Master batch composition and method for producing ink composition using said master batch composition

Abstract

According to the present disclosure, by using a master batch composition which has a specific composition, it is possible to provide an ink composition which exhibits excellent storage stability and maintains excellent color developability and low viscosity for a long period of time.　The present disclosure provides: a master batch composition which contains a colorant, a polyurethane resin and / or a (meth)acrylic resin, and an organic solvent; and a method for producing an ink composition using the composition.

Description

Masterbatch composition and method for producing an ink composition using the masterbatch composition

[0001] The present invention relates to a masterbatch composition and a method for producing an ink composition using the masterbatch composition.

[0002] Gravure inks or flexographic inks are widely used to impart aesthetic appeal and functionality to substrates. With the diversification of packaging materials and the advancement of packaging technology, the performance requirements for various printing inks have also diversified according to their applications. For example, there is surface printing, where the printing ink layer is printed on the surface of a plastic film, and reverse printing, where the ink layer is provided between plastic films and laminated. Conventionally, printing inks using polyurethane resin and vinyl chloride-vinyl acetate copolymer resin (hereinafter referred to as "PVC") as binders have been widely used for laminated products. These resins are a binder combination that can achieve both excellent dispersibility and high film properties, and are indispensable ink raw materials for achieving good printability and various physical properties required for laminating inks, such as adhesion to the substrate, lamination strength, and boil retort resistance. For example, Patent Document 1 is cited as a technology for an ink composition containing polyurethane resin and vinyl chloride-vinyl acetate copolymer resin. Patent Document 1 discloses a technique for using a compound in which the amino group of a polyamine compound has been ketiminated by a ketone compound, because low molecular weight polyurethane polyurea resins tend to generate a lot of free amines, which makes them prone to odor generation and reduces their stability over time.

[0003] Furthermore, in recent years, there has been a demand for printing inks in which the ink layer applied to the plastic film can be detached in order to improve the recycling rate. If the detachment of the ink layer can be made possible and this problem can be solved, the value of recycled plastics will increase, leading to the entry of new recycling companies and the improvement of separate collection by local governments. For example, Patent Document 2 is cited as a technology relating to an aqueous ink in which the ink coating can be detached from the substrate. Patent Document 2 discloses an aqueous liquid ink in which the acid value in the solid content is in the range of 3 to 150 mg KOH / g.

[0004] Japanese Patent Publication No. 2022-157067, International Publication No. 2021 / 192749

[0005] Generally, printing inks undergo transportation or long-term storage after preparation before reaching the printing process. Such transportation or long-term storage can lead to problems with color development, making it necessary to improve the storage stability of printing inks. However, the technology described in Patent Document 2 does not consider the time-dependent stability of aqueous liquid inks at all. On the other hand, while the technology described in Patent Document 1 evaluates time-dependent stability, it requires amine compounds and ketimination treatment, resulting in a large number of product types and a complicated manufacturing process.

[0006] Particularly in recent years, as mentioned above, the trend of diversifying the required characteristics of printing inks in conjunction with the diversification of packaging materials has led to the need for a wide variety of resins and additives in printing inks. However, it has been confirmed that the coexistence of multiple types of resins, pigments, and additives in a composition can cause problems such as changes in the properties of the ink composition itself over time due to chemical reactions between the resins, pigments, or additives, resulting in issues such as storage stability and deterioration of color development over time. Additives, in particular, usually have reactive functional groups to exhibit their function, but transportation or long-term storage can not only cause a decrease in functionality due to the deactivation of these reactive functional groups, but can also lead to an increase in the viscosity of the printing ink or re-aggregation of pigments. Furthermore, because printing inks are made by dispersing powdered raw materials, it has been confirmed that they are prone to re-aggregation during long-term storage, and the formation of precipitates can easily cause problems in the preparation of the printing ink.

[0007] Therefore, the present disclosure aims to provide a masterbatch composition capable of preparing an ink composition that exhibits excellent storage stability and maintains excellent color development and low viscosity for a long period of time, as well as a method for producing an ink composition from said masterbatch composition.

[0008] The inventors of this invention, after diligent research, discovered that the above problems can be solved by using a masterbatch composition of a predetermined composition, and thus came to present the present invention.

[0009] [1] A masterbatch composition containing a colorant, a polyurethane resin and / or a (meth)acrylic resin, and an organic solvent.

[0010] [2] A masterbatch composition for preparing an ink composition by blending an additive, wherein the additive is blended in an amount of 1 to 10 parts by mass per 100 parts by mass of the masterbatch composition, as described in [1].

[0011] [3] The masterbatch composition according to [2], wherein the additive contains one or more selected from the group consisting of an acidic resin, a curing agent, an antiblocking agent, an antistatic agent, a coating reinforcing agent, and an antifoaming agent.

[0012] [4] The masterbatch composition according to any one of [1] to [3], wherein the content of the coloring agent is 5 to 40% by mass with respect to the total amount (100% by mass) of the masterbatch composition.

[0013] [5] The masterbatch composition according to any one of [1] to [4], wherein the content of the polyurethane resin and / or the (meth)acrylic resin is 5 to 30% by mass with respect to the total amount (100% by mass) of the masterbatch composition.

[0014] [6] The masterbatch composition according to any one of [1] to [5], wherein the concentration of urethane groups in the polyurethane resin in the entire masterbatch composition is 0.3 mmol / g or more and 1.5 mmol / g or less.

[0015] [7] A masterbatch composition used to prepare an ink composition by blending an additive with the masterbatch composition, wherein the white color difference ΔE*ab calculated from L*, a*, and b* measured by the SCE method using a spectrophotometer before and after blending with the additive is 2 or less, and the urethane group concentration in the tan resin is 0.3 mmol / g or more and 1.5 mmol / g or less, according to any one of [1] to [6].

[0016] [8] A masterbatch composition used to prepare an ink composition by compounding an additive with the masterbatch composition, wherein the viscosity change rate (%) of the composition before and after compounding with the additive is given by the following formula (1): Viscosity change rate (%) = | ({η ｍｉｘ -η ｍ} / η ｍ ) | × 100 < 15 (%) (In the above formula (1), η ｍｉｘ η represents the viscosity of the mixture of the masterbatch composition and the additive at 25°C, ｍ represents the viscosity of the masterbatch composition at 25°C.) A masterbatch composition according to any one of [1] to [6] that satisfies the following conditions.

[0017] [9] The masterbatch composition according to claim 1 or 2, wherein the acid value of the entire masterbatch composition is in the range of 0 mg KOH / g or more and 30 mg KOH / g or less.

[0018]

[10] A method for producing an ink composition, comprising: a masterbatch preparation step of preparing a masterbatch composition according to claim 1, which contains a colorant, a polyurethane resin and / or a (meth)acrylic resin, and an organic solvent; an additive preparation step of preparing an additive; and an additive step of adding the additive to the masterbatch composition.

[0019] According to this disclosure, by using a masterbatch composition of a predetermined composition, it is possible to provide an ink composition that exhibits excellent storage stability and maintains excellent color development and low viscosity for a long period of time.

[0020] The embodiments of the present invention (hereinafter referred to as "these embodiments") will be described in detail below, but this disclosure is not limited to the following description and can be implemented in various ways within the scope of its gist.

[0021] [Definitions] In this specification, "ink composition" refers to a liquid printing ink applied to printing methods using printing plates, such as gravure inks and flexographic inks, and is preferably a gravure ink or flexographic ink. Therefore, "ink composition" includes liquid ink compositions (= liquid ink compositions). Also, in the following description, "ink" always refers to "printing ink". In this specification, "parts" always refers to "parts by mass", "total ink" refers to the total amount of ink including all volatile components such as solvents, and "(ink or resin) solids (total)" refers to the total amount of non-volatile components only, excluding volatile components. In this specification, "reaction raw material" refers to a compound used to obtain a target compound by a chemical reaction such as combination or decomposition, and which partially constitutes the chemical structure of the target compound, excluding catalysts and solvents. In particular in this specification, "reaction raw material" refers to a precursor for obtaining a target resin (polyurethane resin, (meth)acrylic resin) by a chemical reaction. In this specification, "constituent unit" refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization. In other words, in a compound formed during a reaction or polymerization, it refers to a substructure other than the chemical bond structure involved in the reaction or polymerization, and is commonly known as a residue.

[0022] [Masterbatch Composition] The masterbatch composition of this embodiment contains a colorant, a polyurethane resin and / or a (meth)acrylic resin, and an organic solvent. Preferably, the masterbatch composition also contains optional additives. This makes it possible to provide an ink composition that exhibits excellent storage stability and maintains excellent color development and low viscosity for a long period of time by using the masterbatch composition.

