WO2018088523A1 - Solvent-based gravure printing ink for lamination, printed matter, and laminate - Google Patents

Abstract

One embodiment of the present invention relates to a solvent-based gravure printing ink for lamination, which contains at least a polyurethane resin (A) and a polyurethane resin (B), and wherein the molar fraction of urea bonds in the polyurethane resin (A) is 0.1 to 0.4 and the molar fraction of urea bonds in the polyurethane resin (B) is 0.45 to 0.65.

Description

Gravure ink for solvent-type lamination, printed matter, and laminate

Embodiments of the present invention relate to a gravure ink for solvent-type lamination, and a printed material and a laminate thereof.

When transparent substrates such as OPP film, PET film, NY film, and their metal oxide vapor-deposited films are used as the base material of the packaging material, printing using printing ink is required for decoration or surface protection of the base material. Applied. The printed substrate is then sent to a laminating process through a slit process, and finally becomes a package for food packaging, cosmetic packaging, and any other use.

In many cases, the gravure printing method is adopted for printing on the above-mentioned base material. The plate used in the gravure printing method is a concave indentation (cell) where characters, patterns, etc. are immersed in the plate to the extent that ink enters this cell, and the surface is rotated by a doctor blade while rotating the plate. Scrape off excess ink, transfer gravure ink to substrate, and make it 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.

The problems of printability of this gravure printing method include (I) base material transferability (plate clogging property) and (II) halftone dot reproducibility. (I) The problem of substrate transferability is poor transfer of the ink to the substrate, and appears on the printed surface in a distorted form. It is also called a plate or phenomenon, and it tends to occur due to ink clogging in a portion where the plate depth is shallow and the cell opening is small (highlight portion). In particular, it occurs remarkably in inks having poor re-solubility in organic solvents. (II) The problem of halftone dot reproducibility is printing failure in overprinting, and the underlying printing part is melted by overprinting ink, and appears as a phenomenon such as halftone dots (dots) bleeding, spreading or blurring. Such printing defects not only lack vivid colors, but are often handled as defective lots by the print converter, causing production loss. Furthermore, as a problem of printability, there is (III) plate fogging property. (III) The problem of plate fogging is that the ink cannot be scraped off by the doctor blade, and as a result, the solid portion of the base material is colored (stained), or a streak-like pattern appears unintentionally. A phenomenon occurs.

Various attempts have been made to improve the printability. For example, a solvent-based gravure ink containing glycol ether or water has been proposed to improve the plate, that is, the properties (see Patent Document 1). In order to improve halftone dot reproducibility, a gravure ink using a special amine-containing urethane resin has also been proposed (see Patent Document 2). However, with these inks, it has been difficult to satisfy all printability.

The gravure ink is classified into a laminating application, a surface printing application, and the like. In the laminating application, 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. Matters concerned about the suitability for laminating include insufficient laminating strength, insufficient retort resistance, and the like, and various measures have been taken to improve them (see Patent Documents 3 to 5). However, it is difficult to achieve both printability and laminateability. Particularly when a resin film such as an OPP film, PET film, silica, or alumina vapor-deposited film is used as the substrate, the laminateability and printability (especially the plate or It has been difficult to achieve compatibility between the image quality, halftone dot reproducibility, and plate fogging property.

Among the above films, silica or alumina vapor-deposited film is a kind of substrate for retort resistance, but unlike a film containing aluminum foil that has been conventionally used, since it can be transparent and the contents can be confirmed, It is attracting attention as a gas barrier packaging material in the food field. Usually, a silica or alumina vapor-deposited film is often used as a transparent packaging material that is printed and then laminated with a nylon film, a polyolefin film, or the like. However, silica or alumina vapor-deposited films have problems such as poor adhesion of ink to the film surface and difficulty in obtaining sufficient laminate strength.

JP-A-9-328646 JP 2014-133840 A JP 2010-270216 A JP 2005-298618 A JP 2013-213109 A

The problem to be solved by the present invention is to provide a solvent-type laminating gravure ink that can achieve both excellent printing suitability and laminating suitability, and a printed matter and a laminate using the ink.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have arrived at the present invention.

That is, one embodiment of the present invention includes at least a polyurethane resin (A) and a polyurethane resin (B), and the mole fraction of urea bonds in the polyurethane resin (A) is 0.1 to 0.4. The present invention relates to a gravure ink for solvent-based laminating having a urea bond molar fraction in the resin (B) of 0.45 to 0.65.

In one embodiment of the present invention, the gravure for solvent-based laminating is such that the mass ratio of the polyurethane resin (A) to the polyurethane resin (B) is (A) :( B) = 95: 5 to 40:60 It relates to ink.

In one embodiment of the present invention, the sum of the urea bond concentration and the urethane bond concentration in the polyurethane resin (A) is 1.4 to 2 mmol / g, and the urea bond concentration and the urethane in the polyurethane resin (B) are The present invention relates to any of the above solvent-type laminating gravure inks, wherein the sum of the bond concentrations is 2.2 to 2.9 mmol / g.

Further, one embodiment of the present invention relates to any one of the above solvent-type laminating gravure inks, wherein the glass transition temperature of the mixture of the polyurethane resin (A) and the polyurethane resin (B) is −30 to 0 ° C.

Moreover, one embodiment of the present invention relates to any one of the above gravure inks for solvent-based laminating, in which the polyurethane resin (A) and / or the polyurethane resin (B) has a partial structure represented by the following general formula (1). .
General formula (1)

（式中、Ｒ^１は、水素原子またはアルキル基を表し、Ｒ^２は、アルキル基を表す。）

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

In one embodiment of the present invention, the storage elastic modulus E ′ at 30 ° C. of the mixture of the polyurethane resin (A) and the polyurethane resin (B) is 1 × 10 ⁷ to 1 × 10 ⁹ Pa. The present invention relates to a gravure ink for solvent type lamination.

In addition, one embodiment of the present invention further relates to any one of the solvent-type laminating gravure inks further containing a vinyl chloride copolymer resin (C) having a hydroxyl group.

Further, one embodiment of the present invention relates to a printed matter having a base material and a printed layer printed on the base material by the solvent-type laminating gravure ink.

Moreover, one Embodiment of this invention is related with the laminated body which has at least the 1st base material, the printing layer printed with the said gravure ink for solvent type | mold laminates, an adhesive bond layer, and a 2nd base material in this order.
The disclosure of the present application is related to the subject matter described in Japanese Patent Application No. 2016-220265 filed on November 11, 2016, the disclosure of which is incorporated herein by reference.

According to the present invention, it is possible to provide a gravure ink for solvent-type laminating that can achieve both excellent printing suitability and laminating suitability, and a printed matter and a laminate using the ink.

Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of embodiments of the present invention, and the present invention is not limited to the following contents as long as the gist thereof is not exceeded. In the present specification, “(meth) acryl” means “methacryl and acryl”, and “(meth) acrylate” means “methacrylate and acrylate”. Further, the “isocyanato group” may be referred to as “isocyanate group” or “NCO group”.

The solvent-type laminating gravure ink according to one embodiment of the present invention is a solvent-type laminating gravure ink containing a polyurethane resin (A) and a polyurethane resin (B). The mole fraction of urea bonds in the polyurethane resin (A) is 0.1 to 0.4, and the mole fraction of urea bonds in the polyurethane resin (B) is 0.45 to 0.65. The “solvent gravure ink for laminating” is a gravure ink used for laminating, and is a gravure ink containing an organic solvent. In the present specification, the solvent-type laminating gravure ink may be referred to as “gravure ink”.

The polyurethane resin (A) has the function of improving the laminate strength and re-solubility (printability) of the base material such as the polyolefin base material and the polyester base material, and the polyurethane resin (B) is a halftone dot in the printability. It plays a function of improving reproducibility (hereinafter sometimes referred to as “dot reproducibility”). It has been found that when two types of polyurethane resins (A) and (B) are mixed and used, both of the above functions can be realized, and a strong laminate strength is exhibited even for a silica or alumina-treated substrate. This synergistic effect is manifested when the two types of polyurethane resins (A) and (B) each have a mole fraction of urea bonds in a specific range. When the molar fraction of the urea bond in the polyurethane resin (A) is 0.1 to 0.4 and the molar fraction of the urea bond in the polyurethane resin (B) is 0.45 to 0.65 The effect is remarkable. In the present specification, the molar fraction of the urea bond is defined by the following formula (1).

