TW201843257A - Rotary printing ink and use thereof - Google Patents

Abstract

This rotary printing ink contains an aqueous urethane resin (A), a coloring agent, a hydrocarbon wax and water, wherein the aqueous urethane resin (A) has an acid value of 25-45 mg KOH/g and contains structural units represented by general formula (1) and general formula (2), and the hydrocarbon wax has a melting point of 90-140 DEG C and an average particle diameter of 0.5-10 [mu]m. General formula (1): In the formula, Ph denotes a substituted or unsubstituted phenyl group. General formula (2): In the formula, R1 and R2 each denote a substituted or unsubstituted aliphatic hydrocarbon group which may be the same as, or different from, each other, and A denotes an alicyclic hydrocarbon group.

Description

Rotary printing ink and its utilization

Embodiments of the present invention relate to a rotary printing ink, a rotary printing ink set, a plastic film rotary printing, and a laminated laminate.

In recent years, in the printing ink industry, there has been an increasing demand for water-based printing inks from the viewpoints of safety and hygiene during work, environmental protection, and reduction of residual solvents in packaging materials. Therefore, there has been proposed a technique in which an aqueous polyurethane resin or a polyurethane urea resin is used in an aqueous ink (Patent Documents 1 to 3).

On the other hand, in the rotary printing, the winding substrate is provided for printing, and the printing can be performed at a high speed and continuously compared with the printing of the page which is provided with the cut-off sheet which is cut one by one. Therefore, it is suitable for a large number of copies. Printing, good productivity. In the rotary printing, it is important to prevent the high-speed printing of the printed matter from sticking (the deposited printed matter is adhered to the non-printing surface of the substrate by the adhesion of the ink by applying the winding pressure, and the ink is reversed. ). Further, the drying step is a method in which the substrate is passed through a drying oven while printing is performed, so that it is required to be carried out in a short time, especially in the case of printing on a plastic film, in view of the heat resistance of the film, it is necessary to avoid drying at a high temperature, and In the case where the drying is insufficient, residual moisture x solvent is generated, so the drying property of the ink also becomes important. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei.

[Problems to be Solved by the Invention] However, the conventional aqueous ink has lower water resistance and lower adhesion to a substrate than a solvent-based ink, and therefore has a low laminate strength when a laminated laminate is formed. . In addition, regarding the blocking resistance (anti-printing resistance), improvement is also required.

An object of an embodiment of the present invention is to provide a rotary printing ink excellent in water resistance, lamination strength, and blocking resistance, and a rotary printing ink set, a plastic film printed matter, and a laminated laminate using the same. [Means for solving the problem]

An embodiment of the present invention relates to a rotary printing ink comprising an aqueous urethane resin (A), a coloring agent, a hydrocarbon wax, and water, and the aqueous printing urethane resin in the rotary printing ink. The acid value of (A) is 25 mgKOH/g to 45 mgKOH/g, and includes a structural unit represented by the following general formula (1) and the general formula (2), and the melting point of the hydrocarbon wax is 90 ° C to 140 ° C. The average particle diameter is from 0.5 μm to 10 μm. [Chemical 1] (wherein Ph represents a substituted or unsubstituted phenyl group) [Chemical 2] (Wherein, R ¹ is and R ² represents a substituted or unsubstituted aliphatic hydrocarbon group, may be identical or different, A represents an alicyclic hydrocarbon group)

Another embodiment relates to a gravure rotary printing ink set comprising: an aqueous urethane resin (A1), an aqueous urethane resin (A2), and a white colorant for gravure printing. a rotary printing ink according to an embodiment; and a coloring agent comprising an aqueous urethane resin (A1) and at least one color selected from the group consisting of cyan, magenta, yellow, and black, and used for gravure printing One or more of the rotary printing inks of one embodiment.

Another embodiment relates to a flexographic rotary printing ink set comprising two or more embodiments of rotary printing ink further comprising an aqueous urethane urea resin (B) for flexographic printing, The aqueous urethane urea resin (B) comprises a polyester polyol unit having a branch, the flexographic rotary ink set being a combination of the following flexographic rotary printing inks: a flexographic rotation comprising a white colorant Printing ink; and one or more flexographic rotary printing inks comprising a coloring agent selected from the group consisting of cyan, magenta, yellow, and black.

Another embodiment relates to a plastic film rotary printing product having a printing layer on a surface of a plastic film, wherein the printing layer is a rotary printing ink of the embodiment, a gravure rotary printing ink set of the embodiment or The flexographic rotary printing ink set of the above embodiment is formed.

Another embodiment relates to a method for manufacturing a plastic film rotary printed matter, comprising: winding a surface of a plastic film, using the rotary printing ink of the embodiment, the gravure rotary printing ink set of the embodiment or the The flexographic rotary printing ink set of the embodiment is used for rotary printing.

Still another embodiment relates to a laminated laminate comprising the plastic film rotary printed product of the embodiment. [Effects of the Invention]

According to the embodiment of the present invention, it is possible to provide a rotary printing ink excellent in water resistance, lamination strength, and blocking resistance.

Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the embodiments. Further, in the present specification, the mass and the weight are used in the same meaning, and therefore the following is unified as "weight". One of the preferred embodiments of the present invention is, for example, the following (1) to (17).

(1) A rotary printing ink comprising an aqueous urethane resin (A), a colorant, a hydrocarbon wax, and water, wherein the acid value of the aqueous urethane resin (A) in the rotary printing ink It is 25 mgKOH/g to 45 mgKOH/g and contains a structural unit represented by the following general formula (1) and the general formula (2), and the hydrocarbon wax has a melting point of 90 ° C to 140 ° C and an average particle diameter of 0.5. Mm ~ 10 μm. [Chemical 3] (wherein, Ph represents a substituted or unsubstituted phenyl group) [Chemical 4] (wherein R ¹ and R ² represent a substituted or unsubstituted aliphatic hydrocarbon group, which may be the same or different, and A represents an alicyclic hydrocarbon group). (2) A rotary printing ink according to (1) above, wherein The aqueous urethane resin (A) contains a structural unit of a compound having three or more functional groups reactive with an isocyanate group in the same molecule. (3) The rotary printing ink according to (1) or (2), wherein the aqueous urethane resin (A) contains an aqueous urethane resin (A1) and an aqueous urethane resin ( At least one of A2), the aqueous urethane resin (A1) has 3% by weight to 7% by weight of a polyethylene glycol unit in the solid content of the aqueous urethane resin (A1), The aqueous urethane resin (A2) has 20 to 30% by weight of a polyethylene glycol unit in the solid content of the aqueous urethane resin (A2).

(1') Use of an ink for rotary printing comprising an aqueous urethane resin (A), a colorant, a hydrocarbon wax and water, and an aqueous urethane resin (A) The acid value is 25 mgKOH/g to 45 mgKOH/g, and includes the structural unit represented by the above formula (1) and the formula (2), and the hydrocarbon wax has a melting point of 90 ° C to 140 ° C and an average particle diameter. It is 0.5 μm to 10 μm. (2') The use of (1'), wherein the aqueous urethane resin (A) comprises a structural unit of a compound having three or more functional groups reactive with an isocyanate group in the same molecule. (3') The use of (1') or (2'), wherein the aqueous urethane resin (A) contains an aqueous urethane resin (A1) and an aqueous urethane resin At least one of (A2).

(4) The rotary printing ink according to (3) above, which comprises an aqueous urethane resin (A1), an aqueous urethane resin (A2), and a white colorant, and is used for gravure printing. (5) The rotary printing ink according to (3) or (4) above, wherein, in the case of containing both the aqueous urethane resin (A1) and the aqueous urethane resin (A2), The solid component weight ratio of the aqueous urethane resin (A1) to the aqueous urethane resin (A2) is from 30/70 to 50/50. (6) The rotary printing ink according to (3) above, which comprises an aqueous urethane resin (A1) and a coloring agent selected from at least one color selected from the group consisting of cyan, magenta, yellow, and black. And used for gravure printing.

(4') Use of a rotary printing ink for gravure printing, the rotary printing ink being the rotary printing ink of (3) and comprising an aqueous urethane resin (A1), an aqueous urethane Ester resin (A2) and white colorant. (5') The use of (4'), wherein the weight ratio of the aqueous urethane resin (A1) to the aqueous urethane resin (A2) is 30/70 to 50/50 . (6') Use of a rotary printing ink for gravure printing, the rotary printing ink being the rotary printing ink of (3) and comprising an aqueous urethane resin (A1) and selected from the group consisting of cyan and foreign A coloring agent of at least one color in a group consisting of red, yellow, and black.

(7) The rotary printing ink according to any one of (1) to (3) further comprising an aqueous urethane urea resin (B), the aqueous urethane urea resin (B) A polyester polyol unit having branches is included. (8) The rotary printing ink according to (7), wherein the solid urethane resin (A) and the aqueous urethane urea resin (B) have a solid content weight ratio of 25/75 to 45/ 55. (9) The rotary printing ink according to (7) or (8), wherein the aqueous urethane resin (A) contains an aqueous urethane resin (A2), the aqueous urethane The resin (A2) has 20 to 30% by weight of a polyethylene glycol unit in the solid content of the aqueous urethane resin (A2). (10) The rotary printing ink according to any one of (7) to (9) further comprising a urethane/acrylic composite resin (C). (11) The rotary printing ink according to (10), wherein the solid urethane resin (A) and the urethane/acrylic composite resin (C) have a solid content weight ratio of 85/15 to 99 /1. (12) The rotary printing ink according to any one of (7) to (11), which is used for flexographic printing. (12') Use of a rotary printing ink for flexographic printing, the rotary printing ink being the rotary printing ink of any one of (7) to (11).

(13) A gravure rotary printing ink set comprising the rotary printing ink of (4) as described above and one or more of the rotary printing inks of (6). (13') Use of a rotary printing ink set for gravure printing, the rotary printing ink set comprising a rotary printing ink as described in (4) and more than one of rotary printing as described in (6) ink. (14) A flexographic rotary printing ink set comprising two or more types of rotary printing inks as described in (12), wherein the flexographic rotary printing ink set is a combination of the following flexographic rotary printing inks: comprising white a flexographic rotary printing ink of a colorant; and one or more flexographic rotary printing inks comprising a coloring agent selected from the group consisting of cyan, magenta, yellow, and black. (14') Use of a rotary printing ink set for flexographic printing, the rotary printing ink set comprising two or more of the (12) rotary printing inks, and the rotary printing ink set is a combination of flexographic rotary printing inks as follows: a flexographic rotary printing ink comprising a white colorant; and one or more softening agents comprising at least one color selected from the group consisting of cyan, magenta, yellow, and black Version of rotary printing ink.