[0023] In the masterbatch composition of this embodiment, the total content of the colorant (solids), polyurethane resin (solids), and / or (meth)acrylic resin (solids), and the organic solvent is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, even more preferably 50 to 100% by mass, even more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass, based on the total amount (100% by mass) of the masterbatch composition. In the masterbatch composition of this embodiment, the total content of the colorant (solids), polyurethane resin (solids), and / or (meth)acrylic resin (solids), the organic solvent, and any additional components is preferably 40 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass, based on the total amount (100% by mass) of the masterbatch composition.

[0024] The masterbatch composition of this embodiment is preferably a masterbatch composition for ink compositions, which is prepared by blending an additive with the masterbatch composition. By preparing an ink composition using the masterbatch composition, re-aggregation can be suppressed, resulting in a homogeneous ink composition that exhibits excellent storage stability and maintains excellent color development and low viscosity for a long period of time. In this embodiment, when preparing an ink composition from the masterbatch composition of this embodiment, it is preferable that the additive is blended in an amount of 1 to 15 parts by mass per 100 parts by mass of the masterbatch composition, more preferably 1 to 13 parts by mass, even more preferably 1 to 10 parts by mass, and particularly preferably 1 to 8 parts by mass. In this specification, a composition containing a masterbatch composition and an additive is referred to as an ink composition. In this embodiment, the additive is preferably one or more components selected from the group consisting of acidic resins, curing agents, anti-blocking agents, antistatic agents, film reinforcing agents, and defoaming agents.

[0025] When the masterbatch composition of this embodiment contains more than 0% by mass of polyurethane resin relative to the total amount (100% by mass) of the masterbatch composition, the concentration of urethane groups in the polyurethane resin in the entire masterbatch composition is preferably 0.3 mmol / g or more and 1.5 mmol / g or less. Maintaining the above range for the concentration of urethane groups in the polyurethane resin in the entire masterbatch composition is preferable from the viewpoint of substrate adhesion. The concentration of urethane groups in the polyurethane resin in the entire masterbatch composition is preferably 0.1 mmol / g or more and 2.5 mmol / g or less, more preferably 0.1 mmol / g or more and 2.3 mmol / g or less, even more preferably 0.1 mmol / g or more and 2.1 mmol / g or less, and even more preferably 0.1 mmol / g or more and 1.9 mmol / g or less. This makes it possible to prepare an ink composition that exhibits better storage stability and maintains better color development and low viscosity for a long period of time. The method for calculating the urethane group concentration is as described in the section (Properties of Polyurethane Resin) below.

[0026] The acid value of the entire masterbatch composition (solids) in this embodiment is preferably in the range of 0 mg KOH / g to 30 mg KOH / g. This makes it possible to prepare an ink composition that exhibits better storage stability and maintains better color development and low viscosity for a long period of time. When the masterbatch composition of this embodiment contains more than 0% by mass of (meth)acrylic resin relative to the total amount (100% by mass) of the masterbatch composition, the acid value of the entire masterbatch composition (solids) is preferably in the range of 1 mg KOH / g to 30 mg KOH / g. Setting the acid value of the entire masterbatch composition within the above range is preferable from the viewpoint of adhesion to aluminum foil and metal vapor-deposited films. The acid value of the entire masterbatch composition (solids) is preferably 1 mg KOH / g or more and 100 mg KOH / g or less, more preferably 1 mg KOH / g or more and 90 mg KOH / g or less, even more preferably 1 mg KOH / g or more and 80 mg KOH / g or less, even more preferably 1 mg KOH / g or more and 70 mg KOH / g or less, and even more preferably 1 mg KOH / g or more and 60 mg KOH / g or less. The method for measuring the acid value described herein is expressed in milligrams as the amount of potassium hydroxide required to neutralize acid groups such as carboxyl groups per gram of sample solids, and is measured in accordance with JIS K 5601-2-1:1999.

[0027] In this embodiment, the masterbatch composition used to prepare an ink composition by blending an additive with the masterbatch composition is preferably such that the white color difference ΔE*ab, calculated from L*, a*, and b* measured by the SCE method using a spectrophotometer before and after the blending of the additive, is 2 or less. This makes it possible to provide a masterbatch composition that can prepare an ink composition that exhibits better storage stability and maintains better color development and low viscosity for a long period of time.

[0028] The above statement that "the white color difference ΔE*ab calculated from L*, a*, b* measured by the SCE method using a spectrophotometer before and after the addition of the additive is 2 or less" means that the white color difference ΔE*ab between the masterbatch composition of the present embodiment and an ink composition, which is a composition obtained by blending an additive into the masterbatch composition, is 2 or less. The white color difference ΔE*ab is preferably 2 or less, more preferably 1.8 or less, still more preferably 1.5 or less. When the white color difference ΔE*ab is 2 or less, it is generally at a level where almost no difference can be distinguished visually. Although the details are unclear, when a highly reactive additive, a polyurethane resin and / or (meth)acrylic resin having lower reactivity than the additive, and a colorant are allowed to coexist, the highly reactive additive becomes dominant, and components present in the system can aggregate, interact, and chemically react with each other. However, when the low-reactivity polyurethane / acrylic resin and the colorant are allowed to coexist first, a so-called metastable state is formed due to the mild interaction between the two, so even if a highly reactive additive is blended later, a large amount of external energy is required for the transition from the metastable state to a state where the additive is dominant. Therefore, it is considered that the interaction of the additive with the colorant can be reduced. As a result, it is considered that the original coloring effect of the colorant can be maintained. The method for measuring the white color difference ΔE*ab is calculated by the method described in the Examples section.

[0029] In the present embodiment, the masterbatch composition is used for preparing an ink composition by blending an additive into the masterbatch composition, wherein the rate of change in viscosity (%) of the composition before and after blending with the additive satisfies the following formula (1): Rate of viscosity change (%) = |({η ｍｉｘ -η ｍ} / η ｍ )|×100<15 (%) (In the above formula (1), η ｍｉｘ represents the viscosity (in seconds) of the mixture of the masterbatch composition and the additive at 25°C, and η ｍ∫ represents the viscosity (seconds) of the masterbatch composition at 25°C. It is preferable that the following conditions are met. The viscosity of the entire masterbatch composition (at Zahn cup #3) is preferably 5 seconds to 60 seconds, more preferably 8 seconds to 55 seconds, even more preferably 8 seconds to 50 seconds, even more preferably 10 seconds to 50 seconds, and even more preferably 10 seconds to 45 seconds. The viscosity of the ink composition is preferably 3 seconds to 65 seconds, more preferably 3 seconds to 60 seconds, even more preferably 5 seconds to 60 seconds, and even more preferably 5 seconds to 55 seconds. This makes it possible to provide a masterbatch composition that can prepare an ink composition that exhibits better storage stability and maintains better color development and low viscosity for a long period of time.

[0030] The above-mentioned "percentage change in viscosity of the composition before and after blending with the additive (%)" refers to the percentage change in viscosity of the masterbatch composition of this embodiment and the ink composition, which is the masterbatch composition blended with the additive. Therefore, the percentage change in viscosity of this embodiment is the viscosity (seconds) of the masterbatch composition of this embodiment at 25°C η ｍ The viscosity (seconds) of the ink composition obtained by blending the additives with the masterbatch composition at 25°C is η ｍｉｘ The two values ​​are measured separately, and the absolute value of the difference between them is the viscosity (seconds) of the masterbatch composition of this embodiment at 25°C. ｍThis is the percentage (%) of the value obtained by dividing by . The viscosity change rate (%) is preferably 15% or less, more preferably 13% or less, and even more preferably 10% or less. When the viscosity change rate (%) is 15% or less, it has the effect of obtaining a stable printed material density with little concentration change. Although the details are unclear, when a highly reactive additive, a polyurethane resin and / or (meth)acrylic resin that is less reactive than the additive, and a colorant coexist, the highly reactive additive becomes dominant, and the components present in the system can aggregate, interact, and chemically react with each other. However, if the less reactive polyurethane / acrylic resin and the colorant are introduced first, a so-called metastable state is formed due to the slow interaction between the two. Therefore, even if a highly reactive additive is added later, a large amount of external energy is required to transition from the metastable state to a state in which the additive is dominant, thus reducing the interaction of the highly reactive additive with the colorant. As a result, it is thought that the morphological changes of the various polymer chains present in the solution are reduced. The viscosity change rate (%) is calculated by the method described in the Examples section.