Formula (1)
Molar fraction of urea bond =
[Urea binding concentration] / [Binding concentration formed by isocyanato groups]

In the mixture of the polyurethane resin (A) and the polyurethane resin (B), the molar fraction of the urea bond is preferably 0.3 to 0.5. More preferably, it is 0.4 to 0.5.
The molar fraction of urea bonds in the polyurethane resin (A) is more preferably 0.2 to 0.37, and still more preferably 0.3 to 0.35. The molar fraction of urea bonds in the polyurethane resin (B) is more preferably 0.48 to 0.60, and still more preferably 0.52 to 0.57.

OPP (polypropylene base material) tends to adhere to a resin having a high elastic modulus, and PET (polyester base material) tends to adhere to a resin having a low elastic modulus. The urea bond has a stronger cohesive force than the urethane bond, and dominates the rheological properties such as the elastic modulus and hardness of the urethane resin. By using together urethane resins having different urea bond ratios (different elastic moduli), it is considered that functional separation can be achieved with respect to adhesiveness, and laminate strength can be improved in various substrates. Further, when the gravure ink contains a pigment, the urea bond is considered to function as an adsorbing group for the pigment, and is effective for improving the printability. The above description is based on scientific considerations and does not limit the present invention in any way.

Examples of the bond formed by the isocyanato group (isocyanate group) include a urethane bond, a urea bond, a thiourethane bond, a thiourea bond, an allophanate bond, a burette bond, an isocyanurate bond, and a uretonimine bond. The polyurethane resin (A) and ( B) preferably has a urea bond and at least one selected from these. Among these, a case having a urethane bond and a urea bond is more preferable.

For example, the polyurethane resins (A) and (B) may be prepared by reacting a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol and a polyisocyanate with an amine chain extender. A polyurethane resin having a group is preferred. In this case, a urethane bond is generated by the reaction of the polyol and the polyisocyanate, and a urea bond is generated by reacting a urethane prepolymer having an isocyanate group at the terminal with the amine chain extender.

In this case, the mol% of the urea bond in 100 mol% of the bond formed by the isocyanato group can be calculated by the following formula (2).

Formula (2)
Molar fraction of urea bond =
[Urea bond concentration] / [Urethane bond concentration + urea bond concentration]

Here, [urethane bond concentration + urea bond concentration] can be calculated by the following equation (2-1).

Formula (2-1)
[Urethane bond concentration + urea bond concentration] =
[Number of moles of NCO group of polyisocyanate (mmol)] / [solid content mass of polyurethane resin (g)]

Here, since the number of moles of hydroxyl groups in the polyol is the same as the number of moles of urethane bonds, the urethane bond concentration can be calculated by the following equation (2-2).

Formula (2-2)
[Urethane bond concentration] =
[Mole number of hydroxyl group of polyol (mmol)] / [Mass of solid content of polyurethane resin (g)]

The urea bond concentration is represented by the formula (2-3).

Formula (2-3)
[Urea binding concentration] =
[Urethane bond concentration + urea bond concentration]-[Urethane bond concentration]

The polyol, polyisocyanate, and amine chain extender may be used alone or in combination of two or more, or different types may be used.

The concentration of the bond formed by the isocyanate group in the polyurethane resin (A) is, for example, 1.4 to 2.1 mmol / g, and preferably 1.4 to 2 mmol / g. The concentration of the bond formed by the isocyanato group in the polyurethane resin (B) is preferably 2.2 to 2.9 mmol / g. More preferably, the polyurethane resin (A) is 1.5 to 1.9 mmol / g, and the polyurethane resin (B) is 2.3 to 2.8 mmol / g. Within the above range, combined with the aforementioned mole fraction of urea bonds, functional separation becomes remarkable, and various properties such as laminate strength (physical properties), printability, and halftone dot reproducibility tend to be improved.

The mixing ratio of the polyurethane resin (A) and the polyurethane resin (B) is not particularly limited. For example, the mass ratio can be (A) :( B) = 98: 2 to 20:80. Further, it is preferable that (A) :( B) = 95: 5 to 40:60 in terms of mass ratio. In particular, the mass ratio is preferably (A) :( B) = 85: 15 to 75:25. In the case of this ratio, high laminate strength is easily obtained for various substrates. Further, when the glass transition temperature (hereinafter sometimes referred to as “Tg”) of the mixture of the polyurethane resin (A) and the polyurethane resin (B) is −30 to 0 ° C., the laminate strength tends to be further improved. is there. In this specification, the glass transition temperature (Tg) of the mixture of the polyurethane resin (A) and the polyurethane resin (B) is the maximum value of the curve of the temperature and loss tangent (Tanδ) obtained in the dynamic viscoelasticity measurement ( It is the temperature at the peak top). The glass transition temperature is more preferably −20 to 0 ° C.

The polyurethane resin (A) and / or the polyurethane resin (B) preferably has a partial structure represented by the following general formula (1).
General formula (1)

（式中、Ｒ^１は、水素原子またはアルキル基を表し、Ｒ^２は、アルキル基を表す。）

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

When the partial structure represented by the general formula (1) is introduced into the polyurethane resin (A) and / or the polyurethane resin (B), a polyol having the partial structure of the general formula (1) is used when synthesizing the polyurethane resin. do it. Thereby, the partial structure represented by the general formula (1) can be easily introduced into the polyurethane resin, and the laminate strength can be improved. This is because the alkyl group present in the side chain suppresses the rotation of the ether bond of the polyurethane resin main chain, promotes the improvement of the crystallinity of the polyurethane resin, and achieves both solubility and cohesion. It is done. Examples of the polyol containing the partial structure represented by the general formula (1) include polyether polyol, polyester polyol, and polycarbonate polyol.

The polyurethane resin (A) and / or the polyurethane resin (B) preferably has a partial structure represented by the following general formula (2).
General formula (2)

（式中、Ｒ^３は、水素原子またはアルキル基を表し、Ｒ^４は、アルキル基を表す。）

(In the formula, R ³ represents a hydrogen atom or an alkyl group, and R ⁴ represents an alkyl group.)

Examples of the polyol having a partial structure represented by the general formula (2) include neopentyl glycol, 2-methyl-1,3-propanediol, and / or 3-methyl-1,5-pentanediol, dibasic acid A polyester polyol obtained by reacting 2-butyl-2-ethyl-1,3-propanediol with a dibasic acid, and the like, preferably neopentyl glycol and / or Another example is a polyester polyol obtained by reacting 2-methyl-1,3-propanediol with a dibasic acid. More preferably, it is a polyester polyol obtained by reacting neopentyl glycol and adipic acid. For example, it can be introduced by using a polyester polyol composed of neopentyl glycol and a dibasic acid as a raw material when producing the polyurethane resin (A) and / or the polyurethane resin (B).

Examples of the alkyl group represented by R ¹ to R ⁴ in the general formula (1) and the general formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, and a sec-butyl group. . Among these, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

It is preferable that the polyester structure derived from the polyester polyol by reaction of neopentyl glycol and a dibasic acid is introduced into either or both of the polyurethane resin (A) and the polyurethane resin (B). The case where the polyurethane resin (A) has a polyester structure derived from a polyester polyol by a reaction between neopentyl glycol and a dibasic acid is more preferable. The content of the polyester structure derived from the polyester polyol by the reaction of neopentyl glycol and dibasic acid is preferably 1 to 85% by mass, particularly 20 to 80% by mass, in 100% by mass of the polyurethane resin. preferable.
In the present specification, the content of the polyester structure derived from the polyester polyol by the reaction between neopentyl glycol and dibasic acid is the polyol, polyisocyanate, amine chain extender, etc. containing the polyester polyol in the synthesis of the polyurethane resin. It can calculate as content (mass%) in the total mass of the compound (however, except an organic solvent) used as a raw material. Specifically, the content of the polyester structure is the content (% by mass) of the polyester polyol by the reaction of neopentyl glycol and dibasic acid in the total mass of the compound used as a raw material for constituting the polyurethane resin. ).