(15) A plastic film rotary printing having a printing layer on a surface of a plastic film, the printing layer being a rotary printing ink according to any one of (1) to (12), as described (13) The gravure rotary printing ink set or any one of the flexographic rotary printing ink sets of (14) is formed. (16) A method of producing a plastic film rotary printed article, comprising: winding a surface of a plastic film, using the rotary printing ink according to any one of (1) to (12), intaglio according to (13) The rotary printing ink set or the flexographic rotary ink set as described in (14) is used for the rotary printing. (17) A laminated laminate comprising the plastic film rotary printed matter of (15).

(15') A rotary printing ink according to any one of (1) to (12), a gravure rotary printing ink set according to (13) or a flexographic rotary printing ink according to (14) The use of any of the sets for forming the printed layer of a plastic film rotary print having a printed layer on the surface of the plastic film. (17') A rotary printing ink according to any one of (1) to (12), a gravure rotary printing ink set according to (13) or a flexographic rotary printing ink according to (14) Use of any of the kits for a laminated laminate comprising a plastic film web print as described in (15), and for forming a printed layer on the surface of the plastic film of the plastic film web print.

<Rotary Printing Ink> The rotary printing ink contains at least an aqueous urethane resin (A), a coloring agent, a hydrocarbon wax, and water. The rotary printing ink can also form an excellent printed image by high-speed printing, and various types of substrates can be selected as the type of the substrate, and are also suitable for non-permeability groups other than ordinary printing paper. Printing of materials such as coated paper and plastic film (including plastic sheets). Hereinafter, each component contained in the ink and a method of synthesizing the same as needed will be described.

1. Aqueous urethane resin (A) A urethane is usually a resin obtained by a polyisocyanate having two or more isocyanate groups in one molecule and two or more in one molecule. The hydroxyl group-containing compound of the hydroxyl group is reacted. The aqueous urethane resin (A) of the present embodiment has the following constitution. As described later, such a configuration can be preferably introduced by appropriately selecting the structure and type of the hydroxyl group-containing compound. The aqueous urethane resin (A) does not contain a urea bond, and is different from the "urethane urea resin" described later in this respect.

The aqueous urethane resin (A) has an acidic group (carboxy group), and the acid value is preferably from 25 mgKOH/g to 45 mgKOH/g. The acid valency of the aqueous urethane resin (A) is 25 mgKOH/g or more, and the acidic functional group is neutralized by a base, whereby the dispersibility and solubility to water are sufficient and the storage stability of the ink can be obtained. It is also excellent in pigment dispersibility and resolubility. In addition, since the acid value of the aqueous urethane resin (A) is 45 mgKOH/g or less, the water resistance of the ink film when used as a binder can be ensured. The acid value is further preferably 40 mgKOH/g or less.

In order to make the aqueous urethane resin (A) the acid value, a compound containing a carboxyl group and containing a functional group (other than a carboxyl group) reactive with an isocyanate group is preferably used as a synthetic raw material. As the functional group reactive with the isocyanate group, a hydroxyl group is preferred.

Examples of such a hydroxyl group-containing compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dihydroxyl. One or more of these may be used in combination, such as a dimethylol alkane acid such as valeric acid. Among them, in terms of compatibility with other urethane raw materials and reactivity, it is preferred to use 2,2-dimethylolpropionic acid and/or 2,2-dimethylolbutanoic acid. Here, since the isocyanate group preferentially reacts with the hydroxyl group of the carboxyl group-containing compound, most of the carboxyl group remains in the side chain of the aqueous urethane resin (A) under mild reaction conditions of from 60 ° C to 140 ° C.

The aqueous urethane resin (A) contains a structural unit represented by the following formula (1) and formula (2). By combining the two structural units, the cohesive force of the ink film is improved, and the water resistance, blocking resistance, and lamination strength of the ink film can be improved. [Chemical 5] (wherein, Ph represents a substituted or unsubstituted phenyl group) [Chemical 6] (wherein R ¹ and R ² represent a substituted or unsubstituted aliphatic hydrocarbon group, which may be the same or different, and A represents an alicyclic hydrocarbon group)

With respect to the structural unit of the above formula (1), it is considered that the tertiary amine group and the carboxyl group form a quasi-crosslinking in the coating film (film), and the adhesion resistance and lamination strength of the coating film can be improved. Preferably. The substituent for the phenyl group may, for example, be a methyl group, an ethyl group, a propyl group, a methoxy group or an ethoxy group, or may have two or more substituents. Further, the substituted portion of the phenyl group may be any of an ortho, meta and para.

The structural unit of the formula (1) can be preferably introduced by using a compound containing a tertiary amino group of the formula (1) and containing a functional group reactive with an isocyanate group as a synthetic raw material. The functional group reactive with the isocyanate group may, for example, be a hydroxyl group or a carboxyl group, and is preferably a hydroxyl group from the viewpoint of reactivity with an isocyanate group.

Examples of the compound whose functional group reactive with an isocyanate group is a hydroxyl group include N,N-bis(2-hydroxypropyl)aniline having two hydroxyl groups, N,N-bis(2-hydroxyethyl)aniline, and N. , N-bis(2-hydroxyethyl)-3-chloroaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-o-toluidine , N,N-bis(2-hydroxyethyl)-m-toluidine, N,N-bis(2-hydroxyethyl)-m-xylyleneamine and N,N-bis(2-hydroxyethyl)-pair Xylidine, etc., as a compound having one hydroxyl group, N-hydroxyethylaniline, N-(2-cyanoethyl)-N-(2-hydroxyethyl)aniline, and 2-(N-ethyl group) An aniline) ethanol or the like may be used alone or in combination of two or more. From the viewpoints of stability of the aqueous resin, adhesion to a plastic film, and the like, N,N-bis(2-hydroxypropyl)aniline is preferred.

Examples of the compound having a carboxyl group reactive with an isocyanate group include N,N-bis(2-carboxyethyl)aniline, and the like, and one or a combination of two or more of them may be used.

The structural unit of the above formula (2) is preferred in terms of improving the water resistance and blocking resistance of the coating film. The structural unit can be preferably introduced by using a compound containing a structural unit of the formula (2) and containing a functional group reactive with an isocyanate group as a synthetic raw material. The raw material having the structural unit of the formula (2) brings about rigidity of the structure caused by the alicyclic hydrocarbon group to the molecule of the aqueous urethane resin (A) by reacting with the isocyanate compound, and further, a large amount of the amine group The formate bond is introduced into the molecule and the coating film is firmly formed. In this respect, it is also considered to contribute to improvement in water resistance and blocking resistance.

In the formula (2), R ¹ and R ^{2 each} represent a substituted or unsubstituted divalent aliphatic hydrocarbon group, and the two may be the same or different from each other. In other words, R ¹ and R ² are a divalent hydrocarbon group which does not have aromaticity and contains carbon and hydrogen other than the substituent, and may have an unsaturated bond. The carbon number of the aliphatic hydrocarbon group (excluding the carbon number contained in the substituent) is preferably from 1 to 5, more preferably from 1 to 3. Examples of the substituent in the case of having a substituent include an alkyl group and an unsaturated bond group. Specific examples of R ¹ and R ² include a methylene group, an exoethyl group, and a propyl group.

In the formula (2), A represents a divalent alicyclic hydrocarbon group. That is, A is a monocyclic or polycyclic group which does not have aromaticity and contains carbon and hydrogen, and may have an unsaturated bond. The number of ring members of the alicyclic hydrocarbon group is preferably from 5 to 10, particularly preferably a 6-membered ring. Specific examples of A include a cyclopentane ring, a cyclohexane ring, a cyclodecane ring, and the like. A is preferably a cycloalkyl group and a bicycloalkyl group, and examples thereof include a cyclohexyl group and a methylene-dicyclohexyl group, and may also be a mixture of structural isomers.

Furthermore, the raw material compound which can introduce the structural unit of the general formula (2) is 1,4-cyclohexane dimethanol and 1,1-cyclohexane diethanol. It is also possible to use two or more of these.

In the aqueous urethane resin (A), as the structural unit of the above formula (1), it is preferred to contain a structure derived from N,N-bis(2-hydroxypropyl)aniline as the The structural unit of the formula (2) preferably contains a structure derived from 1,4-cyclohexanedimethanol. Further, the aqueous urethane resin (A) is not particularly limited, and the structural unit of the above formula (1) preferably contains 5% by weight to 10% by weight of the resin solid content. The structural unit of the formula (2) preferably contains 0.5% by weight to 5% by weight based on the resin solid content. This ratio can be calculated based on the total weight of all the raw materials used in the synthesis of the aqueous urethane resin (A) and the weight of each raw material to be introduced into each structural unit.

In one embodiment, the aqueous urethane resin (A) preferably contains a structural unit derived from a compound having three or more functional groups reactive with an isocyanate group in the same molecule. By using such a compound, three-dimensional cross-linking can be realized in the urethane resin, and the ink film (coating film) becomes firm, and the blocking resistance of the ink film, the lamination strength, and the cohesive force of the ink film can be further improved. Wait. The aqueous urethane (A) of the embodiment preferably contains 0.05% by weight or more based on the total weight of the solid urethane resin (A), and has three or more from the same molecule. More preferably, the structural unit of the isocyanate-reactive functional group is contained in an amount of 0.1% by weight or more, more preferably 0.8% by weight or less, still more preferably 0.6% by weight or less, and more specifically, preferably It is contained in the range of 0.05% by weight to 0.8% by weight, and more preferably in the range of 0.1% by weight to 0.6% by weight.

In the compound having three or more functional groups capable of reacting with an isocyanate group in the same molecule, as described above, examples of the functional group reactive with the isocyanate group include a hydroxyl group and a carboxyl group, and the reactivity is controlled and produced. In terms of the bonding group, a hydroxyl group is preferred.

Examples of the compound having three or more hydroxyl groups include trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, and pentaerythritol. The polyol having three or more hydroxyl groups is preferably used as needed within a range in which the urethane resin is not gelated. Trimethylolpropane is preferred.

