (slightly poor)
2 ... Ink film peeling area of 20% or more and less than 50% (defect)
1 ... The ink film peels 50% or more (very bad)
In addition, 5 and 4 are ranges in which there is no practical problem.

<Laminate appearance>
About the laminate which is a dry laminate using the obtained printed materials GG1 to GG21 and HH1 to HH8, immediately after lamination and after hot water boil treatment at 100 ° C. for 30 minutes, observed from the non-printing surface side of the printing substrate The appearance was confirmed and evaluated.
5 ... No delamination and unevenness in the printed part of the laminate 4 ... ... Delamination and unevenness in the printed part of the laminate in an area of 1% to less than 3% 3・ Delamination and unevenness are present in the printed part of the laminate in an area of 3% to less than 20% 2... Delamination and unevenness are present in the printed part of the laminate in an area of 20% to less than 50% 1... There is an overall delamination and unevenness in the printed portion of the laminate in an area of 50% or more, and 5 and 4 are ranges where there is no practical problem.

<Trapability>
The obtained printed materials G1 to G21 (Examples) and the printed materials H1 to H8 (Comparative Examples) were visually evaluated for overprinting unevenness (trapping property) using a microscope (VHX-5000) manufactured by Keyence Corporation.
5 ... There is almost no unevenness in the printing section.
4... Uneven area in printing section is less than 10% 3... Uneven area in printing section is 10% or more and less than 20% 2... Unevenness in printing section The area is 20% or more and less than 40% 1... There is a large unevenness of 40% or more in the entire printing part.

From the evaluation results, it was found that the gravure ink for laminating of the present invention is a gravure ink excellent in blocking resistance and trapping property in overprinting, and further excellent in appearance after lamination.

Claims (7)

A gravure ink for laminating for forming a printed layer of a laminate having a substrate 1, a printing layer, an adhesive layer, and a substrate 2 in this order, an organic pigment (A), a binder resin (B), silica A gravure ink for laminating comprising particles (C), fatty acid amide (D), and an organic solvent and satisfying the following (1), (2) and (3).
(1) The binder resin (B) contains a polyurethane resin (b1), a vinyl chloride copolymer resin (b2) and / or a cellulose resin (b3).
(2) 0.1 to 2% by mass of silica particles (C) is contained in 100% by mass of the gravure ink.
(3) In 100% by mass of the gravure ink, 0.01 to 0.8% by mass of the fatty acid amide (D) is contained. In 100 mass% of the binder resin (B), the polyurethane resin (b1) and the vinyl chloride copolymer resin (b2) are included in a total of 80 to 100 mass%, and the solid content mass ratio (b1) / (b2) is It is 95 / 5-40 / 60, The gravure ink for lamination of Claim 1 characterized by the above-mentioned. The gravure ink for lamination according to claim 1 or 2, wherein the silica particles (C) have an average particle size of 1 to 5 µm. The fatty acid amide (D) is composed of a saturated fatty acid having 10 to 20 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms, for laminating according to any one of claims 1 to 3 Gravure ink. The substrate gravure ink according to any one of claims 1 to 4, wherein the substrate 1 is a double-sided corona discharge treatment substrate. The printed matter which has the printing layer formed from the gravure ink for lamination in any one of Claims 1-5 on the base material 1. A laminate comprising an adhesive layer and a substrate 2 in this order on the printed layer of the printed matter according to claim 6.