[0031] The masterbatch composition of this embodiment may contain other binder resins in addition to the colorant, polyurethane resin and / or (meth)acrylic resin, organic solvent, and optional additive components. That is, the masterbatch composition of this disclosure may be defined as containing a colorant, a binder resin, and an organic solvent, and the binder resin may contain polyurethane resin and / or (meth)acrylic resin. In this specification, "binder resin" means a masterbatch composition, an ink, or a binding resin contained in an ink composition. Furthermore, the binder resin may be dissolved in a solvent or in an emulsion state. Accordingly, the binder resin must contain polyurethane resin and / or (meth)acrylic resin as components, and may optionally contain other binder resins other than the polyurethane resin and / or (meth)acrylic resin (hereinafter referred to as "other binder resins"). Optional additives in this embodiment include components other than the aforementioned additives (which may be referred to as other additives), such as colorant additives, pigment dispersants, surfactants other than the aforementioned pigment dispersants, dispersion resins for dispersing pigments, known bluing agents, and known stabilizers. Examples of the aforementioned colorant additives include the colorant additives described later. Examples of the aforementioned pigment dispersants include the pigment dispersants described later. Examples of the aforementioned dispersion resins for dispersing pigments include the dispersion resins described later. These optional additives may be included in the masterbatch composition or the ink composition, and these optional additives may, for example, be included as part of the colorant.

[0032] In the masterbatch composition of this embodiment, the proportion of polyurethane resin to the total binder resin contained in the masterbatch composition is preferably 0% by mass or more and 100% by mass or less. If the masterbatch composition contains polyurethane resin, the proportion of polyurethane resin to the total binder resin contained in the masterbatch composition is preferably 0% by mass or more and 98% by mass or less, more preferably 1% by mass or more and 95% by mass or less, and even more preferably 2% by mass or more and 90% by mass or less. In the masterbatch composition of this embodiment, the proportion of (meth)acrylic resin (solids) to the total binder resin (solids) contained in the masterbatch composition is preferably 0% by mass or more and 100% by mass or less. If the masterbatch composition contains (meth)acrylic resin, the proportion of (meth)acrylic resin (solids) to the total binder resin (solids) contained in the masterbatch composition is preferably 0% by mass or more and 98% by mass or less, more preferably 1% by mass or more and 95% by mass or less, and even more preferably 2% by mass or more and 90% by mass or less.

[0033] In the ink composition of this embodiment, the proportion of polyurethane resin (solids) to the total binder resin (solids) contained in the ink composition is preferably 0% by mass or more and 100% by mass or less. If the ink composition contains polyurethane resin, the proportion of polyurethane resin to the total binder resin contained in the ink composition is preferably 0% by mass or more and 98% by mass or less, more preferably 1% by mass or more and 95% by mass or less, and even more preferably 2% by mass or more and 90% by mass or less. In the ink composition of this embodiment, the proportion of (meth)acrylic resin (solids) to the total binder resin (solids) contained in the ink composition is preferably 0% by mass or more and 100% by mass or less. If the ink composition contains (meth)acrylic resin, the proportion of (meth)acrylic resin to the total binder resin contained in the ink composition is preferably 1% by mass or more and 95% by mass or less, more preferably 2% by mass or more and 93% by mass or less, and even more preferably 3% by mass or more and 90% by mass or less.

[0034] The components of the masterbatch composition or ink composition of this embodiment, namely the colorant, polyurethane resin and / or (meth)acrylic resin, organic solvent, additive, and other binder resins, will be described in detail below.

[0035] (Coloring agent) The coloring agent used in the masterbatch composition or ink composition of this embodiment preferably contains a pigment, and the pigment may be either a coloring pigment or a white pigment. If these pigments are not added, it can also be used for overcoat varnish applications. In this embodiment, the content of the coloring agent is preferably 1 to 50% by mass, more preferably 2 to 48% by mass, even more preferably 3 to 46% by mass, even more preferably 4 to 44% by mass, even more preferably 5 to 42% by mass, and particularly preferably 6 to 40% by mass, based on the total amount (100% by mass) of the masterbatch composition (solids). Setting the total content of the coloring agent in the masterbatch composition to the above range is preferable from the viewpoint of dispersibility. In this embodiment, the content of the coloring agent is preferably 1 to 50% by mass, more preferably 2 to 48% by mass, even more preferably 3 to 46% by mass, even more preferably 4 to 44% by mass, even more preferably 5 to 42% by mass, and particularly preferably 6 to 40% by mass, based on the total amount (100% by mass) of the ink composition (solids).

[0036] In this embodiment, pigments are preferred as colorants, and examples include inorganic pigments and organic pigments commonly used in inks, paints, and recording materials. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthancerone pigments, dianthaquinonyl pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, indanthrone pigments, and carbon black pigments. Other examples include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthal yellow, chromophthal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigobordeaux, thioindigomagenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments. Both unacidified and acidified pigments can be used. Specific examples of preferred organic pigments are given below. In the colorant of this embodiment, the pigment content relative to the total amount of colorant (100% by mass) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass. The colorant of this embodiment is preferably composed of a pigment and a colorant additive. The aforementioned colorants may include, as needed, one or more colorant additives selected from the group consisting of co-used resins, extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, antioxidants, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, and solvents.

[0037] To stably disperse the colorant or pigment in an organic solvent, polyurethane resin or (meth)acrylic resin alone can be used for dispersion, but a pigment dispersant can also be used in combination to further stably disperse the colorant or pigment. As the pigment dispersant, surfactants such as anionic, nonionic, cationic, and amphoteric surfactants can be used. Examples include comb-structured polymer compounds obtained by adding polyester to polyethyleneimine, or alkylamine derivatives of α-olefin maleic acid polymers. Specifically, examples include the Solspers series (ZENECA), Ajisper series (Ajinomoto), and Homogenol series (Kao). In addition, the BYK series (BIK Chemie) and EFKA series (EFKA) can also be used as appropriate. From the viewpoint of storage stability of the ink, the dispersant is preferably included in the composition at a concentration of 0.05% by mass or more relative to the total mass of the composition, and from the viewpoint of lamination suitability, at a concentration of 5% by mass or less, and more preferably in the range of 0.1 to 2% by mass.

[0038] In the colorant of this embodiment, the content of the colorant additive relative to the total amount of colorant (100% by mass) is preferably 0% to 30% by mass, more preferably more than 0% by mass and 25% by mass or less, and even more preferably more than 0% by mass and 20% by mass or less. The pigment of this embodiment may be one or more selected from the group consisting of black pigment, blue pigment, green pigment, red pigment, purple pigment, yellow pigment, orange pigment, brown pigment, and white pigment.

[0039] Examples of the aforementioned black pigments include C.I. Pigment Black 1, C.I. Pigment Black 6, C.I. Pigment Black 7, C.I. Pigment Black 9, and C.I. Pigment Black 20.

[0040] Examples of the aforementioned blue pigments include C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:5, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 17:1, C.I. Pigment Blue 22, C.I. Pigment Blue 24:1, C.I. Pigment Blue 25, C.I. Pigment Blue 26, C.I. Pigment Blue 60, C.I. Pigment Blue 61, C.I. Pigment Blue 62, C.I. Pigment Blue 63, C. Examples include I. Pigment Blue 64, C.I. Pigment Blue 75, C.I. Pigment Blue 79, and C.I. Pigment Blue 80.

[0041] Examples of the aforementioned green pigments include C.I. Pigment Green 1, C.I. Pigment Green 4, C.I. Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 10, and C.I. Pigment Green 36.