Further, as the compound which can be introduced into the structural unit, a compound having a total of three or more hydroxyl groups and a carboxyl group is preferably used. For example, dimethylol propionic acid, 2,2-dimethylol acetic acid, 2,2-dimethylol-butyric acid, 2,2-dihydroxymethyl valeric acid, dihydroxypropionic acid, etc. Alkane acid; dihydroxysuccinic acid and dihydroxybenzoic acid. In these compounds, since the hydroxyl group is preferentially reacted with the isocyanate group, the carboxyl group can be introduced into the urethane resin, and the carboxylic acid can be neutralized by using ammonia or a base to easily achieve water-based resin. In particular, in terms of reactivity and solubility, it is preferred to use dimethylolpropionic acid and 2,2-dimethylolbutyric acid.

As the hydroxyl group-containing compound for synthesizing the aqueous urethane resin (A), it is preferred to use the compound, but it is also preferred to use a usual polyol having no specific structure in combination. For example, a low molecular weight diol having two hydroxyl groups in one molecule and a high molecular weight diol can be used. Specific examples of the low molecular weight diol include diethylene glycol, trimethylene glycol, triethylene glycol, propylene glycol, butanediol, hexamethylene glycol, and neopentyl glycol. Two or more of these.

Examples of the high molecular weight diol include a polyether type, a polyester type, and an epoxy type. Among them, a polyether-based and/or polyester-based high molecular weight diol is preferably used. Examples of the polyether system include polyethylene glycol, polyoxypropylene diol, poly(ethylene/propylene) diol, and polytetramethylene glycol. The polyester diol is obtained by polycondensation of a diol and a dibasic acid. Examples of the raw material diol include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 2- Examples of the raw material dibasic acid such as methyl-1,3-propanediol and neopentyl glycol include adipic acid, sebacic acid, sebacic acid, isophthalic acid, and terephthalic acid. In one embodiment, it is preferred to use a group derived from a group consisting of 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, and neopentyl glycol. A polyester diol having a structure of one or more compounds. Further, examples of the high molecular weight body having two hydroxyl groups include a lactone ring-opening polymer such as polycaprolactone and polyβ-methyl-δ-valerolactone, and polycarbonate.

The hydroxyl group-containing compound described above is preferably used in combination of one type or two or more types. In order to obtain a balance between the adhesion to the film substrate, the physical properties of the film of the ink, the water resistance, and the like, it is preferred to use two or more kinds of chemical structures different in combination or to appropriately select the molecular weights.

As described above, in one embodiment, it is preferred that the aqueous urethane resin (A) contains a structural unit of a polyether-based and/or polyester-based high molecular weight diol and has three or more in the same molecule. A structural unit of a compound of a functional group reactive with an isocyanate group. Further, in another embodiment, it is preferred that the aqueous urethane resin (A) comprises a structural unit of a polyether-based and/or a polyester-based high molecular weight diol, and has three or more in the same molecule. a structural unit of a compound of a functional group reactive with an isocyanate group, wherein the structural unit of the formula (1) contains 5% by weight to 10% by weight in the solid content of the resin, and the structural unit of the formula (2) is in the resin The solid content is contained in an amount of 0.5% by weight to 5% by weight.

In the production of the aqueous urethane resin, polyethylene glycol (hereinafter also referred to as "PEG") is preferably used in combination as a hydroxyl group-containing compound, whereby water solubility can be easily obtained. Stable dispersion, hydrosol or water soluble resin. Further, by using PEG in a specific weight ratio for the production of an aqueous urethane resin, it is possible to impart an appropriate viscosity as an ink, and at the time of printing, it is also possible to improve printability such as transferability to a substrate. . Therefore, the aqueous urethane resin (A) is preferably a structural unit containing a polyether-based high molecular weight diol, and comprises an aqueous urethane resin (A1) and an aqueous urethane resin (A2). In at least one of the above, the aqueous urethane resin (A1) has 3% by weight to 7% by weight of a PEG unit in the solid content of the aqueous urethane resin (A1), the aqueous amine group The acid ester resin (A2) has 20% by weight to 30% by weight of PEG units in the solid content of the aqueous urethane resin (A2). By using the resin (A1) having a small PEG unit, the above-described characteristics of the PEG unit can be exhibited and the water resistance of the film can be improved. By using a resin (A2) having a large PEG unit, the above-described characteristics of the PEG unit can be exhibited and the pigment dispersibility and color developability can be improved. Further, by combining the resin (A1) and the resin (A2), the adhesion of the film to the object to be printed can be improved. Therefore, the resin (A1) and the resin (A2) can be selected depending on the use of the ink.

For example, in gravure printing, the printing ink is supplied to a gravure cylinder in which a cell is formed on the surface, and the excess printing ink on the surface of the drum is scraped off by a doctor blade, and then the printed body is printed, and the intaglio for the gravure printing is used. In the case of the rotary printing ink, the transfer property of the ink in the groove to the printed object and the re-solubility of the ink remaining in the groove are required, and thus the dispersibility of the colorant (especially pigment) and the stability of the dispersion are required. Become important. By using the aqueous urethane resin (A1), the dispersibility of the pigment is improved, and in the case of forming a printed matter, a coating film having excellent cohesive strength can be obtained.

Further, as for the white ink, titanium oxide is usually used as a pigment, and as a result, it is difficult to disperse due to the large specific gravity of titanium oxide, and the content of the white pigment for maintaining the coloring power is more than that of the color ink other than white. Therefore, in the case of a white ink for gravure printing, it is preferred to use an aqueous urethane resin (A1) and an aqueous urethane resin (A2). More preferably, the aqueous urethane resin (A2) is used for dispersion to improve the pigment dispersibility, and then the aqueous urethane resin (A1) is preferably added and mixed. By the combination, the resolubility of the ink component is also improved, so that the accumulation of the white pigment in the concave portion of the intaglio can be prevented or reduced. The solid component weight of the aqueous urethane resin (A1) and the aqueous urethane resin (A2) in combination is preferably from 30/70 to 50/50.

That is, in one embodiment, the rotary printing ink is a gravure rotary printing white ink containing an aqueous urethane resin (A1), an aqueous urethane resin (A2), a white coloring agent, a hydrocarbon wax, and water. . By including the aqueous urethane resin (A2), there is also a reduction in the whiteness of the plate (in the case of intaglio printing, the phenomenon that the ink cannot be transferred to a portion other than the image portion by the doctor blade) effect.

In another embodiment, the rotary printing ink is a gravure rotary printing color ink containing an aqueous urethane resin (A1), a coloring agent other than white, a hydrocarbon wax, and water. In the case where the gravure rotary printing color ink is used, sufficient pigment dispersibility and resolubility can be obtained using only the aqueous urethane resin (A1). The aqueous urethane resin (A2) may be contained. When the aqueous urethane resin (A1) is a main resin, the amount of PEG is small, so that the water resistance of the printed layer is good and the blocking resistance is improved. (anti-print resistance) is better.

In the present specification, an ink containing a white coloring agent is described as "white ink", a coloring agent other than white is described as "coloring coloring agent", and an ink other than white is described as "color ink". The coloring agent preferably contains at least one color selected from the group consisting of cyan, magenta, yellow, and black, or any of the colors, but is not particularly limited thereto, and may be a so-called "special color". That is, other colors than the basic color of the CMYK.

Next, examples of the polyisocyanate to be reacted with the hydroxyl group-containing compound include an aromatic, aliphatic, alicyclic difunctional isocyanate, and a trifunctional isocyanate. Among them, a difunctional isocyanate is preferable, and examples of the difunctional isocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and 4,4'-. Diphenylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene Diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-extended biphenyl diisocyanate, 3,3'-dimethoxy-4,4'- Stretched biphenyl diisocyanate, 3,3'-dichloro-4,4'-extended biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,5 (2,6 )-bicyclo[2.2.1]heptane bis(isocyanatomethyl) (norbornane diisocyanate) or the like, which may be used alone or in combination of two or more.

Examples of the trifunctional isocyanate include: 1) an adduct of trimethylolpropane, such as Takenate D-160N (manufactured by Takeda Pharmaceutical Co., Ltd.) and Sumidule HT (Sumitomo). Bayer Urethane (manufactured by Bayer Urethane); 2) Biuret body, such as Takenate D-165N (made by Takeda Pharmaceutical Co., Ltd.) and Sumidule N3200 (Sumitomo Bayer) Polyurethane (manufactured by Bayer Urethane); 3) Isocyanurate ring type, for example, VESTANAT T1890 (manufactured by Hess (HULS) Co., Ltd.) and the like. In the case of using a trifunctional isocyanate, it is particularly preferably 0.05% by weight to 2% by weight of the solid content of the aqueous urethane resin (A) from the viewpoint of improving the cohesive force and controlling the viscosity during the reaction. .

The reaction molar ratio (NCO/OH) of the isocyanate group of the aqueous urethane resin (A) and the hydroxyl group is not particularly limited, and the molecular weight of the resin and the number of urethane bonds are controlled. It is preferably 0.9 or more, more preferably 0.94 or more, and further preferably 0.99 or less, more preferably 0.98 or less, still more preferably 0.9 to 0.99, still more preferably 0.94 to 0.98.

Next, a method of synthesizing the aqueous urethane resin (A) will be described. The aqueous urethane resin (A) can be obtained by an acetone method using an organic solvent or a solventless synthesis method using no solvent at all, and the production method thereof is not particularly limited. In the latter case, the viscosity generally becomes high, so it is necessary to work on the stirring device, the raw material composition, and the chain extension method. Hereinafter, the acetone method and the solventless synthesis method will be described separately.

The acetone method is a method in which a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone is used in a reaction in which the viscosity is extremely high or partial gelation is likely to be uneven. A solvent; an ester solvent such as ethyl acetate or butyl acetate; or an aromatic organic solvent such as toluene or xylene. When an organic solvent is used, the viscosity of the reaction system is lowered, and the synthesis reaction can be carried out uniformly and smoothly.

It is preferred to use a catalyst in the reaction of the polyisocyanate with the hydroxyl group-containing compound. As the catalyst, a known metal catalyst or an amine catalyst can be used. Examples of the metal-based catalyst include dibutyltin dilaurate, tin octylate, dibutyltin bis(2-ethylhexanoate), lead 2-ethylhexanoate, 2-ethylhexyl titanate, and 2 - Ethylhexanoate iron, cobalt 2-ethylhexanoate, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin, and the like. The amine-based catalyst may, for example, be a tertiary amine such as tetramethylbutanediamine.

The urethanization reaction is preferably carried out at 50 ° C to 100 ° C for 10 minutes to 10 hours. The end point of the reaction can be determined by viscosity measurement, NCO peak obtained by infrared (IR) measurement, NCO% measurement by titration, and the like.