The mixture of the polyurethane resin (A) and the polyurethane resin (B) to be used preferably has a storage elastic modulus E ′ at 30 ° C. of 1 × 10 ⁷ to 1 × 10 ⁹ Pa. More preferably, it is 1 × 10 ⁷ to 1 × 10 ⁸ Pa. Furthermore, it is preferably 1 × 10 ⁷ Pa or more and less than 1 × 10 ⁸ Pa. High laminate strength is obtained when the value is within this range. The storage elastic modulus E ′ can be obtained by measuring dynamic viscoelasticity.

<Polyurethane resin (A)>
The polyurethane resin (A) has a urea bond molar fraction of 0.1 to 0.4, preferably 0.2 to 0.4. The weight average molecular weight of the polyurethane resin (A) is preferably 10,000 to 200,000. The glass transition temperature is preferably −30 to 0 ° C. Further, in the dynamic viscoelasticity measurement, the storage elastic modulus E ′ at 30 ° C. is preferably 1 × 10 ⁷ to 1 × 10 ⁸ Pa.

The polyurethane resin (A) preferably has an amino group and / or a hydroxyl group. In the case of having an amino group, the amine value is preferably 1.0 to 20.0 mgKOH / g, and more preferably 5 to 10 mgKOH / g. In the case of having a hydroxyl group, the hydroxyl value is preferably 1.0 to 20.0 mgKOH / g. The hydroxyl value is more preferably 0.5 to 10 mgKOH / g.

The polyurethane resin (A) preferably contains a structure derived from a polyester polyol. In this case, the content of the structure derived from the polyester polyol is preferably 1 to 85% by mass, more preferably 20 to 80% by mass, and still more preferably 30% in 100% by mass of the solid content of the polyurethane resin (A). ~ 80% by mass. In the present specification, the content of the structure derived from the polyester polyol can be calculated using the mass of the compound used as a raw material for constituting the polyurethane resin in the synthesis of the polyurethane resin. Specifically, the content of the structure derived from the polyester polyol is the content (mass of the polyester polyol) in the total mass of the compound (polyol containing the polyester polyol; polyisocyanate; amine chain extender, etc.) used as a raw material. %).

The polyurethane resin (A) may contain a structure derived from polyether polyol. In this case, the content of the structure derived from the polyether polyol is preferably 1 to 30% by mass, more preferably 1 to 20% by mass in 100% by mass of the solid content of the polyurethane resin (A). The polyurethane resin (A) or the polyurethane resin (B) may include a structure derived from a polyether polyol. In the present specification, the content of the structure derived from the polyether polyol can be calculated using the mass of the compound used as a raw material for constituting the polyurethane resin in the synthesis of the polyurethane resin. Specifically, the content of the structure derived from the polyether polyol is the content of the polyether polyol in the total mass of the compound (polyol including the polyether polyol; polyisocyanate; amine chain extender, etc.) used as a raw material. It can be determined as an amount (mass%).

The polyurethane resin (A) can be produced by a known method. For example, a polyurethane resin obtained by further reacting a urethane prepolymer having an isocyanato group at the terminal obtained by reacting a polyol and a polyisocyanate with an amine chain extender is preferable.

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, polyester polyol is preferred.

Examples of the polyester polyol include a condensate obtained by an esterification reaction of a dibasic acid and a diol. Dibasic acids include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1 4-cyclohexyl dicarboxylic acid, dimer acid, hydrogenated dimer acid and the like. Diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octanediol. 1,9-nonanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 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 Ether, dimer diol, hydrogenated dimer diol.
Among 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. For example, propylene glycol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexane Diol, 2-methyl-1,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octane Examples include diol, 2,2,4-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, and the like. These are preferable for improving printability, printing effect, and laminate strength.

Polyester polyol can be used alone or in admixture of two or more. As the dibasic acid, sebacic acid and adipic acid are particularly preferable. A polyol having 3 or more hydroxyl groups, a polyvalent carboxylic acid having 3 or more carboxyl groups, and the like can also be used in combination. Particularly preferred is a polyester polyol obtained by reacting at least one kind of branched diol selected from the above-mentioned branched diols (diols having a branched structure) with adipic acid, 3-methyl-1,5-pentanediol, Polyester polyols obtained by reacting 2-methyl-1,3-propanediol or neopentyl glycol and adipic acid are preferred, and 2-methyl-1,3-propanediol or neopentyl glycol and adipic acid are preferably used. A polyester polyol obtained by reaction is more preferred. In particular, a polyester polyol obtained by reacting neopentyl glycol and adipic acid is preferable.

The number average molecular weight of the polyester polyol is preferably 500 to 10,000. The number average molecular weight is determined by the following (formula 3). Further, the acid value of the polyester polyol is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less.

(Formula 3)
Number average molecular weight of polyol =
1000x56.1x hydroxyl number / hydroxyl value

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 using the terminal hydroxyl group, and is obtained from the above (formula 3).

The polyurethane resin (A) preferably further has a structure derived from a low molecular diol. The low molecular diol is used for the purpose of controlling the urethane bond concentration. There is no restriction | limiting in content, The storage elastic modulus E 'and / or glass transition temperature of a polyurethane resin (A) can be adjusted with content. The content is preferably 0.01 to 20.0% by mass, more preferably 0.01 to 10.0% by mass in 100% by mass of the solid content of the polyurethane resin (A). The low molecular diol preferably has a molecular weight of 50 to 400, and includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, , 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 and the like are preferable.

The polyisocyanate is preferably a diisocyanate, and various known diisocyanates such as an aromatic diisocyanate, an aliphatic diisocyanate, and an alicyclic diisocyanate 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 diisocyanate, 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 diiso Anate, dimeryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, Examples thereof include bis (chloromethyl) diphenylmethane diisocyanate, 2,6-diisocyanate benzyl chloride, and dimerisocyanate in which the carboxyl group of dimer acid is replaced with an isocyanato group. These trimers may be sufficient and a trimer has an isocyanurate ring structure. These polyisocyanates can be used alone or in admixture of two or more. Among them, preferred are tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate isocyanurate.

The amine chain extender is not limited to the following, but preferably has a molecular weight of 500 or less, a diamine chain extender (bifunctional amine compound), a polyfunctional amine chain extender (polyfunctional amine compound). ) And the like. For example, diamine chain extenders such as ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, p-phenylenediamine; 2- (2-aminoethylamino) ethanol N- (2-hydroxypropyl) ethylenediamine, N- (2-hydroxypropyl) propylenediamine, di-2-hydroxyethylethylenediamine, N, N′-bis (2-hydroxyethyl) ethylenediamine, N, N′-bis A diamine chain extender having a hydroxyl group such as (2-hydroxyethyl) propylenediamine can be used. These amine chain extenders can be used alone or in admixture of two or more.
If necessary, a trifunctional or higher polyfunctional amine chain extender can also be used. Specifically, diethylenetriamine, iminobispropylamine (IBPA, 3,3′-diaminodipropylamine), triethylenetetramine, N- (3-aminopropyl) butane-1,4-diamine (spermidine), 6, Examples include 6-iminodihexylamine, 3,7-diazanonan-1,9-diamine, N, N′-bis (3-aminopropyl) ethylenediamine, and the like. The polyurethane resin (A) preferably has a structure derived from a bifunctional amine compound (diamine) and / or a structure derived from a trifunctional amine compound (triamine), more preferably derived from a bifunctional amine compound. And a structure derived from a trifunctional amine compound. The amine chain extender is preferably at least one selected from the group consisting of isophorone diamine, hexamethylene diamine, iminobispropylamine, spermidine, and 6,6-iminodihexylamine.