[0042] Examples of the aforementioned red pigments include C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 20, C.I. Pigment Red 21, C. I. Pigment Red 22, C. I. Pigment Red 23, C. I. Pigment Red 31, C. I. Pigment Red 32, C. I. Pigment Red 38, C. I. Pigment Red 41, C. I. Pigment Red 43, C. I. Pigment Red 46, C. I. Pigment Red 48, C. I. Pigment Red 48:1, C. I. Pigment Red 48:2, C. I. Pigment Red 48:3, C. I. Pigment Red 48:4, C. I. Pigment Red 48:5, C. I. Pigment Red 48:6, C. I. Pigment Red 49, C. I. Pigment Red 49:1, C. I. Pigment Red 49:2, C.I. Pigment Red 49:3, C.I. Pigment Red 52, C.I. Pigment Red 52:1, C.I. Pigment Red 52:2, C.I. Pigment Red 53, C.I. Pigment Red 53:1, C.I. Pigment Red 53:2, C.I. Pigment Red 53:3, C.I. Pigment Red 54, C.I. Pigment Red 57, C.I. Pigment Red 57:1, C.I. Pigment Red 58, C.I. Pigment Red 58:1, C.I. Pigment Red 58:2, C.I. Pigment Red 58:3, C.I. Pigment Red 58:4, C.I. Pigment Red 60:1, C.I. Pigment Red 63, C.I. Pigment Red 63:1, C.I. Pigment Red 63:2, C.I. Pigment Red 63:3, C.I. Pigment Red 64:1, C.I. Pigment Red 68, C.I. Pigment Red 68, C.I. Pigment Red 81:1C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 89, C.I. Pigment Red 95, C.I. Pigment Red 112, C.I. Pigment Red 114, C.I. Pigment Red 119, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 136, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 147, C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 164, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 169, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 172, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 181, C.I. Pigment Red 182, C.I. Pigment Red 183, C.I. Pigment Red 184, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 188, C.I. Pigment Red 190, C.I. Pigment Red 192, C.I. Pigment Red 193, C.I. Pigment Red 194, C.I. Pigment Red 200, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 210, C.I. Pigment Red 211, C.I. Pigment Red 213, C.I. Pigment Red 214, C.I. Pigment Red 216, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 223, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 237, C.I. Pigment Red 238, C.I. Pigment Red 239, C.I. Pigment Red 240, C.I. Pigment Red 242,C.I. Pigment Red 245, C.I. Pigment Red 247, C.I. Pigment Red 248, C.I. Pigment Red 251, C.I. Pigment Red 253, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 256, C.I. Pigment Red 257, C.I. Pigment Red 258, C.I. Pigment Red 260, C.I. Pigment Red 262, C.I. Pigment Red 263, C.I. Pigment Red 264, C.I. Pigment Red 266, C.I. Pigment Red 268, C.I. Pigment Red 269, C.I. Examples include Pigment Red 270, C.I. Pigment Red 271, C.I. Pigment Red 272, C.I. Pigment Red 279, and others.

[0043] Examples of the aforementioned purple pigments include C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 3:1, C.I. Pigment Violet 3:3, C.I. Pigment Violet 5:1, C.I. Pigment Violet 13, C.I. Pigment Violet 19 (γ-type, β-type), C.I. Pigment Violet 23, C.I. Pigment Violet 25, C.I. Pigment Violet 27, C.I. Pigment Violet 29, C.I. Pigment Violet 31, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 37, C.I. Examples include Pigment Violet 38, C.I. Pigment Violet 42, C.I. Pigment Violet 50, and others.

[0044] Examples of the aforementioned yellow pigments include C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, Pigment Yellow 17, C.I. Pigment Yellow 24, C.I. Pigment Yellow 42, C.I. Pigment Yellow 55, C.I. Pigment Yellow 62, C.I. Pigment Yellow 65, C.I. Pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 120, Pigment Yellow 125, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C. Examples include I. Pigment Yellow 174, C. I. Pigment Yellow 180, C. I. Pigment Yellow 185, and C. I. Pigment Yellow 213.

[0045] Examples of the aforementioned orange pigments include C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 16, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 37, C.I. Pigment Orange 38, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 71, or C.I. Pigment Orange 74.

[0046] Examples of the brown pigments include C.I. Pigment Brown 23, C.I. Pigment Brown 25, or C.I. Pigment Brown 26.

[0047] Among them, suitable pigments include: C.I. Pigment Black 7 as a black pigment; C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6 as indigo pigments; C.I. Pigment Green 7 as a green pigment; and C.I. Pigment Red 57:1, C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 146, C.I. Pigment Red 242, C.I. Pigment Red 185, C.I. Examples include Pigment Red 122, C.I. Pigment Red 178, C.I. Pigment Red 149, C.I. Pigment Red 144, C.I. Pigment Red 166, as purple pigments C.I. Pigment Violet 23, C.I. Pigment Violet 37, as yellow pigments C.I. Pigment Yellow 83, C.I. Pigment Yellow 14, C.I. Pigment Yellow 180, C.I. Pigment Yellow 139, as orange pigments C.I. Pigment Orange 38, C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Orange 64, etc. It is preferable to use at least one or more selected from this group.

[0048] Examples of the inorganic pigments include white inorganic pigments such as titanium dioxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, litsubone, antimony white, and gypsum. Titanium dioxide is particularly preferred as a suitable inorganic pigment. Titanium dioxide is preferred because it exhibits a white color, and is desirable in terms of coloring power, opacity, chemical resistance, and weather resistance. From the viewpoint of printing performance, titanium dioxide treated with silica and / or alumina is preferred.

[0049] Examples of inorganic pigments other than white include carbon black, aluminum particles, mica, bronze powder, chrome vermilion, lead yellow, cadmium yellow, cadmium red, ultramarine, Prussian blue, red iron oxide, yellow iron oxide, iron black, and zircon. Aluminum is available in powder or paste form, but it is preferable to use it in paste form for ease of handling and safety reasons. Whether to use leafing or non-leafing aluminum is selected appropriately from the viewpoint of brightness and density.

[0050] In the masterbatch composition of this embodiment, the pigment (solid content) content is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass, relative to the total amount (100% by mass) of the masterbatch composition (solid content). In the ink composition of this embodiment, the pigment (solid content) content is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass, relative to the total amount (100% by mass) of the ink composition (solid content).

[0051] The amount of the pigment is preferably sufficient to ensure the concentration and coloring power of the masterbatch composition or ink composition. Specifically, the pigment is preferably present in an amount of 10 to 90% by mass in terms of solid weight ratio in the ink composition. The colorants can be used alone or in combination of two or more types.

[0052] (Polyurethane resin and / or (meth)acrylic resin) In the masterbatch composition or ink composition of this embodiment, it is preferable to contain one or more selected from the group consisting of polyurethane resin and (meth)acrylic resin. When lamination strength is important, it is preferable to select polyurethane resin; when blocking resistance is important, it is preferable to select (meth)acrylic resin; and when a balance between lamination strength and blocking resistance is important, it is preferable to mix polyurethane resin and (meth)acrylic resin.

[0053] In the masterbatch composition of this embodiment, the content of polyurethane resin and / or (meth)acrylic resin (solids) is preferably 5 to 30% by mass, more preferably 7 to 28% by mass, and even more preferably 9 to 26% by mass, based on the total solids content (100% by mass) of the masterbatch composition. In the ink composition of this embodiment, the content of polyurethane resin and / or (meth)acrylic resin (solids) is preferably 5 to 30% by mass, more preferably 7 to 28% by mass, and even more preferably 9 to 26% by mass, based on the total solids content (100% by mass) of the ink composition. In the masterbatch composition of this embodiment, the total content of polyurethane resin (solids) and (meth)acrylic resin (solids) based on the total solids content (100% by mass) of the masterbatch composition is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, and even more preferably 15 to 80% by mass. In the ink composition of this embodiment, the total content of polyurethane resin and (meth)acrylic resin relative to the total solid content (100% by mass) of the ink composition is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, and even more preferably 15 to 80% by mass.

[0054] <Polyurethane Resin> In this embodiment, the masterbatch composition preferably contains polyurethane resin when lamination suitability is a priority. The inclusion of polyurethane resin in the masterbatch composition improves the lamination strength. Furthermore, the polyurethane resin may have urea bonds. This provides good resistance to boiling, retorting, and blocking.

[0055] The masterbatch composition of this embodiment preferably contains a polyurethane resin having a number average molecular weight of 1,000 to 100,000. The polyurethane resin is a compound that uses an isocyanate compound and a polyol component as reaction raw materials (1). In other words, the polyurethane resin in this embodiment has a structure in which constituent units derived from the isocyanate compound and constituent units derived from the polyol component are directly or indirectly chemically bonded. The polyurethane resin has the function of improving the adhesion of ink as a binder resin and can also function as a pigment dispersion resin. The polyurethane resin is a resin having urethane bonds, and only needs to have a number average molecular weight of 1,000 to 100,000, and may optionally have urea bonds (-NH-C(=O)-NH-). As will be described later, the polyurethane resin may be a mixture of multiple types of polyurethane resins. In this specification, "constituent unit" refers to a repeating unit of the chemical structure formed during reaction or polymerization when synthesizing the polyurethane resin.

[0056] The polyurethane resin of this embodiment is preferably a compound in which an isocyanate compound and a polyol component (for example, a polyester polyol compound, a polyether polyol compound, and a polyol compound (1)) are used as reaction raw materials (1). After describing the components of the reaction raw materials (1) of the polyurethane resin (isocyanate compound and polyol component), a preferred form of the polyurethane resin will be described.