After obtaining a urethane resin having a predetermined molecular weight, in order to make it aqueous, it is preferred to neutralize a carboxyl group in the resin with a basic compound. Examples of the basic compound include inorganic hydroxides such as sodium hydroxide and potassium hydroxide; ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, and propanol. Amine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1 An amine compound such as propanol, 2-amino-2-methyl-1-propanol or morpholine may be used alone or in combination of two or more. Depending on the type of the basic compound, there are cases in which the ease of permeation of the polyurethane solution or the stability after the aqueous solution is different, and therefore it is necessary to appropriately select it. Among these, an amine compound is preferred, and ammonia is preferred in terms of water resistance and residual odor of the printed matter.

In the neutralization of a compound having a carboxyl group such as a dimethylol alkane acid, it is preferred to use 0.4 to 1.2 equivalents of a basic compound per equivalent of the carboxyl group. A method of aqueousizing a urethane resin is a method of using the carboxyl group-containing diol and neutralizing with a base, a method of using a polyethylene glycol having a high water solubility, and the like. In particular, when both are used in combination, a resin which is stable as a water-soluble resin and which is balanced in water resistance as an ink can be obtained.

In the acetone method, it is necessary to carry out solvent removal depending on the kind or amount of the solvent to be used. The solvent removal can be carried out, for example, by adding water and a basic compound as a neutralizing agent to the reaction solution, raising the temperature, and distilling off the necessary amount of the solvent under normal pressure or under reduced pressure.

In the solventless synthesis method, the polyol and the isocyanate may be initially charged, or the isocyanate may be added after the polyol is charged. In the synthesis reaction, since the viscosity is usually a problem, it is preferred to increase the temperature to a sufficient degree of agitation to lower the viscosity. It is preferred that the resin raw material is sufficiently dissolved or melted and the reaction is started in a uniform state. When the reaction initiation temperature is low or the compatibility between the resin raw materials or the raw material/formation resin is insufficient, a part of the raw materials is dispersed in the molten raw material, and the appearance is slightly opaque. That is, it can be produced in this state. For example, in the case of a polyol containing polyethylene glycol, when the reaction temperature is equal to or higher than the compatible temperature, even a poorly compatible diol can be obtained. A uniform resin.

The urethanization reaction is preferably carried out at 90 ° C to 200 ° C for 10 minutes to 5 hours. The end point of the reaction can be determined by viscosity measurement, NCO peak obtained by IR measurement, or NCO% measurement by titration.

The aqueous formation of the urethane resin can be carried out by neutralizing the carboxyl group of the basic compound or by using water such as polyethylene glycol. When the reaction is carried out without a solvent, water can be achieved even by using only water and a basic compound. However, since the organic solvent has a function of temporarily forming a reactant having a high viscosity into a resin solution and smoothly performing the aqueous solution, it is easy to use an organic solvent as an auxiliary agent before the aqueous solution of the urethane resin is used. Water-based. In this case, the urethane resin may be directly added after completion of the synthesis of the urethane resin, and the urethane resin may be added to the organic solvent and dissolved.

When an alcohol is used as an organic solvent, since it is usually used in combination with an aqueous printing ink, there is an advantage that it can be used as it is without being subjected to solvent removal. Examples of the alcohol include polyhydric alcohols such as monohydric alcohols and diols, and glycol ethers. Further, specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-n-hexyl ether and 2,2,4-trimethylpentanediol-1,3-monoisobutyrate (Tesanoru) (TEXANOL), manufactured by Eastman Chemical Co., Ltd., etc., particularly preferably isopropanol, n-propanol, n-butanol, ethanol, and methanol. These may be used alone or in combination of two or more. The solvent removal process can be omitted by appropriately selecting an alcohol suitable for the printing viscosity (dilution property), drying property, and film forming property of the target printing ink from the alcohols.

The solventless synthesis method as the second method for obtaining an aqueous urethane resin can reduce the cost and the like due to the use of a solvent to zero, and thus has great advantages in productivity and cost. In particular, in the case where the amount of residual solvent of the printed matter becomes a problem, the proportion of the solvent removal step in all the production steps increases, which is a major factor for increasing the production cost of the aqueous urethane resin.

The number of urethane bonds (mmol/g) of the aqueous urethane resin (A) is not particularly limited, and is preferably 2.2 mmol from the viewpoints of adjustment of the molecular weight of the resin and the hardness of the coating film. More preferably, it is 2.3 mmol/g or more, and further preferably 3.0 mmol/g or less, more preferably 2.9 mmol/g or less. More specifically, the number of urethane bonds is preferably from 2.2 mmol/g to 3.0 mmol/g, more preferably from 2.3 mmol/g to 2.9 mmol/g. The number of urethane bonds can be set to a desired range by appropriately adjusting the amount of the hydroxyl group-containing compound and the polyisocyanate and the reaction conditions.

The glass transition temperature (Tg) of the aqueous urethane resin (A) and the aqueous urethane urea resin (B) to be described later is not particularly limited, and is preferably an aqueous urethane resin (A). The aqueous urethane urea resin (B) is -50 ° C or lower at -70 ° C or lower. In the aqueous urethane resin (A), the aqueous urethane resin (A1) preferably has a Tg of -70 ° C or lower, more preferably -70 ° C to -90 ° C, and an aqueous urethane. The Tg of the resin (A2) is preferably -90 ° C or lower. When the Tg of the aqueous urethane resin (A) is -70 ° C or lower, the film formability of the ink is improved, and the adhesion of the coating film is improved. The aqueous urethane urea resin (B) is used in combination with an aqueous urethane resin (A) by using a Tg of -50 ° C or lower, preferably -50 ° C to -70 ° C, after printing. The printability is improved, so it is preferred. The Tg of the aqueous urethane resin (A) and the aqueous urethane urea resin (B) can be measured by a scanning type differential thermal analysis method at a temperature increase rate of 10 ° C / min.

The weight average molecular weight (Gel Permeation Chromatography (GPC) measurement, standard polystyrene conversion) of the aqueous urethane resin (A) is not particularly limited, but is preferably 10,000 or more, and more preferably 30,000. The above is preferably 100,000 or less, more preferably 70,000 or less. More specifically, the weight average molecular weight is preferably from 10,000 to 100,000, more preferably from 30,000 to 70,000.

The hydroxyl value (mgKOH/g) of the aqueous urethane resin (A) is not particularly limited, and is preferably from 0.0 mgKOH/g to 3.0 mgKOH/g, more preferably from 0.0 mgKOH, from the viewpoint of water resistance and the like. /g ~ 2.0 mgKOH / g.

The aqueous urethane resin (A) is preferably contained in an amount of 3% by weight or more, more preferably 5% by weight or more, and particularly preferably 7% by weight or more based on the total amount of the rotary printing ink. On the other hand, the content of the aqueous urethane resin (A) is preferably 25% by weight or less, more preferably 20% by weight or less, and still more preferably 17% by weight or less based on the total amount of the rotary printing ink.

2. Aqueous urethane urea resin (B) The aqueous urethane resin (A) does not contain a urea bond. In one embodiment, the rotary printing ink may further comprise an aqueous amine group containing a urea bond. Acid ester urea resin (B).

In particular, the aqueous urethane urea resin (B) preferably contains a branched polyester polyol unit from the viewpoints of printability and plate-washing properties in flexographic printing. Here, the branch is an alkyl group, and the branched polyol refers to a structure in which at least one of hydrogen atoms on the alkyl group contained in the polyol is substituted with an alkyl group. The branched polyester polyol unit can be preferably introduced by: neopentyl glycol, 1,2-propanediol, 2-ethyl-2-butyl-propanediol, 2-methyl-1 A polyester polyol synthesized from a branched polyol and a polyvalent carboxylic acid such as 3-propanediol and 3-methyl-1,5-pentanediol is used as a synthetic raw material of the urethane urea resin.

The urea bond can be preferably introduced by performing a chain extension reaction using any diamine. Examples of the chain extender include aliphatic diamines such as ethylenediamine, hexamethylenediamine, and 2,2,4-trimethylhexamethylenediamine; isophorone diamine and 1,4 - alicyclic diamines such as diaminocyclohexane; diammonium malonate, diterpene succinate, diammonium glutarate, diammonium adipate and diterpene sebacate;肼 compounds, etc. Further, examples thereof include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, and 2-hydroxypropyl group. A diamine having a hydroxyl group such as ethylenediamine or di-2-hydroxypropylethylenediamine. By using a diamine having a hydroxyl group, a hydroxyl group can be introduced into the aqueous urethane urea resin (B), and there is an advantage in that, in the case of using a hardener reactive with a hydroxyl group, the coating film can be improved. Crosslink density and improved resistance to blocking and water resistance. One or two or more of these may be used. Further, a polyamine such as diethylenetriamine or triethylenetetramine may be used insofar as the urethane resin is not gelled. Among them, isophorone diamine and 2-hydroxyethylethylenediamine (2-aminoethylethanolamine) are preferably used.

A reaction stopper can also be used in the chain extension reaction. As the reaction stopping agent, in addition to a dialkylamine such as di-n-butylamine, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, or tris(hydroxyl) can also be used. An amine having a hydroxyl group such as aminomethane or 2-amino-2-ethyl-1,3-propanediol. By using a reaction stopper and a chain extender in combination, the molecular weight can be easily controlled, and the introduction of a functional group to the terminal can be carried out.

The chain extension reaction is preferably carried out at 30 ° C to 80 ° C for 10 minutes to 10 hours. The end point of the reaction can be determined by viscosity measurement, NCO peak obtained by IR measurement, or determination of the amine value obtained by titration.

The reaction molar ratio (NCO/OH) of the isocyanate group of the aqueous urethane urea resin (B) to the hydroxyl group is not particularly limited, and the balance of the softness and hardness of the resin caused by the urethane bond concentration is not particularly limited. From the viewpoints of blocking resistance at the time of coating film formation, substrate adhesion in flexible packaging applications, and substrate followability, etc., it is preferably 1.2 or more, more preferably 1.5 or more, and preferably 2.5 or less. More preferably, it is 1.8 or less, and more specifically, it is preferably 1.2 to 2.5, more preferably 1.5 to 1.8. By setting the reaction molar ratio of both to 1.2 to 2.5, for example, a urethane prepolymer having an isocyanate group at the terminal can be preferably obtained.