According to one embodiment, the polyurethane resin (A) preferably has a urea bond derived from a trifunctional amine compound among the amine compounds that are amine chain extenders. The urea bond derived from the trifunctional amine compound has very high polarity and cohesion. Therefore, in gravure printing, the dot on the base is not melted even in overprinting, and the halftone dot reproducibility is extremely good. There is also an effect of improving the strength. More preferably, the polyurethane resin (A) has a urea bond derived from a bifunctional amine compound and a trifunctional amine compound. In this case, the mass ratio represented by the bifunctional amine compound / 3 trifunctional amine compound is 95/5 to 70/30. The bifunctional amine compound is preferably hexamethylenediamine, isophoronediamine, 2-hydroxyethylethylenediamine, and the trifunctional amine compound is preferably diethylenetriamine, iminobispropylamine (IBPA, 3,3′-diaminodiamine). Propylamine), triethylenetetramine, N- (3-aminopropyl) butane-1,4-diamine (spermidine), 6,6-iminodihexylamine.

Also, a monovalent active hydrogen compound can be used as a polymerization terminator for the purpose of terminating the excess reaction. As the monovalent active hydrogen compound, for example, a monoamine compound having a primary or secondary amino group is preferable, and examples thereof include dialkylamines such as di-n-butylamine and aminoalcohols such as 2-ethanolamine. . Furthermore, when it is desired to introduce a carboxyl group into the polyurethane resin, amino acids such as glycine and L-alanine can be used as a polymerization terminator. When a polymerization terminator is used, the chain terminator and chain extender may be used together to carry out a chain extension reaction, and after a certain amount of chain extension reaction is performed with the chain extender, the polymerization terminator is used alone. It may be added to stop the chain extension reaction. On the other hand, the molecular weight can be controlled without using a polymerization terminator, but in this case, a method of adding a urethane prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

The polyurethane resin (A) is preferably produced by reacting a polyol with polyisocyanate and then reacting with an amine chain extender and, if necessary, a polymerization terminator to make a polyurethane resin. An amine chain extender can also be used in a urethanization reaction with a polyisocyanate together with a polyol. For example, it can be produced by a known method such as a prepolymer method or a one-shot method. Specifically, in the prepolymer method, first, polyol and polyisocyanate are used at a temperature of 50 ° C. to 150 ° C. using a solvent inert to the isocyanato group as necessary, and further using a urethanization catalyst if necessary. The reaction is carried out at a temperature of 0 ° C. (urethane reaction) to produce a urethane prepolymer having an isocyanato group at the terminal. Next, the urethane prepolymer is reacted with an amine chain extender to obtain a polyurethane resin. In the one-shot method, the polyol, polyisocyanate, and amine chain extender are reacted in one step with a polymerization terminator as necessary to obtain a polyurethane resin (A).

In the production of the urethane prepolymer, the amount of polyol and polyisocyanate is the ratio of the number of moles of isocyanate groups of the polyisocyanate to the number of moles of hydroxyl groups of the polyol. It is preferable to be in the range.

Also, in the synthesis of the urethane prepolymer, it is preferable in terms of reaction control to use an organic solvent as a solvent. The organic solvent that can be used is preferably an organic solvent that is inert to the isocyanato 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; esters such as ethyl acetate and butyl acetate; And halogenated hydrocarbons. 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 urethane 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% based on the polyol.

By reacting the obtained urethane prepolymer having an isocyanato group with an amine chain extender such as diamine or triamine at a temperature of about 10 to 60 ° C., a high molecular weight compound containing an active hydrogen group at the terminal is obtained. A polyurethane resin (A) is obtained.

The ratio of the total number of moles of amino groups of the amine chain extender to the number of moles of isocyanato groups in the urethane prepolymer is preferably 1.01 to 2.00, more preferably 1.03 to 1.06. React so that it is within range.

<Polyurethane resin (B)>
The polyurethane resin (B) has a urea bond molar fraction of 0.45 to 0.65. The weight average molecular weight of the polyurethane resin (B) is preferably 10,000 to 100,000. The glass transition temperature is preferably 0 to −30 ° C. Further, the storage elastic modulus E ′ at 30 ° C. in the dynamic viscoelasticity measurement is preferably 1 × 10 ⁷ to 1 × 10 ⁹ Pa.

The polyurethane resin (B) preferably has an amino group and / or a hydroxyl group. In the case of having an amino group, the amine value is preferably 1 to 25 mgKOH / g, more preferably 10 to 20 mgKOH / g, and still more preferably 14 to 20 mgKOH / g. In the case of having a hydroxyl group, the hydroxyl value is preferably 1 to 20 mgKOH / g. The polyurethane resin (B) may have a hydroxyl value of 0 mgKOH / g.

The polyurethane resin (B) preferably contains a structure derived from a polyester polyol. In that case, the content of the structure derived from the polyester polyol is preferably 1 to 85% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 30% by mass in 100% by mass of the solid content of the polyurethane resin (B). 80% by mass.

The polyurethane resin (B) may contain a structure derived from a polyether polyol as necessary, and the content of the structure derived from the polyether polyol in that case is 1 in 100% by mass of the solid content of the polyurethane resin (B). It is preferably ˜30% by mass, more preferably 1˜20% by mass.

The polyurethane resin (B) can be produced by a known method. For example, like the polyurethane resin (A), a polyurethane resin obtained by further reacting a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol and polyisocyanate with an amine chain extender is preferable.

Examples of the polyol include the same as those in the case of the polyurethane resin (A), and among them, a polyester polyol is preferable. The number average molecular weight of the polyester polyol is preferably 500 to 10,000.

Examples of the polyester polyol include those similar to those of the polyurethane resin (A), but a polyester obtained by reacting neopentyl glycol and / or 2-methyl-1,3-propanediol with adipic acid. Polyols are preferable, and the polyurethane resin (B) preferably has those structures. Polyester polyols obtained by reacting 2-methyl-1,3-propanediol and / or 3-methyl-1,5-pentanediol with adipic acid are preferred, and the polyurethane resin (B) is preferably used Those having a structure are preferred.

The polyurethane resin (B) may contain a polyether structure, and preferably has a structure derived from a polyether polyol. 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 the above (formula 3).

The polyurethane resin (B) may further have a structure derived from a low molecular diol. The preferred low molecular diol is the same as in the case of the polyurethane resin (A).

Examples of the polyisocyanate that can be used in the production of the polyurethane resin (B) include the same polyisocyanates as in the case of the polyurethane resin (A). Preferably, it is at least one selected from the group consisting of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isocyanurate of hexamethylene diisocyanate.

Examples of the amine chain extender that can be used in the production of the polyurethane resin (B) include the same ones as in the case of the polyurethane resin (A). Among these, at least one selected from the group consisting of isophoronediamine, hexamethylenediamine, iminobispropylamine, N- (3-aminopropyl) butane-1,4-diamine (spermidine), and 6,6-iminodihexylamine is preferable. It is a seed or two or more. Further, as the polymerization terminator for the purpose of terminating the excess reaction, the same one as in the case of the polyurethane resin (A) can be used.

The production method of the polyurethane resin (B) includes the same method as the polyurethane resin (A). For example, a polyol is reacted with polyisocyanate to obtain a urethane prepolymer having an isocyanato group at the end, and then reacted with an amine chain extender and, if necessary, a polymerization terminator to obtain a polyurethane resin (B).

In producing the urethane prepolymer, the amount of polyol and polyisocyanate is such that the NCO / OH ratio = 1.9 to 2.6, which is the ratio of the number of moles of isocyanate groups of the polyisocyanate to the number of moles of hydroxyl groups of the polyol. It is preferable to be in the range.

<Vinyl chloride copolymer resin (C) having a hydroxyl group>
According to one embodiment, the gravure ink for solvent-based laminating preferably further contains a vinyl chloride copolymer resin (C) having a hydroxyl group in addition to the polyurethane resin (A) and the polyurethane resin (B). Examples of the vinyl chloride copolymer resin (C) include vinyl chloride-vinyl acetate copolymer resin and vinyl chloride-acrylic copolymer resin.