[0057] <<Isocyanate Compound>> The reaction raw material (1) of the polyurethane resin in this embodiment contains an isocyanate compound. The isocyanate compound used in the polyurethane resin in the masterbatch composition of this embodiment is preferably a compound having two or more isocyanate groups, and a diisocyanate compound is more preferably a diisocyanate compound. Examples of such isocyanate compounds include various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc., which are commonly used in the production of known polyurethane resins. The isocyanate compound of this embodiment is the following general formula (i): (In the above general formula (i), L １ and L ２ Each of these independently represents a single bond or an alkylene group with 1 to 5 carbon atoms, M １ represents a divalent organic group. ) It is preferable to represent it as . In the above general formula (i), L １ It is preferable that L is a single bond or an alkylene group having 1 to 3 carbon atoms. In the above general formula (i), ２ The is preferably a single bond or an alkylene group having 1 to 3 carbon atoms. In the above general formula (i), the divalent organic group preferably has 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 17 carbon atoms. "Organic group" means a group having 1 or more carbon atoms, and is preferably a hydrocarbon group having 1 to 20 carbon atoms. The above divalent organic group is preferably an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 1 to 20 carbon atoms, an alkylene oxy group having 1 to 20 carbon atoms, or an arylene group having 6 to 18 carbon atoms. Furthermore, one or more non-adjacent -CH groups in the alkylene group, alkenylene group, alkylene oxy group, or arylene group. ２ - may be replaced with -O-, -COO-, or -OCO-. In the above general formula (i), M １The alkylene group having 3 to 12 carbon atoms is preferred, excluding the number of carbon atoms of the substituent. Specific examples of the isocyanate compounds of this embodiment include, for example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylu isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples include diisocyanates, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and dimer diisocyanates obtained by converting the carboxyl groups of dimer acids to isocyanate groups. These isocyanate compounds can be used individually or in combination of two or more.

[0058] In the polyurethane resin reaction material (1) of this embodiment, the proportion of the isocyanate compound is preferably 1% to 40% by mass, and more preferably 5% to 30% by mass, based on the total amount (100% by mass) of the reaction material (1). Furthermore, the content of constituent units of the isocyanate compound in the polyurethane resin is preferably in the range of 1% to 40% by mass, and more preferably in the range of 5% to 30% by mass, relative to the polyurethane resin. If the isocyanate compound is 1% by mass or more, a tough ink film can be obtained. If it is 40% by mass or less, a flexible ink film can be obtained.

[0059] (Polyol component) The polyol component in this embodiment is not particularly limited as long as it is a compound having two or more hydroxyl groups. Preferably, the polyol component in this embodiment is one or more selected from the group consisting of polyester polyol compounds, polyether polyol compounds, and polyol compound (1). The polyurethane resin in this embodiment has constituent units derived from the polyol component as constituent units. The constituent units derived from the polyol component may be one or more selected from the group consisting of constituent units derived from polyester polyol compounds, constituent units derived from polyether polyol compounds, and constituent units derived from polyol compound (1). In the polyurethane resin of this embodiment, the content of constituent units of the polyol component relative to the total amount of polyurethane resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass. When the content of constituent units of the polyol component in the polyurethane resin is 30 to 70% by mass, the effect of improved substrate adhesion due to high flexibility is achieved.

[0060] <Polyester Polyol Compounds> The reaction raw material (1) of the polyurethane resin of this embodiment preferably contains a polyester polyol compound. That is, it is preferable that the polyurethane resin has constituent units derived from a polyol component, and that the constituent units derived from the polyol component contain constituent units derived from a polyester polyol compound (so-called polyester polyol compound residues). If necessary, the reaction raw material (1) may further contain one or more selected from the group consisting of a polyether polyol compound, a polyol compound (1), and a polyol compound (2) used in combination. In one embodiment of the polyurethane resin of this embodiment, when a polyester polyol compound and a polyether polyol compound are used as part of the reaction raw material (1), it is preferable that the mass proportion of the polyester polyol compound is large in the total mass of the polyester polyol compound and the polyether polyol compound. In the reaction raw material (1) of the polyurethane resin of this embodiment, the total proportion of the polyester polyol compound and the polyether polyol compound is preferably 40% to 99% by mass, and more preferably 50% to 95% by mass, relative to the total amount (100% by mass) of the reaction raw material (1). In the polyurethane resin reaction material (1) of this embodiment, the proportion of the polyester polyol compound is preferably 0% to 95% by mass, more preferably 40% to 95% by mass, and even more preferably 50% to 95% by mass, relative to the total amount (100% by mass) of the reaction material (1). That is, it is preferable that the total polyol component in the polyurethane resin has constituent units derived from the polyester polyol compound, as this improves the lamination strength. Furthermore, it is preferable that the constituent units derived from the polyether polyol compound further improve the dispersibility and fluidity of the ink, and also improve adhesion.

[0061] In this embodiment, when a polyester polyol compound and a polyether polyol compound are used as reaction raw materials (1), the mass ratio of the polyester polyol compound and the polyether polyol compound (polyester polyol compound: polyether polyol compound) in the polyol component (component having a structure with two or more hydroxyl groups) is preferably in the range of 45:55 to 100:0, more preferably in the range of 50:50 to 100:0, and even more preferably in the range of 55:45 to 99:1. If the mass ratio of the polyester polyol compound and the polyether polyol compound is in the range of 45:55 to 100:0, it is preferable to obtain a printed material that is less prone to blocking. If the mass ratio is in the range of 55:45 to 99:1, it is preferable to obtain an ink that is particularly excellent in lamination strength, adhesion, and ink dispersibility. Furthermore, when using the masterbatch composition or ink composition of this embodiment in combination with a polyvinyl butyral resin described later, good compatibility can be obtained if the mass ratio of the polyester polyol compound and the polyether polyol compound is within the range of 55:45 to 99:1, thus providing suitable storage stability and fluidity.

[0062] The polyester polyol compound of this embodiment is preferably a compound obtained by dehydration condensation or polymerization of a low molecular weight polyol and a polycarboxylic acid or an anhydride thereof. In other words, the polyester polyol compound of this embodiment is preferably a compound in which a low molecular weight polyol and a polycarboxylic acid or an anhydride thereof are used as reaction raw materials (2). The lamination strength of the polyester polyol compound can be further increased by introducing ester groups to increase the cohesive energy.

[0063] As the low molecular weight polyol mentioned above, various known compounds having two or more hydroxyl groups that are commonly used in the production of known polyester polyol compounds can be used. For example, one or more compounds may be used in combination as the polyester polyol compound. Specifically, as the low molecular weight polyol, for example, glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2- Branched glycols such as ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, and 2-methyl-1,8-octanediol can be used; glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, etc. can also be used.

[0064] As the polycarboxylic acid or its anhydride, various known polycarboxylic acids commonly used in the production of known polyester polyols can be used. In addition, one or more compounds may be used in combination as the polycarboxylic acid or its anhydride. Specifically, for example, polycarboxylic acids having 6 or fewer carbon atoms and 2 or more carboxyl groups, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and anhydrides of these acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and anhydrides of these acids; aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, sebacic acid, and dimer acid; tricarboxylic acids such as trimellitic acid and its anhydride; benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid and anhydrides of these acids can be used.

[0065] Furthermore, the polyester polyol compound may be any known polyester polyol commonly used in the production of polyurethane resins, such as cyclic ester compounds, including polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone), or one or more compounds may be used in combination.

[0066] The number average molecular weight of the polyester polyol compound is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 7,000, even more preferably in the range of 900 to 6,000, and still more preferably in the range of over 900 and 6,000 or less.

[0067] When a polyester polyol compound is used as the reaction raw material (1) for the polyurethane resin in this embodiment, the content of the constituent units of the polyester polyol compound is preferably in the range of 40% to 85% by mass, more preferably in the range of 50% to 80% by mass, relative to the polyurethane resin. When the polyester polyol compound is 40% by mass or more relative to the entire polyurethane resin, the solubility of the polyurethane resin (B) in ketone, ester, and alcohol-based solvents is ensured, and adhesion on the high-performance barrier film is good. Furthermore, the resolubility of the ink film in the solvent is good, improving the tone reproducibility of the printed material. When it is 85% by mass or less, the ink film has appropriate flexibility, making it easier to achieve good blocking resistance.

[0068] The hydroxyl value of the polyester polyol compound in this embodiment is preferably 15 mg KOH / g to 285 mg KOH / g, more preferably 18 mg KOH / g to 285 mg KOH / g, even more preferably 20 mg KOH / g to 165 mg KOH / g, and even more preferably 20 mg KOH / g to 115 mg KOH / g. When the hydroxyl value of the polyester polyol compound is within the above range, it is easier to control the urethane bond concentration above a predetermined value, which can further improve the laminate strength. In this specification, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of the sample is acetylated, and is measured in accordance with JIS K 0070.

[0069] <Polyether Polyol Compounds> The polyurethane resin of this embodiment may contain a polyether polyol compound as the reaction raw material (1). As the polyether polyol compound, which is an optional component of the reaction raw material (1), various polyether polyols commonly used in the production of known polyurethane resins can be used, and one or more types may be used in combination. For example, polyether polyols of polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, etc. Specifically, known and commonly used ones such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used. By including a polyether polyol, adhesion, especially on high-performance barrier films, is greatly improved, resulting in superior blocking resistance and lamination strength.