The urethane prepolymer having an isocyanate group at the terminal is a urethane urea resin (B) by chain extension using a chain extender having an amine group. The reaction molar ratio (NH/residual NCO) of the amino group of the chain extender to the isocyanate group (residual NCO) of the urethane prepolymer is not particularly limited, and the molecular weight, the terminal group, and the urea bond concentration are controlled. The viewpoint is preferably 0.8 or more, more preferably 0.9 or more, further preferably 1.2 or less, more preferably 1.1 or less, still more preferably 0.8 to 1.2, still more preferably 0.9 to 1.1. Further, the isocyanate group associated with the urea bond is a residual isocyanate group (residual NCO) after the formation of the urethane bond.

The weight average molecular weight (GPC measurement, standard polystyrene conversion) of the aqueous urethane urea resin (B) is not particularly limited, and is preferably 10,000 or more from the viewpoints of resolubility and blocking resistance. More preferably, it is 30,000 or more, and further preferably 100,000 or less, more preferably 70,000 or less. More specifically, it is preferably 10,000 to 100,000, more preferably 30,000 to 70,000.

The acid value (mgKOH/g) of the aqueous urethane urea resin (B) is not particularly limited, and is preferably 25 mgKOH/g or more, and more preferably 30, from the viewpoints of resolubility and water resistance. The amount of MgKOH/g or more is preferably 45 mgKOH/g or less, more preferably 40 mgKOH/g or less, and more specifically 25 mgKOH/g to 45 mgKOH/g, more preferably 30 mgKOH/g. ~40 mgKOH/g. The acid value is a value obtained by converting the amount of acid in 1 g of the resin calculated by using an alkali titration acid into the number of mg of potassium hydroxide, and is a value measured according to Japanese Industrial Standards (JIS) K0070:1992. .

The aqueous urethane urea resin (B) preferably has a hydroxyl value (mgKOH/g). The hydroxyl group valence of the aqueous urethane urea resin (B) is not particularly limited, and is preferably 35 mgKOH/g from the viewpoints of water resistance, blocking resistance, and introduction of a crosslinked structure in a coating film. Hereinafter, it is more preferably 25 mgKOH/g or less, further preferably 1 mgKOH/g or more, and still more preferably 5 mgKOH/g or more. More specifically, the valence of the hydroxyl group is preferably from 0 mgKOH/g to 35 mgKOH/g, more preferably from 0 mgKOH/g to 25 mgKOH/g, still more preferably from 1 mgKOH/g to 35 mgKOH/g. More preferably, it is 5 mgKOH/g to 25 mgKOH/g. The hydroxyl value is a value obtained by converting the hydroxyl group in the resin to the number of mg of potassium hydroxide calculated by esterifying or acetylating the hydroxyl group in the resin and calculating the acid remaining in the resin by reverse titration. According to the measured value of JIS K0070:1992.

If a large amount of an amine group is present in the aqueous polyurethane urea resin (B), the carboxyl group and the salt structure of the aqueous urethane urea resin are easily obtained, and the stability with time and the pigment dispersibility of the ink are lowered. Case. Further, when the amount of the amine group is large, when the isocyanate-based curing agent is used, the tendency of the ink to deteriorate with time is observed. On the other hand, by the presence of an amine group, the adhesion to the substrate, in particular, the adhesion to the polyolefin film and the blocking resistance are improved. Therefore, the amine valence of the aqueous polyurethane urea resin (B) is preferably in the range of from 0 mgKOH/g to 13 mgKOH/g. More preferably, it is 0 mgKOH/g - 10 mgKOH/g. The amine group in the aqueous urethane urea resin (B) can be introduced to the side chain and/or the terminal.

The amine valence can be determined by a known titration method in accordance with JIS K0070:1992. That is, accurately weigh 0.5 g to 2 g of sample (sample size: S g, solid content: Z%), add 30 mL of neutral ethanol (BDG neutral) to the accurately weighed sample and dissolve. 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 amount of the amine was determined by the following titration (A mL) and the following (Formula 1). (Formula 1) Amine Price = (A × f × 0.2 × 56.108) / (S × Z / 100)

Regarding the aqueous urethane urea resin (B), it is preferable to further improve the adhesion of the ink film to the object to be printed. In the case where the rotary printing ink contains the aqueous urethane urea resin (B), the solid component weight of the aqueous urethane resin (A) and the aqueous urethane urea resin (B) is preferably 25 Further, it is preferably 45/55 or less, and more specifically, 25/75 to 45/55. On the other hand, the preparation of the aqueous urethane urea resin (B) leads to an increase in the production cost of the ink, and further, according to the study by the inventors of the present invention, the printing suitability of the resin (B) is not included in the gravure printing. Excellent.

Therefore, in the case of flexographic rotary printing ink for flexographic printing, it is preferred to contain an aqueous urethane urea resin (B). Further, in the case of use in flexographic printing, the aqueous urethane resin (A) of the rotary printing ink preferably contains an aqueous urethane having a large PEG content from the viewpoint of the washing property and the like. Resin (A2). Further, it is also preferable to contain a urethane/acrylic composite resin (C) which will be described later.

That is, in one embodiment, the rotary printing ink is a flexographic rotary printing containing an aqueous urethane resin (A2), an aqueous urethane urea resin (B), a white coloring agent, a hydrocarbon wax, and water. White ink. In another embodiment, the rotary printing ink is a flexographic film containing an aqueous urethane resin (A2), an aqueous urethane urea resin (B), a coloring agent other than white, a hydrocarbon wax, and water. Rotate printing color inks.

3. Aurethane/Acrylic Composite Resin (C) The rotary printing ink may further contain a urethane/acrylic composite resin (C). By including the urethane/acrylic composite resin (C), in particular, in the flexographic ink, the advantage of improving the plate-washing property can be obtained.

The urethane/acrylic composite resin (C) is a composite resin composed of a urethane component and an acrylic component as essential constituents. The urethane component of the urethane/acrylic composite resin is not particularly limited, and is, for example, a polyisocyanate compound and a polyol compound as a raw material component. As the polyisocyanate compound, for example, one of a known diisocyanate selected from the group consisting of an aromatic diisocyanate, an aliphatic diisocyanate, and an alicyclic diisocyanate, or a mixture of two or more kinds thereof can be used. By using the polyisocyanate compound with a low molecular weight glycol, a polyether diol, a polyester diol as a polyol compound, or a polycaprolactone diol, a polyvalerolactone diol, a lactone block A known diol such as a lactone diol such as a copolymer diol is reacted to obtain a urethane component. Further, as the polyol compound, an acrylic polyol can also be used.

Examples of the monomer component of the acrylic component constituting the urethane/acrylic composite resin (C) include a (meth)acrylic acid alkyl ester having a linear or branched alkyl group, and a carboxyl group-containing ( Methyl)acrylic acid, a hydroxyl group-containing (meth) acrylate, a (meth)acrylic acid decylamine derivative, and a (meth)acrylic acid dialkylaminoalkyl ester, preferably one or more of these are used. An acrylic monolith or a polymerizable unsaturated compound such as a styrene compound, a vinyl ester or a cyano group-containing vinyl compound may be used in combination.

The aqueous formation of the urethane/acrylic composite resin (C) can be achieved by using an aqueous component, such as a urethane, in the carbamate component and/or the acrylic component. As the component, dimethylolpropionic acid or dimethylolbutanoic acid or the like is used, and (meth)acrylic acid or itaconic acid or the like is used for the acrylic component. Preferably, the urethane component is chemically bonded to the acrylic component. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and acrylic-4 are used in the acrylic component. A urethane/acrylic composite resin (C) obtained by chemically bonding a urethane component and an acrylic component to an acrylic polyol such as hydroxybutyl ester.

A commercially available product can also be used as the urethane/acrylic composite resin (C). For example, WEM-031U, 200U, 202U, 321, 3000, and 290A; WAN-6000 and ACRIT 8UA-140 (above, manufactured by Taisei Fine Chemical Co., Ltd.) and the like can be cited.

In the case where the rotary printing ink contains the urethane/acrylic composite resin (C), the solid urethane resin (A) and the urethane/acrylic composite resin (C) have a relatively good solid component weight. It is 85/15 or more, more preferably 90/10 or more, and further preferably 99/1 or less, more specifically, preferably 85/15 to 99/1, more preferably 90/10 to 99/1. .

4. Colorant A known dye or pigment, preferably a pigment, can be used as the colorant, and is not particularly limited. The color is white, cyan (C), magenta (M), yellow (Y), black (K), orange, purple, and green, and is not particularly limited. For example, the color index can be arbitrarily used (Colour Index International, slightly The coloring agent described in CI). If necessary, any combination of different color couplers can be used. As the colorant, one of a white colorant, a cyan colorant, a magenta colorant, a yellow colorant, and a black colorant is preferably used.

The content of the coloring agent in the rotary printing ink is not particularly limited, and in the case of a color ink, it is preferably 10% by weight or more, more preferably 15% by weight or more, and further preferably 30% by weight or less, more preferably 25 wt% or less. In the case of white ink, it is preferably 25% by weight or more, more preferably 30% by weight or more, and is preferably 50% by weight or less, more preferably 45% by weight or less. More specifically, in the case of a color ink, it is preferably 10% by weight to 30% by weight, more preferably 15% by weight to 25% by weight. In the case of white ink, it is preferably 25% by weight to 50% by weight, more preferably 30% by weight to 45% by weight.

5. Hydrocarbon-based wax The hydrocarbon-based wax preferably has a melting point of from 90 ° C to 140 ° C, more preferably from 100 ° C to 140 ° C, from the viewpoints of abrasion resistance and blocking resistance. Further, the average particle diameter of the hydrocarbon wax is preferably from 0.5 μm to 10 μm from the viewpoints of blocking resistance, surface gloss, and the like. In the selection of the average particle diameter of the hydrocarbon wax, it is preferably selected in accordance with the relationship with the thickness of the coating film. When the particle diameter is excessively smaller than the thickness of the coating film, the wax is buried in the coating film and tends to have poor gloss resistance but poor adhesion. On the other hand, when the particle diameter is excessively larger than the thickness of the coating film, it is observed that although the blocking resistance is improved, the gloss tends to be lowered. In addition, when the hardness of the penetration wax method is 10 or less according to JIS K2235:1991, the hydrocarbon-based wax is preferred because it has improved blocking resistance.

The melting point of the hydrocarbon wax can be measured, for example, using a differential scanning calorimeter "DSC6200" (manufactured by Seiko Instruments Co., Ltd.) at a temperature elevation rate of 10 ° C/min. The average particle diameter of the hydrocarbon wax can be measured, for example, by a laser diffraction/scattering particle size distribution measuring apparatus "LA-920 type" (manufactured by Horiba, Ltd.).