(Vinyl chloride-vinyl acetate copolymer resin)
The vinyl chloride-vinyl acetate copolymer resin is a resin in which at least vinyl chloride and vinyl acetate are copolymerized. The vinyl chloride-vinyl acetate copolymer resin preferably has a weight average molecular weight of 5,000 to 100,000, more preferably 20,000 to 70,000. 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. The vinyl chloride-vinyl acetate copolymer resin has a hydroxyl group. In one embodiment, the vinyl chloride-vinyl acetate copolymer resin preferably contains a hydroxyl group derived from vinyl alcohol by a saponification reaction or copolymerization in order to improve solubility in an organic solvent. The hydroxyl value of the vinyl chloride-vinyl acetate copolymer resin is preferably 20 to 200 mgKOH / g. The glass transition temperature is preferably 50 to 90 ° C. In one embodiment, the vinyl chloride-vinyl acetate copolymer resin is preferably a resin obtained by copolymerizing an acrylic monomer in addition to vinyl chloride and vinyl acetate, and the acrylic monomer contains an acrylic monomer having a hydroxyl group. Is preferred.

(Vinyl chloride-acrylic copolymer resin)
The vinyl chloride-acrylic copolymer resin is mainly composed of a copolymer of vinyl chloride and an acrylic monomer. As the acrylic monomer, an acrylic monomer having a hydroxyl group is preferably included. The vinyl chloride-acrylic copolymer resin may be a block copolymer or a random copolymer of vinyl chloride and an acrylic monomer, or may be a graft copolymer in which an acrylic monomer is grafted on a side chain of polyvinyl chloride. The vinyl chloride-acrylic copolymer resin preferably has a weight average molecular weight of 10,000 to 100,000, and more preferably 30,000 to 70,000. The vinyl chloride-derived structure in the vinyl chloride-acrylic copolymer resin is preferably 70-95% by mass in 100% by mass of the vinyl chloride-acrylic copolymer resin solid content. The structure derived from the acrylic monomer having a hydroxyl group in the vinyl chloride-acrylic copolymer resin is preferably 5 to 30% by mass in 100% by mass of the vinyl chloride-acrylic copolymer resin solid content. The hydroxyl value of the vinyl chloride-acrylic copolymer resin is preferably 20 to 200 mgKOH / g. In this case, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, laminate strength, and the like are improved.

Examples of the acrylic monomer having a hydroxyl group include hydroxyalkyl (meth) acrylate, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( Such as 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, etc. (Meth) acrylic acid hydroxyalkyl ester; glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate; Lactone-modified (meth) acrylate, hydroxyethyl acrylamide. Of these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are preferred. These can be used alone or in combination of two or more.

The acrylic monomer may also contain (meth) acrylic acid alkyl ester. The alkyl group in the (meth) acrylic acid alkyl ester 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 And octadecyl. The alkyl group may have an aromatic ring structure substituted with an aryl group or the like. These can be used alone or in combination of two or more.

In addition, the acrylic monomer may have a functional group other than a hydroxyl group, and examples of such a functional group include a carboxyl group, an amide group, an amino group, and an alkylene oxide group.

<Cellulosic resin>
The solvent-type laminating gravure ink may further contain a cellulose resin. Examples of the cellulose resin include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose, and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group. Furthermore, the alkyl group may have a substituent. Among these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable. The weight average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 200,000. The glass transition temperature is preferably 120 ° C to 180 ° C.

The gravure ink for solvent-type lamination is composed of a total of polyurethane resin (A) and polyurethane resin (B) and vinyl chloride copolymer resin (C) in a mass ratio (total of (A) and (B) / (C)) 95 / It is preferably contained at 5 to 40/60, more preferably 90/10 to 50/50. More preferably, it is included at 90/10 to 60/40. When it is within these ranges, printability, substrate adhesion, coating film properties and laminate strength are good. When the above (A), (B) and (C) are used in combination, the total of the above resins (A), (B) and (C) is 3 to 25 mass as a solid content in 100% by mass of the gravure ink. %, Preferably 6 to 18% by mass.

<Pigment>
In one embodiment, it is preferable to use a pigment as a colorant in the gravure ink for solvent-based lamination. There are inorganic pigments and organic pigments. Organic pigments are not limited to the following examples, but soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, ansanthrone, dianthraquinonyl, anthrapyrimidine, perylene , Perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, carbon black, etc. Is mentioned. 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 preferred organic pigments are shown below by generic names of color indexes. The organic pigment is preferably at least one 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. At least one or more selected from the group consisting of a pigment, an indigo pigment, a red pigment, and a yellow pigment are preferred. In particular, the use of indigo pigment and / or red pigment improves the printing effect (trapping property) of overprinting, and it is preferable to use these.

<Black pigment>
Specifically, C.I. I. Of the black pigments of CI Pigment Black 1 to 34, black pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. 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. Of the cyan pigments of CI Pigment Blue 1 to 80, an indigo pigment which is an organic compound or an organometallic complex is preferable. For example, 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: 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. Of the green pigments of CI Pigment Green 1 to 50, green pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. 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 preferred. For example, C.I. 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. And CI Pigment Red 279.

<Purple pigment>
Specifically, C.I. I. Of the purple pigments of CI Pigment Violet 1 to 50, purple pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. 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. And CI Pigment Violet 50.

<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 preferred. For example, C.I. 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 which is an organic compound or an organometallic complex is preferable. For example, C.I. 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 orange 38, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 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>
Examples of brown pigments include C.I. 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 cocoon 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 cocoon 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 at least one selected from these groups or two or more are preferably used.

Solvent-type gravure ink is available in other hues as necessary (in addition to white as a basic color, a total of five colors: yellow, red, indigo and black; red (orange), grass (outside process gamut) (Green) and purple (3 colors; transparent yellow, peony, vermilion, brown, or pearl ink).

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

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

The pigment is preferably used in an amount sufficient to ensure the density and coloring power of the gravure ink. For example, the pigment is preferably contained at 1 to 50% by mass with respect to the total mass of the gravure ink. Further, in terms of the solid content mass ratio in the gravure ink, the pigment is preferably contained in a proportion of 10 to 90% by mass with respect to the total mass of the solid content in the gravure ink. The pigments can be used alone or in combination of two or more.

<Silica particles>
In one embodiment, the solvent-type laminating gravure ink preferably contains silica particles. Silica includes natural or synthetic products; crystalline or non-crystalline; or hydrophobic or hydrophilic silica. There are dry and wet methods for synthesizing silica, combustion methods and arc methods are known for dry methods, precipitation methods and gel methods are known for wet methods, and any of these methods may be synthesized. The silica may be hydrophilic silica having a hydrophilic functional group on the surface, or may be hydrophobic silica obtained by modifying the hydrophilic functional group with alkylsilane or the like to make it hydrophobic, but is preferably hydrophilic. Hydrophilic silica has the effect of improving blocking resistance to various substrates. The addition amount of the silica particles is preferably 0.2 to 1.5% by mass in 100% by mass of the gravure ink for solvent-type lamination.

The silica particles preferably have an average particle diameter of 1 to 5 μm when irregularities are formed on the surface of the ink layer. In addition, the average particle diameter of a silica particle means the particle size in the integrated value 50% (D50) in a particle size distribution, and can be calculated | required by the Coulter counter method.

<Organic solvent>
The solvent-type laminating gravure ink contains an organic solvent as a liquid medium. Organic solvents used include aromatic organic solvents such as toluene and xylene; ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate A known organic solvent such as an alcoholic organic solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol propyl ether or the like can be used. These organic solvents may be used as a mixture, and preferably contain at least one selected from propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol propyl ether in an amount of 10% by mass or less in the organic solvent. Furthermore, an organic solvent that does not contain an aromatic organic solvent such as toluene and xylene (non-toluene organic solvent) is preferable because the dot reproducibility is good. More preferably, an organic solvent composed of an ester organic solvent and an alcohol organic solvent is used. According to one embodiment, the solvent-type laminating gravure ink contains an organic solvent as a main component of the liquid medium, but may contain water as the liquid medium. In that case, the content of water is preferably 0.1 to 10% by mass in 100% by mass of the liquid medium. The liquid medium preferably contains 90 to 100% by mass of an organic solvent in 100% by mass of the liquid medium.