[0070] The number-average molecular weight of the polyether polyol compound is preferably 100 to 5000. If the number-average molecular weight of the polyether polyol is less than 100, the polyurethane resin film tends to harden, and its adhesion to the polyester film decreases. If the number-average molecular weight is greater than 3500, the resulting resin film tends to become brittle, and the blocking resistance of the ink film decreases.

[0071] In the polyurethane resin reaction material (1) of this embodiment, the proportion of the polyester polyol compound is preferably 0% to 95% by mass, more preferably 40% to 95% by mass, and even more preferably 50% to 95% by mass, based on the total amount (100% by mass) of the reaction material (1). When the reaction material (1) contains a polyether polyol compound, the constituent units of the polyether polyol compound are preferably contained in an amount of 1% to 40% by mass relative to the entire polyurethane resin. When the constituent units of the polyether polyol compound are 1% by mass or more relative to the entire polyurethane resin, the solubility of the polyurethane resin in ketone, ester, and alcohol-based solvents is ensured, and adhesion on the high-performance barrier film is improved. Furthermore, the resolubility of the ink film in the solvent is improved, and the tone reproducibility of printed materials is enhanced. When it is 40% by mass or less, the ink film has appropriate flexibility, making it easier to achieve good blocking resistance.

[0072] The reaction raw material (1) of the polyurethane resin in this embodiment may further contain a combined polyol as needed. As the combined polyol used as needed in the polyurethane resin used in the masterbatch composition of this embodiment, various known polyols commonly used in the production of polyurethane resins can be used, and one or more may be used in combination. Examples of the combined polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentae Examples include saturated or unsaturated low molecular weight polyols such as slitol (1); polycarbonate polyols obtained by reacting the low molecular weight polyols with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. (2); polybutadiene glycols (3); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (4); and acrylic polyols obtained by copolymerizing one or more hydroxyethyl acrylates, hydroxypropyl acrylates, hydroxybutyl acrylates, etc., or their corresponding methacrylic acid derivatives, etc., with, for example, acrylic acid, methacrylic acid, or their esters (4).

[0073] Furthermore, if the aforementioned combined polyol includes a polyol component (one or more compounds selected from the group consisting of polyester polyol compounds, polyether polyol compounds, and polyol compound (1)), the content of the polyol component (polyester polyol compound, polyether polyol compound, and polyol compound (1)) contained in the combined polyol shall also be calculated as being included in the mass of polyester polyol compounds, polyether polyol compounds, and polyol compound (1) in the polyol component of the polyurethane resin. In addition, the reaction raw material (1) of the polyurethane resin may contain amine compounds such as chain extenders. Examples of the amine compounds include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and amines having hydroxyl groups in their molecules, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyropyrethylenediamine, di-2-hydroxypyropyrethylenediamine, cyclohexylamine, di-2-hydroxypropylethylenediamine, and di-n-butylamine, as well as other dialkylamines. By including the above amine compounds in the reaction raw material (1) of the polyurethane resin, it becomes easier to introduce urea bonds into the polyurethane resin. Furthermore, because the urea bonds in the polyurethane resin have a low degree of rotational freedom due to their molecular structure, it becomes easier to ensure high rigidity of the entire composition. Therefore, the polyurethane resin of this embodiment, having both urethane bonds and urea bonds, is more likely to have improved rigidity and elongation performance.

[0074] The hydroxyl value of the polyether polyol compound in this embodiment is preferably 15 mg KOH / g to 285 mg KOH / g, more preferably 18 mg KOH / g to 285 mg KOH / g, even more preferably 20 mg KOH / g to 165 mg KOH / g, and even more preferably 20 mg KOH / g to 115 mg KOH / g. When the hydroxyl value of the polyether polyol compound is within the above range, it is easier to control the urethane bond concentration above a predetermined value, which can further improve the laminate strength.

[0075] <Polyol compound (1)> The polyol compound (1) of this embodiment preferably has a substructure represented by the following general formula (ii). (In the above general formula (ii), D １ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 15 carbon atoms, provided that the alkyl group contains one or more -CH groups. ２ - may be substituted with -O-, -COO-, or -OCO-, L ４ and L ５ Each of these independently represents a single bond or an alkylene group having 1 to 5 carbon atoms, provided that the alkylene group contains one or more -CH groups. ２ - may be substituted with -O-, -COO-, or -OCO-, L ３ Each of these independently represents a single bond or a group represented by the following general formula (a): (In the above general formula (a), L ６ represents a mezine group (-CH=) or a trivalent organic group, R １ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a monovalent aromatic group, while * represents M in general formula (ii). ２ The first symbol (*) represents a chemical bond with the second symbol (*), while the second symbol (*) represents a chemical bond with the OH (hydroxyl group) in general formula (ii). ２ Each of these independently represents a mezine group (-CH=), a trivalent alicyclic group with 3 to 15 carbon atoms, or a trivalent aromatic group, where nii is the number of repeating units and represents an integer of 2 or more. Note that in the above general formula (ii), * represents a bond with another atom.

[0076] In this embodiment, in the above general formula (ii), D １It is preferably a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. In the above general formula (ii), L ４ The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and a methylene group is particularly preferred. However, the alkylene group contains 1 or more -CH groups. ２ - may be replaced with -O-, -COO-, or -OCO-. In the above general formula (ii), L ５ The alkylene group is preferably a single bond or has 1 to 3 carbon atoms, and a single bond is more preferred. However, the alkylene group may contain 1 or more -CH ２ - may be replaced with -O-, -COO-, or -OCO-. In the above general formula (ii), L ３ It is preferable that L is a single bond or a group represented by the above general formula (a). ３ If L is a group represented by the above general formula (a), ６ It is preferable that it is a mezine group. And R １ It is preferably a monovalent aromatic group that is unsubstituted or has 1 to 4 hydrogen atoms substituted by a substituent, and more preferably a phenyl group, naphthyl group, phenalenyl group, phenantrenyl group, anthryl group, azlenyl group, indenyl group, indanyl group, or tetralinyl group that is unsubstituted or has 1 to 3 hydrogen atoms substituted by a substituent. The substituent is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a halogen atom. In the above general formula (ii), M ２ It is preferable that is a mezine group or a trivalent alicyclic group having 4 to 8 carbon atoms (for example, cyclohexane-triyl which may be substituted with an alkyl group having 1 to 3 carbon atoms). In the above general formula (ii), the trivalent organic group can be a group obtained by removing one arbitrary hydrogen atom from the above examples of "divalent organic groups". In the above general formula (ii), nii is preferably an integer between 2 and 1000, preferably an integer between 2 and 100, preferably an integer between 2 and 10, and more preferably an integer between 2 and 8.

[0077] The polyol compound (1) of this embodiment preferably has an aromatic ring, and more preferably has an aromatic ring in the general formula (ii). The presence of an aromatic ring in the polyol compound (1) makes it easier to exhibit effects such as improved pigment dispersibility, PEEL strength, and dry laminate strength. Another preferred polyol compound (1) is a polyol having an alkylene oxide skeleton, such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. A preferred embodiment of the polyol compound (1) of this embodiment is that the polyol compound (1) has a substructure represented by the general formula (ii), and L in the general formula (ii) ３ The group is represented by the above general formula (a), and R １ This represents a monovalent aromatic group. That is, the polyol compound (1) of this embodiment preferably has a substructure represented by the following general formula (ii-1). (In the above general formula (ii-1), D １ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 15 carbon atoms, provided that the alkyl group contains one or more -CH groups. ２ - may be substituted with -O-, -COO-, or -OCO-, L ４ and L ５ Each of these independently represents a single bond or an alkylene group with 1 to 5 carbon atoms, L ６ Each of these independently represents a mezine group (-CH=), and R １’ Each of these independently represents a monovalent aromatic group, M ２ Each of these independently represents a mezine group (-CH=), a trivalent alicyclic group with 3 to 15 carbon atoms, or a trivalent aromatic group, and nii represents the number of repeating units, an integer of 2 or more. Note that in the above general formula (ii-1), * represents a bond with another atom.

[0078] In the above general formula (ii-1), R １’It is preferable that the group is unsubstituted or has one to three hydrogen atoms substituted by substituents, and is a phenyl group, naphthyl group, phenalenyl group, phenantrenyl group, anthryl group, azlenyl group, or indenyl group. The other symbols of general formula (ii-1) are the same as those of general formula (ii).