As the hydrocarbon-based wax, for example, a polyethylene wax, a polypropylene wax, a paraffin wax, a fischer tropsch wax, a microcrystalline wax, or the like can be used, and a plurality of these may be used in combination. As a commercial item, "WF640", "W300", and "W310" (all trade names) manufactured by Mitsui Chemicals Co., Ltd. can be preferably used.

The content of the hydrocarbon-based wax in the rotary printing ink is not particularly limited, and it is ensured with the aqueous urethane resin (A) and the optionally formulated aqueous urethane urea resin (B) and urethane. From the viewpoint of further improving the adhesion resistance of the ester/acrylic composite resin (C) and further improving the blocking resistance, it is preferably 0.5% by weight or more, more preferably 1% by weight or more, based on the total weight of the rotary printing ink. It is preferably 7% by weight or less, more preferably 4% by weight or less, still more preferably 0.5% by weight to 7% by weight, and still more preferably 1% by weight to 4% by weight.

6. The water is preferably from 40% by weight to 70% by weight in the rotary printing ink. Further, the color ink is preferably 40% by weight to 60% by weight, and the white ink is preferably 50% by weight to 70% by weight.

7. Antimony Compound In one embodiment, the rotary printing ink preferably contains a bismuth compound. The hydrazine compound further enhances the cohesive force in the aqueous urethane resin (A) or the aqueous urethane urea resin (B) in the ink, so that the ink film becomes firm, and the lamination strength and stick resistance can be improved. Connected and so on. The content of the ruthenium compound is preferably 0.1% by weight or more based on the total weight of the rotary printing ink, and is preferably 0.8% by weight or less, and more specifically, preferably 0.1% by weight to 0.8% by weight. The hydrazine compound is not particularly limited, and examples of preferred compounds include diammonium malonate, diterpene succinate, diterpene glutarate, diammonium adipate, and bismuth sebacate. Among them, diammonium adipate is preferred.

8. Other Components Further, the rotary printing ink may contain a known additive such as an antifoaming agent, a tackifier, a leveling agent, a pigment dispersing agent, and a UV absorber, as needed. Further, an organic solvent such as an alcohol, a ketone or an ester may be contained, and an alcohol system is preferred in terms of environmental compatibility and printing plate resistance (flexographic printing). Specifically, n-propanol and isopropanol are preferred. In the case where an organic solvent is contained, the content thereof is preferably 20% by weight or less, more preferably 10% by weight or less in the ink.

Further, a resin other than the aqueous urethane resin (A), the aqueous urethane urea resin (B), and the urethane/acrylic composite resin (C) may be contained as an adhesive for the ink. ingredient. Examples of the resin that can be optionally contained include a conventional aqueous urethane resin other than the aqueous urethane resin (A), a polyester resin, an acrylic resin, a styrene-acrylic resin, and a styrene- An aqueous resin such as a maleic anhydride resin, a rosin-modified maleic acid resin, a cellulose resin, or a chlorinated polyolefin may be used in combination.

The method for producing the rotary printing ink is not particularly limited, and can be preferably produced by mixing the blending components using, for example, a ball mill, an attritor or a sand mill.

<Use of Ink> An embodiment of the present invention relates to a use of the above-described rotary printing ink, which is used for rotary printing. That is, the use of an ink (rotary printing ink) for rotary printing containing an aqueous urethane resin (A), a coloring agent, a hydrocarbon wax, and water. The details of the ink (rotary printing ink) used for this purpose are as described above.

<Use of Rotary Printing Ink> An embodiment of the present invention relates to the use of one of the rotary printing inks. That is, a use of a rotary printing ink for gravure printing, the rotary printing ink comprising an aqueous urethane resin (A1), an aqueous urethane resin (A2), and a white colorant and used for intaglio printing print. In this case, as described above, the solid component weight of the aqueous urethane resin (A1) and the aqueous urethane resin (A2) in the rotary printing ink is preferably from 30/70 to 50/50. Further, as described above, the rotary printing ink is preferably a coloring agent comprising an aqueous urethane resin (A1) and at least one color selected from the group consisting of cyan, magenta, yellow, and black. Further, the details of the rotary printing ink for gravure printing purposes are as described above. Further, another embodiment is the use of a rotary printing ink for flexographic printing, which in turn comprises an aqueous urethane urea resin (B) and is used for the flexographic printing. The details of the rotary printing ink for flexographic printing purposes are as described above. Still another embodiment relates to the use of the above-described rotary printing ink for forming the printing layer of a plastic film rotary printed matter (described later) having a printing layer on a surface of a plastic film. Similarly, another embodiment relates to the use of a rotary printing ink for a laminated laminate (described later) comprising a plastic film rotary printed matter, and for printing a plastic film surface for forming a plastic film rotary printed matter. Floor.

<Gravure Rotary Printing Ink Set> The gravure rotary printing ink set of one embodiment comprises a gravure rotary printing white ink and one or more gravure rotary printing color inks. As described above, the gravure rotary printing white ink preferably contains an aqueous urethane resin (A1), an aqueous urethane resin (A2), a white coloring agent, a hydrocarbon wax, and water.

As described above, the gravure rotary printing color ink preferably contains an aqueous urethane resin (A1), a coloring agent, a hydrocarbon wax, and water. The ink set can also contain multiple color inks of different colors (ie, different colorants contained). The coloring agent is preferably a coloring agent containing at least one color selected from the group consisting of cyan, magenta, yellow, and black, or a coloring agent of one of the colors, and may also include coloring containing other colors. The ink set of the color ink of the agent.

<Flexible Rotary Printing Ink Set> The flexographic rotary printing ink set of one embodiment comprises a flexographic rotary printing white ink and one or more flexographic rotary printing color inks. As described above, the flexographic rotary printing white ink preferably contains an aqueous urethane resin (A2), an aqueous urethane urea resin (B), a coloring agent, a hydrocarbon wax, and water. Further, it is also preferred to contain a urethane/acrylic composite resin (C).

As described above, the flexographic rotary printing color ink preferably contains an aqueous urethane resin (A2), an aqueous urethane urea resin (B), a coloring agent, a hydrocarbon wax, and water. Further, it is also preferred to contain a urethane/acrylic composite resin (C). The ink set can also contain multiple color inks of different colors (ie, different colorants contained). The coloring agent is preferably a coloring agent containing at least one color selected from the group consisting of cyan, magenta, yellow, and black, or a coloring agent of one of the colors, and may also include coloring containing other colors. The ink set of the color ink of the agent.

<Use of Rotary Printing Ink Set> An embodiment of the present invention relates to the use of one of the rotary printing ink sets. That is, the use of the intaglio rotary printing ink set for gravure printing, the gravure rotary printing ink set comprising a gravure rotary printing white ink and one or more intaglio rotary printing color inks. Another embodiment is the use of the flexographic rotary printing ink set for flexographic printing, the flexographic rotary printing ink set comprising flexographic rotary printing white ink and more than one flexographic rotary printing color ink. Still another embodiment relates to the use of a rotary printing ink set for forming a printed layer of a plastic film rotary print (described later) having a printed layer on a surface of a plastic film. Similarly, another embodiment relates to the use of a rotary printing ink set for a laminated laminate comprising a plastic film rotary print (described later) and for forming a plastic film surface of a plastic film rotary print. Printed layer. Here, the rotary printing ink set includes a gravure rotary printing color ink set and a flexographic rotary printing ink set.

<Plastic film rotary printed matter> The plastic film rotary printed matter of one embodiment has a printed layer on the surface of the plastic film, and the printed layer uses the various rotary printing inks or the gravure rotary printing ink set or flexographic rotary printing ink. Formed by sets. Rotary printing inks can also be used in either version of gravure and flexographic printing depending on the intended print.

The type and thickness of the plastic film are not particularly limited, and examples of the type of the film include a polyester film, a nylon film, a polyolefin film, and a vapor-deposited product of the metal oxide. In the case of a polyolefin film, if a polyolefin film is treated by a corona discharge having a functional group such as a hydroxyl group or a carbonyl group, a good printed matter can be obtained. As the plastic film, a film which is uniaxially or biaxially stretched is preferable. The printed matter is often processed into a take up product, which is then cut to a specific size by a lamination step, a slitting step, or the like, as needed.

<Manufacturing Method of Plastic Film Rotating Printed Material> The manufacturing method of the plastic film rotary printed matter according to the embodiment includes winding the surface of the plastic film, using the rotary printing ink, the gravure rotary printing ink set or the flexographic rotary printing ink set To carry out rotary printing. After printing, lamination, slitting (unnecessary portions of the cut width portion), bag making (cutting and heat sealing to form a bag), and the like can be performed.

By printing the printing ink to the take-up plastic film, high-speed printing can be realized, and the productivity is excellent. The gravure rotary printing is generally a printing method in which a concave plate in which a groove (recessed portion) such as a pattern and/or a character is displayed on a circumferential surface of a cylindrical drum is used, and the printing ink is filled in the groove, and a metal blade is used. The ink adhered to the outside of the groove portion is scraped off, and the object to be printed (plastic film) is pressed between the intaglio plate and the impression cylinder, thereby transferring the printing ink filled in the groove to the object to be printed, thereby The pattern and/or the text are reproduced on the printed body. In the flexographic rotary printing, the ink is supplied to the container of the printing ink directly or via an ink supply pump or the like to an anilox roller having a concave-convex shape on the surface, and the ink supplied to the anilox roller is supported by the layout. The contact of the convex portion is transferred to the layout, and finally transferred to the plastic film by contact of the layout with the plastic film to form a pattern and/or a character. Further, in the present specification, the term "rotary printing" means gravure rotary printing and flexographic rotary printing, and does not include inkjet printing and screen printing as other printing methods.

The winding of the plastic film refers to a roll-shaped plastic film having a predetermined width, and is a film for rotary printing which is different from the continuous cut sheet which is cut one by one. The width of the film can be suitably selected based on the width of the rotary printing press used and the width of the image (pattern) portion of the intaglio plate. In the case where a plurality of colors of the rotary printing ink are used and the colors are overlapped, the printing order is not particularly limited.

In the gravure rotary printing and the flexographic rotary printing method, in the case of performing back printing, the color ink is usually printed on the take-up plastic film, and then the white ink is printed. In the case where color inks of a plurality of colors are present, for example, printing may be performed in the order of black, cyan, magenta, and yellow, but is not particularly limited. Further, in the large printing machine, in addition to the basic color, a special color or the like may be used. In other words, the large printing machine has a plurality of printing units corresponding to five colors to ten colors, and one printing unit includes one color of ink, and can perform superimposition printing of five colors to ten colors at a time. The laminated laminate can be obtained by applying a tackifier coating agent, an adhesive or the like to the printing surface of the rotary printed matter obtained by the above method, and if necessary, bonding to a film or the like after drying.