<Other resins>
In one embodiment, the solvent-type laminating gravure ink may contain other resins. Other resins include, for example, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic acid resin, terpene resin, phenol modified terpene resin, ketone Examples thereof include resins, cyclized rubbers, chlorinated rubbers, polyvinyl acetal resins, petroleum resins, and modified resins thereof. These other resins can be used alone or in admixture of two or more. When other resins are contained, the content thereof is preferably 1 to 20% by mass in 100% by mass of the solid content of the binder resin (B). Among them, it is preferable to contain 0.1 to 1% by mass of chlorinated polypropylene resin.

<Additives>
In one embodiment, the gravure ink can appropriately contain known additives. Examples of additives include pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, waxes, isocyanate curing agents, silane coupling agents, and the like. Is mentioned.

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 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.

<Manufacture of ink>
According to one embodiment, the gravure ink for solvent-based laminating can be produced by dissolving and / or dispersing the polyurethane resin (A) and the polyurethane resin (B) in a liquid medium. Specifically, for example, a pigment dispersion in which an organic pigment, polyurethane resins (A) and (B), a vinyl chloride copolymer resin (C), and a dispersant as necessary are mixed and dispersed in an organic solvent. Producing a gravure ink for solvent-type laminating by further blending polyurethane resins (A) and (B), and other resins, additives, etc., if necessary, in the pigment dispersion obtained. Can do. 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 treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the disperser, for example, commonly used dispersers such as a roller mill, a ball mill, a pebble mill, an attritor, and a sand mill can be used. If the ink contains bubbles, coarse particles, etc., 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 solvent-type laminating gravure ink is in a 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) in the gravure printing method. It is preferable. More preferably, it is 50 to 400 cps. This viscosity range corresponds to a viscosity in the Zahn cup # 4 of about 9 to 50 seconds. The viscosity of the gravure ink can be adjusted by appropriately selecting the type and amount of raw materials used, for example, the amount of organic pigment, polyurethane resins (A) and (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 is suitable for printing by a gravure printing method, diluted to a viscosity and concentration suitable for gravure printing, and supplied alone or mixed to each printing unit. After printing with a gravure ink on a substrate, a printed layer can be formed by removing volatile components to obtain a printed matter.

<Base material>
According to one embodiment, the base material that can be used for the printed material is, for example, 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, Examples include polyamide, polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., and film-like substrates made of these composite materials. Also, inorganic compounds such as silica, alumina, aluminum, etc. are converted into polyethylene terephthalate and nylon films. Vapor-deposited substrates can also be used. Furthermore, polyvinyl alcohol or the like may be coated on the vapor deposition surface of the inorganic compound or the like, and surface treatment such as corona treatment may be further performed.

<Laminate>
According to one embodiment, the laminate is a laminate in which a first substrate, a printed layer printed with gravure ink, an adhesive layer, and a second substrate are laminated in this order. The said base material can be made into a 1st base material. The laminate may have an arbitrary layer. An arbitrary layer includes an anchor coat layer obtained by applying an anchor coat agent. The laminate can be produced, for example, by laminating the second substrate on the printing surface printed with the gravure ink on the first substrate by the following method. As a method of laminating the second base material, an extrusion laminate (extrusion) in which the molten polyethylene resin and the second base material are laminated via various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium. Laminating) method; a dry laminating method in which an adhesive such as urethane is applied to the printing surface and a second substrate is laminated thereon; or a non-solvent laminating method. The second substrate may be the same as or different from the first substrate. Examples of the second base material include unstretched polypropylene (CPP), linear polyethylene (LLDPE), nylon, aluminum-deposited polyethylene terephthalate, and aluminum foil.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. “Part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified.

(Hydroxyl value)
It was determined according to JIS K0070 (1992).
(Acid value)
It was determined according to JIS K0070 (1992).
(Amine number)
The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The amine value was measured by the following method according to JIS K0070 (1992).
0.5-2 g of the sample was accurately 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 used as the end point, and the titer (AmL) at this time was used to determine the amine value by the following formula.
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 the 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: Dimethylformamide Flow rate: 1.0 mL / min

<Synthesis of polyurethane resin (A)>
(Synthesis Example 1)
[Polyurethane resin A1]
190 parts of a polyester polyol (hereinafter referred to as “PMPA”) which is a condensate of adipic acid having a number average molecular weight of 2000 and 3-methyl-1,5-pentanediol, 1,4-butanediol (hereinafter referred to as “1,4-BD”) ) 10.0 parts, 64.1 parts of isophorone diisocyanate (hereinafter “IPDI”) and 66.0 parts of ethyl acetate were reacted at 80 ° C. for 4 hours under a nitrogen stream to obtain a urethane prepolymer having an isocyanato group at the terminal. A solution containing was obtained. Subsequently, 14.87 parts of isophorone diamine (hereinafter “IPDA”) and 584.9 parts of a mixed solvent of ethyl acetate / 2-propanol (hereinafter “IPA”) = 50/50 (mass ratio) were mixed with the above. The urethane prepolymer solution was gradually added at 40 ° C. Then, it was made to react at 80 degreeC for 1 hour, and the solution of polyurethane resin A1 which is a polyurethane resin (A) of 30% of solid content, an amine number of 6.0 mgKOH / g, and a weight average molecular weight of 52000 was obtained.

The urethane bond concentration, the urea bond concentration, and the mole fraction of the urea bond in the polyurethane resin A1 were calculated based on the following calculation formula. The total solid content mass is the total mass of the compounds used as raw materials in the synthesis of the polyurethane resin.

Urethane bond concentration in A1 = [(190 g (PMPA mass) / 2000 (PMPA molecular weight)) × 2 (PMPA hydroxyl number) + (10.0 g (1,4-BD mass) /90.12 ( 1,4-BD molecular weight)) × 2 (number of 1,4-BD hydroxyl groups)] / 279 g (total solid content of polyurethane resin A1) = 0.148 mol / g = 1.48 mmol / g

Sum of urethane bond concentration and urea bond concentration in A1 = [(64.1 g (mass of IPDI) /222.29 (molecular weight of IPDI)) × 2 (number of isocyanato groups of IPDI)] / 279 g (total of polyurethane resin A1) (Mass of solid content) = 0.00207 mol / g = 2.07 mmol / g

Urea bond concentration in A1 = sum of urethane bond concentration and urea bond concentration in A1−urethane bond concentration in A1 = 2.07 mmol / g−1.48 mmol / g = 0.59 mmol / g

Molar fraction of urea bonds in A1 = urea bond concentration in A1 / sum of urethane bond concentration and urea bond concentration in A1 = 0.59 mmol / g / 2.07 mmol / g = 0.29

(Synthesis Examples 2 to 6, Comparative Synthesis Examples 7 and 8)
[Polyurethane resins A2 to A8]
Polyurethane resins A2 to A8 were obtained in the same manner as in Synthesis Example 1 except that the materials shown in Table 1-1 were used. In Table 1-1, NPA, MPO, PPG, IBPA, and 2EtAm represent the following, respectively.
NPA: Polyester polyol which is a condensate of adipic acid and neopentyl glycol MPO: Polyester polyol which is a condensate of adipic acid and 2-methyl-1,3-propanediol PPG: Polypropylene glycol IBPA: Iminobispropylamine 2 EtAm: 2 -Aminoethanol In the table, the molecular weight of the material and the urethane bond concentration, urea bond concentration, mole fraction of urea bond, hydroxyl value, amine value, and weight average molecular weight of the obtained polyurethane resins A2 to A8 are shown together. . The blanks in the table indicate that no compound is included, and the numerical values without the unit description mean “parts”. Among the polyurethane resins, polyurethane resins A1 to A6 are polyurethane resins (A), and polyurethane resins A7 and A8 are polyurethane resins that are neither polyurethane resin (A) nor polyurethane resin (B). Of the above materials, NPA and MPO are materials having a partial structure represented by the general formula (1).

<Synthesis of polyurethane resin (B)>
(Synthesis Examples 9 to 14, Comparative Synthesis Examples 15 and 16)
[Polyurethane resins B1 to B8]
Solutions of polyurethane resins B1 to B8 were obtained in the same manner as in Synthesis Example 1, except that the materials shown in Table 1-2 were used. Of the polyurethane resins, polyurethane resins B1 to B6 are polyurethane resins (B), and polyurethane resins B7 and B8 are polyurethane resins that are neither polyurethane resin (A) nor polyurethane resin (B).