[0079] A particularly preferred embodiment of the polyol compound (1) of this embodiment is that it has a substructure represented by the following general formula (ii-1.1). (In the above general formula (ii-1.1), D １ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 15 carbon atoms, provided that the alkyl group contains one or more -CH groups. ２ The - can be replaced with -O-, -COO-, or -OCO-, R ２ Each of these can be independently unsubstituted or substituted R ３ The substituent R represents a phenyl group, naphthyl group, or phenalenyl group, which may be substituted with 1 to 5 hydrogen atoms. ３ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a halogen atom, and nii is the number of repeating units, representing an integer of 2 or more. Note that in the above general formula (ii-1.1), * represents a bond with another atom.) In the above general formula (ii-1.1), D １ R is preferably a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. In the above general formula (ii-1.1), ２ Each of these can be independently unsubstituted or substituted R ５ The substituent R represents a phenyl group or a naphthyl group, which may be substituted with 1 to 3 hydrogen atoms. ５ This represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a halogen atom.

[0080] In this embodiment, the number-average molecular weight (Mn) of the polyol compound (1) is preferably 700 to 900. A number-average molecular weight (Mn) of 700 to 900 for the polyol compound (1) is preferable from the viewpoint of balancing adhesion to the film and blocking resistance. If the number-average molecular weight of the polyol compound (1) is too small, the cured polyurethane resin film tends to become hard, reducing its adhesion to the film. On the other hand, if the number-average molecular weight is too large, the cured polyurethane resin film tends to become brittle, reducing the blocking resistance of the ink film. In this specification, the number-average molecular weight and weight-average molecular weight are the values ​​measured by the gel permeation chromatography (GPC) method described in the Examples section below.

[0081] The hydroxyl value of the polyol compound (1) in this embodiment is preferably 80 to 450 mg KOH / g, more preferably 100 to 400 mg KOH / g, and even more preferably 105 to 385 mg KOH / g. When the hydroxyl value of the polyol compound (1) is within the above range, it is easier to control the urethane bond concentration to a predetermined value or higher, which can further improve the laminate strength.

[0082] In the reaction raw material (1) of the polyurethane resin of this embodiment, the proportion of polyol compound (1) is preferably 0% to 99% by mass, more preferably 60% to 99% by mass, and even more preferably 65% ​​to 95% by mass, relative to the total amount (100% by mass) of the reaction raw material (1). That is, it is preferable that the polyol structure of the polyurethane resin has constituent units derived from polyol compound (1), as this improves the lamination strength. Furthermore, it is preferable that the polyurethane resin further contains constituent units derived from polyol components used in combination as needed, as this improves the dispersibility and fluidity of the ink and also improves adhesion. When polyol compound (1) is used as the reaction raw material (1) of the polyurethane resin of this embodiment, the content of constituent units of polyol compound (1) (constituent units derived from polyol compound (1), so-called polyol compound (1) residues) is preferably in the range of 60% to 99% by mass, and more preferably 65% ​​to 95% by mass, relative to the total amount of the polyurethane resin. When the content of the constituent units of polyol compound (1) relative to the entire polyurethane resin is 60% by mass or more, the solubility of the polyurethane resin in ketone, ester, and alcohol-based solvents is ensured, and adhesion on high-performance barrier films is improved. Furthermore, the resolubility of the ink film in these solvents is improved, and the tone reproduction of printed materials is enhanced. If the content is 99% by mass or less, the ink film has appropriate flexibility, which tends to result in good blocking resistance.

[0083] <Preferred Form of Polyol Component> In the polyurethane resin of this embodiment, the reaction raw material (1) may contain a biomass-derived raw material. The polyurethane resin of this embodiment is preferably a resin in which the reaction raw material (1) is an isocyanate compound and a polyol component (for example, one or more selected from the group consisting of polyester polyol compounds, polyether polyol compounds, and polyol compounds (1)). In the reaction raw material (1), the biomass may be any material. Preferably, at least one component or raw material constituting one or more selected from the group consisting of polyester polyol compounds, polyether polyol compounds, and polyol compounds (1) is biomass. More specifically, "at least one or more raw materials constituting the polyester polyol compound is biomass" means that at least a portion of the total carbon atoms constituting the polyester polyol compound include carbon atoms derived from biomass. Furthermore, if the polyester polyol compound is a compound obtained by dehydration condensation or polymerization of a low molecular weight polyol and a polycarboxylic acid or its anhydride, then the low molecular weight polyol and / or polycarboxylic acid or its anhydride is considered to be biomass (in other words, the total carbon atoms in the low molecular weight polyol and / or polycarboxylic acid or its anhydride contain carbon atoms derived from biomass). Similarly, if at least one component or raw material constituting a polyether polyol compound is biomass, then at least a portion of the total carbon atoms constituting the polyether polyol compound contains carbon atoms derived from biomass. Note that biomass refers to organic resources produced from plants and animals that can be recycled into energy or matter (for example, agricultural, forestry, and fishery products or parts thereof, rice straw, rice husks, food waste, livestock excrement, or wood chips, etc.), and excludes fossil fuels such as petroleum and coal. For example, if a polyester polyol compound is composed of biomass, it is preferable that the polycarboxylic acid or its anhydride, which is the raw material for the polyester polyol compound, contains carbon atoms derived from biomass.Examples of polycarboxylic acids containing carbon atoms derived from biomass include adipic acid (e.g., adipic acid obtained using microorganisms, see International Publication No. 2012 / 137771), azelaic acid (e.g., azelaic acid obtained by ozonolysis of oleic acid isolated from olive oil), sebacic acid (e.g., sebacic acid obtained by alkali treatment of ricinoleic acid obtained from castor oil at high temperature, see Japanese Patent Publication No. 2001-511809), dodecanedicarboxylic acid, maleic anhydride (e.g., maleic anhydride obtained by the method of International Publication No. 2016 / 198744), fumaric acid (e.g., Biomass-derived raw materials can include fumaric acid obtained from the cob of corn (see International Publication No. 2011 / 059013), succinic acid (obtained by hydrogenating the fumaric acid), 1,4-butanediol (obtained by hydrogenating the fumaric acid), 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid (obtained by the method described in International Publication No. 2014 / 043468 or Japanese Patent Publication No. 2019-507757), and anhydrides of these acids. These polybasic acids may be used individually or in combination of two or more. Various biomass-derived alcohols known as low molecular weight polyols may also be used. Furthermore, the polyether polyol compound itself or its raw materials may be biomass; for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., can be used. To obtain a more environmentally friendly ink, it is desirable to have a high proportion of biomass in the polyurethane resin. For example, in polyurethane resin, when biomass is used as the polyester polyol compound of the reaction raw material (1), it is preferable that the proportion of biomass-derived solid components in the polyester polyol compound be 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more.For example, if the polyester polyol compound is a compound obtained by dehydration condensation or polymerization using a low molecular weight polyol from biomass and / or a polycarboxylic acid from biomass or their anhydrides, the total content (solid component) of low molecular weight polyol residues from biomass and polycarboxylic acid residues from biomass or their anhydrides in the polyester polyol compound is preferably 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. The proportion of biomass-derived solid components in the polyester polyol compound can be calculated from the amount used.