For surface printing, white ink is usually printed as needed, and then color ink is printed. In the case where color inks of a plurality of colors are present, for example, printing may be performed in the order of yellow, magenta, cyan, and black, but is not particularly limited. In the case of the surface printing composition, an overcoating agent is applied to the printing surface of the rotary printed matter as needed, whereby abrasion resistance, water resistance, and the like can be improved. In the case where the substrate is white, that is, for example, in the case of a paper substrate and a plastic film in which a white pigment is blended, printing using only color ink may be performed as needed.

The laminated laminate of one embodiment comprises the plastic film rotary print. That is, it can be preferably obtained by laminating the plastic film rotary printed matter. Examples of the lamination processing method include the following methods: 1) extrusion lamination method, in which the tackifier coating agent is applied as needed on the printing surface of the obtained printed matter, and then the order of the molten resin or the plastic film is carried out. Or a 2) dry lamination method, after applying an adhesive to the printed surface of the obtained printed matter, drying as needed, and laminating a plastic film. As the molten resin, a low-density polyethylene, a polypropylene, an ethylene-vinyl acetate copolymer, or the like can be used, and examples of the binder include an imide-based, an isocyanate-based, a polybutadiene-based, and a titanate-based compound.

The laminated laminate can be preferably used as a packaging material, and can be particularly preferably used as a packaging material for food use in addition to usual packaging materials. [Examples]

In the following, the embodiments of the present invention are described, but the present invention is not limited to the embodiments, and of course, a large number of embodiments other than those based on the gist of the invention are included. In addition, "part" and "%" are weight basis unless otherwise specified. In addition, the rotary printing ink can also be simply referred to as "ink".

<Synthesis of Aqueous Urethane Resin (A)> (Synthesis Example 1) 74.3 parts of a 2000 ml flask equipped with a reflux cooling tube, a dropping funnel, a gas introduction tube, a stirring device, and a thermometer was placed. Polytetramethylene glycol having a number average molecular weight of 2000, 3 parts of polyethylene glycol having a number average molecular weight of 2000, 13 parts of dimethylolbutanoic acid, 8 parts of bis(2-hydroxypropyl)aniline and 1.7 The 1,4-cyclohexanedimethanol was replaced with dry nitrogen and heated to 100 °C. Under stirring, 41.3 parts of isophorone diisocyanate was added dropwise over 20 minutes, and the temperature was gradually raised to 140 ° C (NCO / OH = 0.98). Further, the reaction was carried out for 30 minutes to obtain a urethane resin. Then, while cooling, 750 parts of distilled water containing 8.9 parts of 28% aqueous ammonia was added to obtain an aqueous urethane resin (A1-1) (weight average molecular weight: about 40,000).

The weight average molecular weight was measured by a gel permeation chromatography (GPC) apparatus (HLC-8220, manufactured by Tosoh Corporation), and was determined in the form of a molecular weight converted from polystyrene used for a standard substance. The measurement conditions are shown below. Column: The following columns are connected in series for use. TSLgelG5000HXL manufactured by Tosoh Corporation, TSKgelG5000HXL manufactured by Tosoh Corporation, TSKgelG4000HXL manufactured by Tosoh Corporation, TSKgelG3000HXL manufactured by Tosoh Corporation, TSKgelG2000HXL Apparatus: RI (differential refractometer) Measurement conditions: column temperature 40 ° C Dissolution: tetrahydrofuran flow rate: 1.0 mL / min

(Synthesis Example 2 to Synthesis Example 9) Aqueous urethane resin (A1-2) to aqueous urethane resin (A1) was synthesized using the starting material compounds shown in Table 1 in the same manner as in Synthesis Example 1. -9). In addition, the neutralization by 28% aqueous ammonia was carried out in the same manner as in Synthesis Example 1 in such a manner that the carboxyl group derived from dimethylolbutanoic acid became equimolar. The ellipsis of each raw material compound of Table 1 respectively represent the following compounds.

MPD/AA: 3-methyl-1,5-pentanediol/adipic acid (polyester polyol) PTG: polytetramethylene glycol (polyether polyol) PEG: polyethylene glycol (polyether) Polyol) DMBA: Dimethylolbutyric acid Bis-HPA: bis(2-hydroxypropylaniline) CHDM: 1,4-cyclohexanedimethanol TMP: Trimethylolpropane IPDI: Isophorone diisocyanate

[Table 1]

(Synthesis Example 10 to Synthesis Example 14) Aqueous urethane resin (A2-1) to aqueous urethane resin (A2) was synthesized using the starting material compounds shown in Table 2 in the same manner as in Synthesis Example 1. -5).

[Table 2]

(Comparative Synthesis Example 1 to Comparative Synthesis Example 6) The raw material compounds shown in Table 3 were used in the same manner as in Synthesis Example 1 to synthesize a comparative aqueous urethane resin (PU1) to a comparative aqueous urethane resin. (PU6).

[table 3]

<Synthesis of Aqueous Urethane Urea Resin (B)> (Synthesis Example 15) In a reactor equipped with a reflux cooling tube, a dropping funnel, a gas introduction tube, a stirring device, and a thermometer, nitrogen gas was introduced while mixing 77.6. A portion of poly(pivalate adipate) diol (NPG/AA) having an average molecular weight of 2000, 8 parts of polyethylene glycol (PEG) having a number average molecular weight of 2000, and 14.4 parts of 2,2-dihydroxyl Butyl acid (DMBA) and 40.6 parts of methyl ethyl ketone (MEK) were stirred while heating. At a boiling temperature, 62.2 parts of isophorone diisocyanate (IPDI) was added dropwise over 1 hour, and further, a boiling reaction was carried out for 4 hours to obtain a terminal isocyanate prepolymer, and then, after cooling to 30 ° C, 100 was added. A portion of isopropanol to obtain a solvent solution of the terminal isocyanate prepolymer. In a mixture of 25.7 parts of isophorone diamine (IPDA) and 400 parts of isopropanol, the total amount of the terminal isocyanate prepolymer solution obtained was gradually added at room temperature, and reacted at 40 ° C. A solvent-type polyurethane resin solution was obtained in 2 hours. Then, 5.9 parts of 28% ammonia water and 485.8 parts of ion-exchanged water were gradually added to the solvent-type polyurethane resin solution to neutralize, thereby performing water-solubilization and further azeotropy. Methyl ethyl ketone and isopropyl alcohol were distilled off, and then water was added for viscosity adjustment to obtain an aqueous urethane urea resin having an acid value of 29 mgKOH/g, a solid content of 25%, and a weight average molecular weight of 45,000. B-1).

(Synthesis Example 16) An aqueous urethane urea resin (B-2) was synthesized in the same manner as in the above Synthesis Example 15 using the starting compounds shown in Table 4. Further, the neutralization with 28% aqueous ammonia was carried out in the same manner as in Synthesis Example 11 so that the carboxyl group derived from DMBA became equimolar. In Table 4, AEA is 2-aminoethylethanolamine.

[Table 4]

<Production of Ink of Comparative Example and Comparative Example> Each of the raw materials shown in Table 5 was stirred for 10 minutes using an Eiger Mill (manufactured by EIGER) to produce an ink of the example. Further, the ink of the comparative example was produced in the same manner using the raw materials shown in Table 6. The details of the hydrocarbon wax used are shown in Table 7. Examples 1 to 8 of Table 5-1 are examples of color inks which are particularly preferable for gravure printing applications, and Examples 9 to 13 are examples of white inks which are particularly preferable for gravure printing applications. Examples 14 to 23 of Table 5-2 are examples of color inks which are particularly preferable for flexographic printing applications, and Examples 24 to 26 are examples of white inks which are particularly preferable for flexographic printing applications. . Examples 27 to 29 of Table 5-3 are examples of ink sets that are particularly preferable for gravure printing applications, and Examples 30 to 32 are excellent ink set applications for flexographic printing applications. Examples, Examples 33 and 34 are examples of color inks which are particularly preferable for gravure printing applications, Example 35 is an example of white ink which is particularly preferable for gravure printing applications, and Example 36 is used as flexographic printing. An embodiment of white ink that is particularly useful for use. The urethane/acrylic composite resin (C) used was "WEM-202U" manufactured by Taisei Fine Chemical Co., Ltd.

[Table 5-1]

[Table 5-2]

[Table 5-3]

[Table 6]

[Table 7]

<Evaluation Method and Evaluation Criteria> The printing in the examples and comparative examples was carried out in the following manner. Gravure rotary printing: A plastic printing film was printed at a speed of 50 m/min using a small printing machine of a rock printing machine (stock), and dried at 60 to 70 ° C to obtain a printed matter. The version uses a corrosion-resistant 200-line version of the 20 μm full-face version. Flexo Rotary Printing: Using a central roller type 6 color flexo press "SOLOFLEX" manufactured by Windmoller & Holscher, at a speed of 100 m/min for plastic film Printing is carried out and dried at 60 ° C to 70 ° C to obtain a printed matter. As an anilox roller, 350 lb/cm was used as a plate cylinder, and DuPont (Cyrel) was attached to Du Pont by using double-sided tape ("DF7382T" manufactured by Toyo Ink Co., Ltd., thickness 0.50 mm). DPU" (thickness 1.14 mm) is used as a full-face version.

(1) Ink stability After the ink was stored at 40 ° C for 3 months, the Zahn cup No. 4 (25 ° C) was used to measure the viscosity over time, and the difference between the evaluation and the completion (initial) viscosity was evaluated. . The evaluation criteria are shown below. The practical level is above C. A: The difference between the viscosity and the time-dependent viscosity is less than 2 seconds. B: The difference between the viscosity and the time-dependent viscosity is 2 seconds or more, and the difference is 4 seconds or less. C: The difference between the viscosity and the time-dependent viscosity is 4 seconds or more. For less than 6 seconds, D: The difference between the viscosity and the time-dependent viscosity is 6 seconds or more, and the difference is 8 seconds or less. E: The difference between the viscosity and the time-dependent viscosity is 8 seconds or more.

(2) Color rendering The ink was spread on a PET film (polyethylene terephthalate film, E-5102, 12 μm manufactured by Toyobo Co., Ltd.) using a Mayer bar. The degree of transparency, concentration, and gloss is determined by visual inspection. The higher the transparency, the higher the concentration, and the higher the gloss, the better the color rendering property was judged. The evaluation criteria are shown below. The practical level is above C. A: high transparency, high concentration, and high gloss. B: It has a transparent feeling, a concentration, and a high gloss. C: a transparent feeling, a slightly poor concentration, and a moderate degree of gloss. D: transparency, poor concentration, and insufficient gloss. E: No transparency, concentration, and no gloss.