(Synthesis Example 17)
[Vinyl chloride-acrylic copolymer resin]
In an autoclave, 1.0 part of potassium peroxodisulfate (K ₂ S ₂ O ₈ ) was dissolved in 500 parts of water and deaerated. After the temperature was raised to 60 ° C., 425 parts of a mixture comprising 357 parts of vinyl chloride, 63 parts of 2-hydroxypropyl acrylate, and 5.0 parts of sodium di-2-ethylhexylsulfosuccinate (product name: Aerosol OT) was placed in the autoclave. In addition, the reaction was carried out at 60 ° C. and 6.5 atm. The reaction was continued until the autoclave reached 2.5 atm. Sodium chloride was added to the obtained emulsion to precipitate a reaction product, which was filtered, washed and dried to obtain a vinyl chloride-acrylic copolymer resin having a hydroxyl group. Further, ethyl acetate was added to obtain a 30% solid solution (PVAc1). The content of 2-hydroxypropyl acrylate in the obtained resin was 14.0%, the hydroxyl value was 60 mgKOH / g, the weight average molecular weight was 50000, and the glass transition temperature was 70 ° C.

Example 1
[Preparation of solvent-type laminating gravure ink S1]
36 parts of polyurethane resin solution A1 (solid content 30%), 9 parts of polyurethane resin solution B1 (solid content 30%), C.I. I. 11 parts of Pigment Blue 15: 3 (Lionol Blue FG7330 manufactured by Toyocolor Co., Ltd.) and 44 parts of a solvent consisting of n-propyl acetate (NPAC) / IPA = 70/30 (mass ratio) were mixed and mixed for 30 minutes with an Eiger mill. Dispersion was carried out to obtain a gravure ink S1 for solvent-type lamination.

(Examples 2 to 25)
[Preparation of solvent-type laminating gravure inks S2 to S25]
Except for the materials shown in Table 2-1 and Table 2-2, solvent-type laminating gravure inks S2 to S24 were obtained in the same manner as in Example 1, respectively. C. in the table. I. As pigment yellow 14, Lionol Yellow TT1405G manufactured by Toyo Color Co., Ltd. was used, and as titanium oxide, Titanics JR-805 manufactured by Teika Co., Ltd. was used. Abbreviations in the table represent the following.
Solvain TA3: vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group (manufactured by Nissin Chemical Industry Co., Ltd., vinyl chloride / vinyl acetate / hydroxyalkyl acrylate = 83/4/13 (mass ratio), hydroxyl value 70 mgKOH / g, solid content 30% ethyl acetate solution)
Solvain TAO: Vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group (manufactured by Nissin Chemical Industry Co., Ltd., vinyl chloride / vinyl acetate / vinyl alcohol = 91/2/7 (mass ratio), hydroxyl value 95 mgKOH / g, solid content 30 % Ethyl acetate solution)

(Comparative Examples 1 to 18)
[Creation of gravure inks T1 to T18]
Gravure inks T1 to T18 were obtained in the same manner as in Example 1 except that the materials shown in Table 3 were changed.

<Storage elastic modulus (E ') and glass transition temperature (Tg)>
The polyurethane resin (A) solution and the polyurethane resin (B) with the same mixing ratio as the polyurethane resin (A) solution and the polyurethane resin (B) solution (gravure ink) in Examples 1 to 25 and Comparative Examples 1 to 18 A solution (mixed solution) was prepared, and the mixed solution was applied and dried to form a dry film having a thickness of 0.5 mm. Using a dynamic viscoelasticity automatic measuring machine (DDV-GP series (Leovibron) manufactured by A & D Co., Ltd.) for each, the temperature range is -60 ° C to 200 ° C, and the measurement is performed at a heating rate of 10 ° C / min. The storage elastic modulus E ′ (Pa) at 30 ° C. was determined. The peak top temperature of the loss tangent tan δ was defined as Tg (° C.). Incidentally, E ′ (Pa) at 30 ° C. is shown by the following criteria. The results are shown in Table 2-1, Table 2-2 and Table 3.
A ... 1 x 10 ⁷ Pa or more and less than 1 x 10 ⁸ Pa B ... 1 x 10 ⁸ Pa or more and less than 1 x 10 ⁹ Pa C ... 1 x 10 ⁶ Pa or more 1 x 10 ⁷ Pa Less than D ... 1 x 10 ⁹ Pa or more and less than 1 x 10 ¹⁰ Pa E ... 1 x 10 ⁵ Pa or more and less than 1 x 10 ⁶ Pa

(Example 26)
<Printing of gravure ink for solvent lamination>
The solvent-type laminating gravure inks S1 and S25 obtained above were mixed with a mixed solvent consisting of methyl ethyl ketone (MEK): NPAC: IPA = 40: 40: 20 (mass ratio) for a viscosity of 16 seconds (25 ° C., Zaan cup). It diluted so that it might become No.3). S1 is a Helio 175 line gradation version (plate-compressed, 100% to 3% gradation pattern), and S25 is a corrosive 175 line (plate depth 25 μm) half-solid version. On the surface, 1000 m was overprinted in the order of S1 and S25 at a printing speed of 100 m / min to obtain printed matter F1 (OPP), G1 (PET), and H1 (silica vapor-deposited nylon). The printing environment was a temperature of 25 ° C. and a humidity of 55% RH.
<Base material>
-Corona discharge treated biaxially oriented polypropylene (OPP) film (FOR TOYOBO Co., Ltd., FOR thickness 20 μm)
-Corona discharge treated polyester (PET) film (E-5100, thickness 12μm, manufactured by Toyobo Co., Ltd.)
・ Silica vapor-deposited nylon film (Mitsubishi Resin Tech Barrier TX thickness 15μm)

(Extrusion laminate processing)
Solid content 1% (weight ratio, methanol) obtained by diluting polyethyleneimine anchor coating agent (EL420 manufactured by Toyo Morton Co., Ltd.) with a solvent consisting of methanol: water = 70: 30 (mass ratio) on the printed surface of printed matter F1 and G1 / Water = 70/30) was applied. At the same time as the low density polyethylene melted at 315 ° C. (Novatech LC600, manufactured by Nippon Polychem Co., Ltd.) is overlaid on the coated surface, unstretched polypropylene (FCMN, Mitsui Chemicals Tosero Co., Ltd., FCMN, film thickness 40 μm) is also applied on the low density polyethylene. By combining, an extrusion lamination process was performed to obtain a laminate.

(Dry laminating)
On the printed surface of the printed material H1, a 20% solid content ethyl acetate solution obtained by diluting a polyester urethane laminate adhesive (TM250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) The coating was applied to 2.0 g / m ² and dried. After drying, 80 μm-thick unstretched polypropylene (CPP) was bonded to the adhesive layer and subjected to dry lamination to obtain a laminate.

(Examples 27 to 50)
Printed materials F2 to F25, G2 to G25, and H2 to H25 were obtained in the same manner as in Example 26, except that S2 to S25 were used instead of S1. Each printed matter was subjected to extrusion laminating and dry laminating in the same manner as described above to obtain a laminate. In addition, evaluation was performed after hold | maintaining a laminated body for 40 hours at 40 degreeC.

(Comparative Examples 19 to 36)
Printed materials FF1 to FF18, GG1 to GG18, and HH1 to HH18 were obtained in the same manner as in Example 26 except that T1 to T18 were used instead of S1 and T18 was used instead of S25. Each printed matter was subjected to extrusion laminating and dry laminating in the same manner as described above to obtain a laminate. In addition, evaluation was performed after hold | maintaining a laminated body for 40 hours at 40 degreeC.

The following evaluations were performed on the obtained gravure ink for solvent-type lamination, printed matter, and laminate, and the results are shown in Table 4-1, Table 4-2, and Table 5.

<Base material transferability>
Regarding the obtained printed materials G1 to G25 (Examples) and printed materials GG1 to GG18 (Comparative Examples), the substrate transferability was evaluated based on the area% of the transferred ink for the 5% gradation portion.
A: The ink transfer area is 100% (good)
B ... Ink transfer area is 80% or more and less than 100% (practical)
C: The ink transfer area is 60% or more and less than 80% (slightly poor)
D: The ink transfer area is 30% or more and less than 60% (defect)
E .... Ink transfer area is less than 30% (very bad)
In addition, A and B are ranges in which there is no practical problem.

<Plate castability>
Plate fogging evaluation was performed on the gravure inks S1 to S25 (Examples) and T1 to T18 (Comparative Examples). The dilution solvent was a mixed solvent of MEK: NPAC: IPA = 40: 40: 20 (mass ratio), and the viscosity was 16 seconds (25 ° C.) with Zahn cup # 3. The area of the plate cover portion after 60 minutes of idling of the plate in the printing press was visually judged and evaluated.
A: The plate covering area is less than 5% (good)
B ... The plate cover area is 5% or more and less than 10% (practical)
C ··· Plate cover area is 10% or more and less than 30% (slightly poor)
D: The plate covering area is 30% or more and less than 50% (defect)
E ··· Plate cover area is 50% or more (very bad)
In addition, A and B are ranges in which there is no practical problem.

<Reproducibility of halftone dots>
For the obtained printed materials G1 to G25 (Example) and printed materials GG1 to GG18 (Comparative Example), the overprinted portion of the 35% gradation portion was observed using a microscope (VHX-5000) manufactured by Keyence Co., Ltd. Reproducibility was evaluated.
A .... No change in halftone dot size (good)
B ... Slightly spread in halftone dot size (practical)
C ... The dots are blotted by 10% or more but less than 20% due to overlapping ink (slightly poor)
D ··· The halftone dots are smeared by 20% or more but less than 30% due to overlapping ink (defect)
E ... All the dots are broken by the overlapping ink (very bad)
In addition, A and B are ranges in which there is no practical problem.

<Blocking resistance>
Printed materials F1 to F25 (OPP), G1 to G25 (PET) and H1 to H25 (silica vapor-deposited nylon), FF1 to FF18 (OPP), GG1 to GG18 (PET) and HH1 to HH18 (silica vapor-deposited nylon) are as follows: The blocking resistance was evaluated under the following conditions.
(Sample and pressure)
Printing surface of OPP printed matter / non-corona-treated surface of OPP substrate 7 kg / cm ²
Printed surface of PET printed matter / Non-corona treated surface of PET substrate 7kg / cm ²
Silica-deposited nylon print / silica-deposited nylon non-deposition surface 7 kg / cm ²
(Standing conditions) 40 ° C.-80% RH 14 hours (Evaluation method) The printed surface and various substrates are peeled off, and the degree of ink film removal (peeling) from the printed surface is judged visually (determination criteria)
A ··· The ink film on the printed surface does not peel at all, and the peel resistance is low (good)
B ···· The peeled area of the ink film is 1% or more and less than 5%, and the peel resistance is small (practical)
C ··· The peeled area of the ink coating is 5% or more and less than 20% (slightly poor)
D ··· Ink film peeling area of 20% or more and less than 50% (defect)
E .... The ink film peels 50% or more (very bad)
In addition, A and B are ranges in which there is no practical problem.

<Lamination strength>
For the printed matter F1 to F25, G1 to G25 and H1 to H25, and the overprinted portion of the laminate laminate of the printed matter FF1 to F18, GG1 to GG18 and HH1 to HH18, the ink part is cut to a width of 15 mm, Peeling was performed on the surface of the material, and the peel strength (laminate strength) was measured with a 2010 universal tensile tester manufactured by Intesco Corporation. The practical level is 0.7 N / 15 mm or more.

<Appearance after retort>
Laminated laminates of printed materials H1 to H25 (Examples) and printed materials HH1 to HH18 (Comparative Examples) were cut out and then heat sealed (150 ° C., 2 seconds), 10 cm × 6 cm bag (content is water) And retort sterilization at 120 ° C. for 30 minutes. The laminate laminate after retorting was hand-rubbed for 60 seconds, and then the appearance was confirmed and evaluated.
A ... No delamination or unevenness (good)
B ・ ・ ・ ・ There are 2 to 3 floats with a diameter of less than 2mm.
C ... 4-10 floats with a diameter of less than 2 mm (somewhat bad)
D ··· Streak-like or wide-range float is observed (defect)
E ... Peeling over 50% area (very bad)
In addition, A and B are ranges in which there is no practical problem.

(Example 51)
<Printing of gravure ink for solvent lamination>
The solvent-type laminating gravure ink S2 obtained above was mixed with a mixed solvent of methyl ethyl ketone (MEK): NPAC: IPA = 40: 40: 20 (mass ratio) for a viscosity of 16 seconds (25 ° C., Zahn Cup No. 1). It diluted so that it might become 3). The diluted ink was printed on the corona discharge treated surface or vapor-deposited surface of the same substrate as that used in Example 26 by Helio 175 line gradation plate (plate-type compressed, 100% to 3% gradation pattern). Printing was performed at 100 m / min for 1000 m to obtain printed matter F26 (OPP), G26 (PET), and H26 (silica-deposited nylon). The printing environment was a temperature of 25 ° C. and a humidity of 55% RH.

For the printed matter F26 (OPP), G26 (PET), and H26 (silica vapor-deposited nylon), extrusion lamination processing and dry lamination processing were performed in the same manner as described above.

Using the printed matter F26 (OPP), G26 (PET), H26 (silica vapor-deposited nylon) and their laminates, the blocking resistance, laminate strength and post-retort appearance were evaluated in the same manner as described above. The same result as in Example 27 was obtained.

From the above evaluation results, the solvent-type laminating gravure ink containing the polyurethane resin (A) and the polyurethane resin (B) has a good laminate strength regardless of the type of substrate, and has a substrate transferability and halftone dot ( It was found that this was a gravure ink for solvent-type lamination with good dot reproducibility.

According to an embodiment of the present invention, regardless of the type of substrate, the laminate has good laminate strength, has good printability and dot (dot) reproducibility, and is particularly excellent for a silica / alumina-deposited substrate. A gravure ink for solvent-type laminating having strength can be provided.

Claims (9)

At least a polyurethane resin (A) and a polyurethane resin (B), the mole fraction of urea bonds in the polyurethane resin (A) is 0.1 to 0.4, and the moles of urea bonds in the polyurethane resin (B) A gravure ink for solvent-type laminating having a fraction of 0.45 to 0.65. The gravure ink for solvent-based laminating according to claim 1, wherein the mass ratio of the polyurethane resin (A) to the polyurethane resin (B) is (A) :( B) = 95: 5 to 40:60. The sum of the urea bond concentration and the urethane bond concentration in the polyurethane resin (A) is 1.4 to 2 mmol / g, and the sum of the urea bond concentration and the urethane bond concentration in the polyurethane resin (B) is 2.2 to 2 The gravure ink for solvent-type laminating according to claim 1 or 2, which is .9 mmol / g. The gravure ink for solvent-based laminating according to any one of claims 1 to 3, wherein the glass transition temperature of the mixture of the polyurethane resin (A) and the polyurethane resin (B) is -30 to 0 ° C. The gravure ink for solvent-based laminating according to any one of claims 1 to 4, wherein the polyurethane resin (A) and / or the polyurethane resin (B) has a partial structure represented by the following general formula (1).
General formula (1)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² represents an alkyl group.) The solvent mold according to any one of claims 1 to 5, wherein the mixture of the polyurethane resin (A) and the polyurethane resin (B) has a storage elastic modulus E 'at 30 ° C of 1 x 10 ⁷ to 1 x 10 ⁹ Pa. Gravure ink for laminating. The gravure ink for solvent-based laminating according to any one of claims 1 to 6, further comprising a vinyl chloride copolymer resin (C) having a hydroxyl group. A printed material having a substrate and a printed layer printed on the substrate with the gravure ink for solvent-based laminating according to any one of claims 1 to 7. A laminate having at least a first substrate, a printed layer printed with the gravure ink for solvent-type lamination according to any one of claims 1 to 7, an adhesive layer, and a second substrate in this order.