(3) Resolubility The ink was applied to the Ballard version, and after air drying, 25 ml of a dilution solvent (water/n-propanol mixed solvent, weight ratio 70/30) was sagged, and the printing ink was visually judged. The dissolution of the film. The practical level is above D. A: All dissolved. B: A slight dissolution residue was confirmed. C: The dissolution residue of an area of less than 10% was confirmed. D: The dissolution residue of an area of 10% or more and less than 30% was confirmed. E: It was confirmed that the dissolution residue of the area of 30% or more was obtained.

(4) Adhesiveness of the substrate A 10 mm-wide adhesive tape manufactured by Nichiban Co., Ltd. was attached to the OPP film (Extended Polypropylene Film, P-2161, 30 μm manufactured by Toyobo Co., Ltd.) The printed matter obtained by printing the ink was subjected to a peeling test. The transfer state (obtained state) of the ink film to the adhesive tape (scotch tape manufactured by Nichiban Co., Ltd.) was visually evaluated on the basis of the following criteria. The evaluation criteria are shown below. The practical level is above C. A: The ink is not transferred to the adhesive tape at all. B: The transfer of less than 5% of the ink was confirmed on the adhesive tape. C: The transfer of ink of 5% or more and less than 10% was confirmed on the adhesive tape. D: The transfer of ink of 10% or more and less than 50% was confirmed on the adhesive tape. E: It was confirmed that more than 50% of the ink was transferred on the adhesive tape.

(5) Blocking resistance The printed matter obtained by printing ink on the OPP film (the P-2161) was sampled at 4 cm × 4 cm, and the printed surface of the sample was not the same as the unprinted film of the same size. The corona-treated surface was combined and pressed at 10 kgf/cm ² for 12 hours at 40 ° C to observe ink transfer and resistance feeling when the sample was peeled off. The evaluation criteria are shown below. The practical level is above C. A: The transfer of ink from the printed matter was not confirmed at all, and there was no sense of resistance at the time of peeling. B: The transfer of ink from the printed matter was not confirmed at all, but there was a feeling of resistance at the time of peeling. C: The transfer of ink from the printed matter was confirmed to be less than 10% in terms of area. D: The transfer of ink from the printed matter was confirmed in an area of 10% or more and less than 50%. E: The transfer of ink from the printed matter was confirmed in an area of 50% or more.

(6) Water resistance The printed matter obtained by printing ink on the OPP film (the P-2161) was gently wiped 10 times with water-containing absorbent cotton, and visually evaluated on the following basis. The evaluation criteria are shown below. The practical level is above C. A: Even if it was wiped 10 times, peeling and dissolution of the ink surface were not confirmed. B: After wiping for 10 times, the ink surface peeled off and dissolved in about half of the area. C: After 10 times of wiping, most of the ink surface peeled off and dissolved. D: When wiped 5 times, most of the ink surface peeled off and dissolved. E: When wiping twice, most of the ink surface peeled off and dissolved.

(7) Laminate strength On a printed matter obtained by printing ink on an OPP film (the P-2161), an imide-based tackifying coating agent (EL manufactured by Toyo Morton Co., Ltd.) was applied. -420), by using an extrusion laminator, a polyethylene melted at 315 ° C, and a CPP film (unstretched polypropylene film having a thickness of 30 μm; a sealant film) was bonded to obtain a laminate processed product ( Extrusion lamination method). The workpiece was cut at a width of 15 mm, and the peel strength at the time of peeling between the ink surface and the OPP film surface was measured using a 2.01 million tensile tester manufactured by INTECCO. The evaluation criteria are shown below. The practical level is above C. A: When the peeling strength is 0.9 N/15 mm or more, B: The peeling strength is 0.7 N/15 mm or more, and less than 0.9 N/15 mm. C: The peeling strength is 0.5 N/15 mm or more and less than 0.7 N/15. M: D: Peel strength is 0.3 N/15 mm or more, less than 0.5 N/15 mm E: Peel strength less than 0.3 N/15 mm

(8) Whitening property (evaluation of gravure ink) A mixed solvent of water/isopropyl alcohol (mixing ratio 1:1) was added to 100 parts of ink, and a Zahn cup (Zahn) manufactured by a clutch was used. Cup) #3 The viscosity is adjusted to 16 seconds, and the winner is used, and a doctor blade with a plate depth of 25 μm and a blade tip thickness of 65 μ (trade name "New Doctor Hyblade"), Fuji The corona discharge printing machine of the PET film (the E-5102) was printed at a printing speed of 100 m/min after being idling for 60 minutes at a drum rotation speed of 100 m/min. Printing was carried out and dried by hot air at 60 ° C to obtain a printed matter.

The amount of ink adhering to the blank portion (non-image portion) of the obtained printing film was visually evaluated on the basis of the following criteria. The evaluation criteria are shown below. The practical level is above C. A: In the non-image section, the transfer of ink was not confirmed at all. B: The transfer of ink was slightly confirmed in a small area (less than 5%) of the non-image portion. C: In the medium area (5% to less than 10%) of the non-image portion, the transfer of the ink was confirmed. D: The transfer of ink was confirmed in a large area (10% or more) of the non-image portion. E: The transfer of ink was confirmed on the entire surface of the non-image portion.

(9) Washability (Evaluation of Flexographic Ink) The ink was developed on an OPP film (the P-2161) and dried at room temperature for 10 minutes. Then, water, n-propanol, and Magiclean (a special solvent for washing, Kao) were dripped on the coating film to investigate the solubility of the coating film, and it was set as a plate-washing property. Simple evaluation. The evaluation criteria are shown below. The practical level is above C. A: Dissolution only occurs in water. B: Dissolution occurred only in n-propanol. C: Dissolution occurs in Wan Wanling. D: Even in Wan Jie Ling, it does not dissolve.

The results obtained are shown in Table 8 (Examples) and Table 9 (Comparative Examples). [Table 8-1]

[Table 8-2]

[Table 8-3]

[Table 9-1]

[Table 9-2]

As shown in Table 8 (Table 8-1 to Table 8-3), in the examples, inks having a blocking resistance, water resistance, and lamination strength of more than a practical level were obtained, and it was confirmed that it was suitable for the plastic film. Rotating printed ink on. On the other hand, as shown in Table 9 (Table 9-1 to Table 9-2), the ink of the comparative example did not satisfy the practical level in any of the blocking resistance, the water resistance, and the lamination strength.

no

no

Claims (15)

A rotary printing ink comprising an aqueous urethane resin (A), a coloring agent, a hydrocarbon wax and water, wherein the aqueous urethane resin (A) has an acid value of 25 mgKOH/ in the rotary printing ink. g to 45 mgKOH/g, and includes a structural unit represented by the following general formula (1) and the general formula (2), the hydrocarbon wax having a melting point of 90 ° C to 140 ° C and an average particle diameter of 0.5 μm to 10 μm ; In the formula (1), Ph represents a substituted or unsubstituted phenyl group, In the formula (2), R ¹ and R ^{2 each} represent a substituted or unsubstituted aliphatic hydrocarbon group, which may be the same or different, and A represents an alicyclic hydrocarbon group. The rotary printing ink according to claim 1, wherein the aqueous urethane resin (A) comprises a structural unit of a polyether-based and/or polyester-based high molecular weight diol and has three in the same molecule. The structural unit of the above compound capable of reacting with an isocyanate group, the structural unit of the formula (1) is contained in the resin solid content in an amount of 5 to 10% by weight, and the structural unit of the formula (2) is in a resin solid content It contains 0.5% by weight to 5% by weight. The rotary printing ink according to claim 1 or 2, wherein the aqueous urethane resin (A) contains an aqueous urethane resin (A1) and an aqueous urethane resin ( At least one of A2), the aqueous urethane resin (A1) has 3% by weight to 7% by weight of a polyethylene glycol unit in the solid content of the aqueous urethane resin (A1), The aqueous urethane resin (A2) has 20 to 30% by weight of a polyethylene glycol unit in the solid content of the aqueous urethane resin (A2). The rotary printing ink according to claim 3, which comprises an aqueous urethane resin (A1), an aqueous urethane resin (A2), and a white colorant, and is used for gravure printing. The rotary printing ink according to claim 3, wherein, in the case of containing both the aqueous urethane resin (A1) and the aqueous urethane resin (A2), The solid component weight ratio of the aqueous urethane resin (A1) to the aqueous urethane resin (A2) is from 30/70 to 50/50. The rotary printing ink according to claim 3, which comprises an aqueous urethane resin (A1) and a coloring agent selected from at least one color selected from the group consisting of cyan, magenta, yellow, and black. And used for gravure printing. The rotary printing ink according to any one of claims 1 to 3, further comprising an aqueous urethane urea resin (B), the aqueous urethane urea resin (B) A polyester polyol unit having branches is included. The rotary printing ink according to claim 7, wherein the aqueous urethane resin (A) and the aqueous urethane urea resin (B) have a solid content weight ratio of 25/75 to 45/ 55. The rotary printing ink according to claim 7 or 8, wherein the aqueous urethane resin (A) contains an aqueous urethane resin (A2), the aqueous urethane The resin (A2) has 20 to 30% by weight of a polyethylene glycol unit in the solid content of the aqueous urethane resin (A2). The rotary printing ink according to any one of claims 7 to 9, which further comprises a urethane/acrylic composite resin (C). The rotary printing ink according to any one of claims 7 to 10, which is used for flexographic printing. A gravure rotary printing ink set comprising the rotary printing ink of claim 4 and more than one of the rotary printing inks of claim 6 of the patent application. A flexographic rotary printing ink set comprising two or more rotary printing inks according to claim 11 of the patent application scope, wherein the flexographic rotary printing ink set is a combination of the following flexographic rotary printing inks: comprising white coloring a flexographic rotary printing ink of the agent; and one or more flexographic rotary printing inks comprising a coloring agent selected from the group consisting of at least one of cyan, magenta, yellow, and black. A plastic film rotary printing having a printing layer on a surface of a plastic film, the printing layer being a rotary printing ink according to any one of the first to eleventh aspects of the patent application, as claimed in claim 12 The intaglio rotary printing ink set of the item or the flexographic rotary printing ink set of claim 13 is formed. A laminated laminate comprising the plastic film rotary print of claim 14.