[0084] The lower limit of the biomass carbon content (%) of the polyurethane resin (solids) in this embodiment is preferably 30% or more, 33% or more, 35% or more, 37% or more, 40% or more, 45% or more, 48% or more, and 50% or more, in that order. On the other hand, the upper limit of the biomass carbon content (%) is preferably 100% or less, 90% or less, 80% or less, 73% or less, and 68% or less, in that order. These upper and lower limits can be combined arbitrarily. For example, the preferred range of biomass carbon content (%) for the polyurethane resin (solids) is preferably 30% or more, more preferably 30% to 90%, even more preferably 32% to 80%, and even more preferably 42% to 73%. When the biomass carbon content (%) of the polyurethane resin is 10% or more, it can exhibit the effect of reducing environmental impact. The lower limit of the biomass carbon content (%) of the masterbatch composition (solids) or ink composition (solids) of this embodiment is preferably 30% or more, 33% or more, 35% or more, 37% or more, 40% or more, 45% or more, 48% or more, and 50% or more, in that order. On the other hand, the upper limit of the biomass carbon content (%) is preferably 100% or less, 90% or less, 80% or less, 73% or less, and 68% or less, in that order. The upper and lower limits can be arbitrarily combined. For example, the range of biomass carbon content (%) of a preferred masterbatch composition (solids) or ink composition (solids) is preferably 30% or more, more preferably 30% or more and 90% or less, even more preferably 32% or more and 80% or less, and even more preferably 42% or more and 73% or less. In this specification, "biomass carbon content (%)" refers to radioactive carbon ( １４ The correction value is obtained by multiplying the content ratio (pMC%) of C) by the correction ratio of 0.93, and if the correction value is 100% or more, it is considered to be 100%. Radioactive carbon in this specification ( １４ The content ratio (pMC%) of C) indicates the carbon concentration (mass ratio) of biomass-derived components and is related to the so-called biomass blending ratio. More specifically, radiocarbon (in accordance with ASTM-D6866 (especially ASTM-D6866 B method) １４ C) Radiocarbon obtained by the measurement method ( １４This is the value of the content ratio of C). Radioactive carbon ( １４ C) has a half-life of 5730 years and nitrogen ( １４ It is known that it has the property of undergoing radioactive decay into N). And, on Earth, radioactive carbon ( １４ C) is carbon dioxide １４ CO ２ After being oxidized and dispersed into the atmosphere, it is taken up by plants and animals through the food chain, and then disappears according to its half-life while circulating in the environment through the food chain. Therefore, radioactive carbon ( １４ C) The measurement method is that fossil fuels are radiocarbon ( １４ C) substantially free of and biomass (or biological)-derived carbon is radioactive carbon in the atmosphere during the period of growth ( １４ It utilizes the fact that C) absorbs radioactive carbon in the carbon contained in biomass (or living organisms) １４ C) Radiocarbon from the ratio ( １４ This is a method for estimating the content ratio (pMC%) of C). Therefore, radioactive carbon ( １４ The higher the content ratio (pMC%) of C), the less fossil fuels are used, and the greater the effect of reducing the environmental burden. Therefore, radioactive carbon ( １４ The content ratio (pMC%) of C) is related to an index indicating the blending ratio of biomass, which is a renewable, bio-derived organic resource (= biomass carbon content (%)). The radioactive carbon contained in the total carbon atoms in the polyurethane resin (solids), masterbatch composition (solids), and ink composition (solids) of this embodiment ( １４ By measuring the proportion of C), the proportion of biomass-derived carbon can be calculated. In this disclosure, using the method described in the Examples section below, the radioactive carbon of polyurethane resin (solids), masterbatch composition (solids), and ink composition (solids) can be calculated using the following formulas (3) to (5). １４ The content ratio (pMC%) of C) is calculated. Then, as shown in the formula (6) below, the radioactive carbon content of polyurethane resin (solids), masterbatch composition (solids), and ink composition (solids) is calculated. １４The content ratio (pMC%) of C) is multiplied by 0.93, and the value obtained by taking into account the influence of atmospheric nuclear tests from 1950 to the present is defined as the biomass carbon content (%). [Mathematical formula (3)]: Radiocarbon ( １４ C) content ratio (pMC%) = [{radiocarbon in polyurethane resin (solid content) ( １４ C) ÷ carbon in polyurethane resin (B) (solid content) ( １２ C)} / {radiocarbon in standard substance ( １４ C) / carbon in standard substance ( １２ C)} × 100] [Mathematical formula (4)]: Radiocarbon ( １４ C) content ratio (pMC%) = [{radiocarbon in masterbatch composition (solid content) ( １４ C) ÷ carbon in masterbatch composition (solid content) ( １２ C)} / {radiocarbon in standard substance ( １４ C) / carbon in standard substance ( １２ C)} × 100] [Mathematical formula (5)]: Radiocarbon ( １４ C) content ratio (pMC%) = [{radiocarbon in ink composition (solid content) ( １４ C) ÷ carbon in ink composition (solid content) ( １２ C)} / {radiocarbon in standard substance ( １４ C) / carbon in standard substance ( １２ C)} × 100] (In the above mathematical formulas (3) to (5), the standard substance used is oxalic acid (SRM4990C) supplied by the National Institute of Standards and Technology as a standard substance for dating methods, which is converted to graphite by the same pretreatment method as that for graphite for measurement described in the Examples section below.) [Mathematical formula (6)]: Biomass carbon content (%) = radiocarbon calculated from the above mathematical formulas (3) to (5) ( １４ C) content ratio (pMC%) × 0.93 It should be noted that, under the influence of atmospheric nuclear tests after 1950, radiocarbon ( １４ C) artificially injected into the atmosphere has resulted in the observation that the amount of radiocarbon ( １４ C) is approximately 1.5 times the normal amount. However, this amount has been gradually decreasing over time, and the current value is around 107.5 (pMC%). Therefore, in the present disclosure, similarly to the standard of ASTM D6866, radiocarbon ( １４The biomass carbon content (%) is defined as the value obtained by multiplying the content ratio (pMC%) of C) by 0.93 (= 100 / 107.5). However, even when using the method with the above formula (4), there are cases where a value of 100% or more is calculated. Therefore, in this disclosure, similar to the ASTM standard, if the value of the biomass carbon content (%) is 100% or more, it is considered to be 100%. In this embodiment, radioactive carbon ( １４ The concentration of C) is measured by accelerator mass spectrometry (AMS), which combines a tandem accelerator and a mass spectrometer, to analyze the isotopes of carbon atoms contained in the sample (specifically, １２ C, １３ C, １４ C is one example.) is measured by physically separating the isotopes using an accelerator based on the weight difference of the atoms and measuring the abundance of each individual atom. The samples to be analyzed are polyurethane resin (solids), masterbatch composition (solids), and ink composition (solids), and pretreatment is required. Specifically, the carbon contained in these samples is oxidized and converted entirely into carbon dioxide. Furthermore, the obtained carbon dioxide is separated from water and nitrogen, and the carbon dioxide is reduced and converted into graphite, which is solid carbon. This obtained graphite is used as the sample for measurement, and Cs is added to the sample. ＋ Negative ions of carbon are generated by irradiating with positive ions, and the carbon ions are accelerated using a 3MV tandem accelerator, and the negative ions are converted to positive ions, and then a mass spectrometer is used to analyze them. １２ C ３＋ , １３ C ３＋ , １４ C ３＋ Separate the trajectory of the moving object, １４ C ３＋ The accelerator mass spectrometry method of this embodiment employs a measurement method using an electrostatic analyzer. Furthermore, the carbon isotopes contained in the graphite obtained from the pre-treated sample... １２ C, １３ C and １４ C is accelerated at the same speed, and its flight path is bent by the magnetic field of the mass spectrometry electromagnet. At that time, １２ C, １３C is on the inside, the heaviest １４ C flies along the outermost edge of the curve. Also, １２ C, １３ Because the amount of C is large, it is expressed as an electric current by a Faraday cup detector. １４ Each C atom is counted individually by an ionization chamber-type ion detector.

[0085] (Preferred Embodiment of Polyurethane Resin) The number-average molecular weight (Mn) of the polyurethane resin in this embodiment is preferably 1,000 to 100,000, and more preferably 1,200 to 70,000. A number-average molecular weight (Mn) of 1,000 to 100,000 of the polyurethane resin is preferable in terms of the blocking resistance of the ink composition, the strength and oil resistance of the printed film, and the gloss of the printed film. The polyurethane resin in this embodiment has the following general formula (I): (In the above general formula (I), R ３ and R ４ Each of the above general formulas (I) independently represents an aromatic group having 6 to 15 carbon atoms, and M represents a divalent organic group, preferably an aliphatic hydrocarbon group (alkylene group or alkenylene group) having 1 to 20 carbon atoms. In the above general formula (I), * represents a bond with another atom. It is preferable to have a substructure represented by the above general formula (I). By having a substructure represented by the above general formula (I), the polyurethane resin can form an ink layer with superior adhesion, blocking resistance, PEEL strength, and dry lamination strength. In the above general formula (I), R ３ and R ４ Each of these independently has 1 to 3 hydrogen atoms that are either unsubstituted or substituted with a substituent R. ５ The substituent R preferably represents a phenyl group or a naphthyl group, which may be substituted by the substituent R. ５ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a halogen atom. In the above general formula (I), M is preferably an alkylene group having 3 to 12 carbon atoms, without including the number of carbon atoms of the substituent.

[0086] (Properties of Polyurethane Resin) The urethane group concentration of the polyurethane resin in this embodiment is preferably 0.1 mmol / g or more, more preferably 0.1 mmol / g or more and 2.0 mmol / g or less, and even more preferably in the range of 0.2 mmol / g or more and 1.8 mmol / g or less. When the urethane group concentration is 0.1 mmol / g or more, the laminate strength is particularly excellent. The urethane group concentration can be calculated by the following formula (2). [Formula (2)]: Urethane group concentration = {(W １ ×OH １ +W ２ ×OH ２ +...+W ｉ ×OH ｉ ) × 1000} / (56100 × S １ In the above equation (2), the following applies to each: W １ : Weight of polyol component (1) OH １ : Hydroxyl value of polyol component (1) W ２ : Weight of polyol component (2) OH ２ : Hydroxyl value of polyol component (2) W ｉ : Weight of polyol component (i) OH ｉ : Hydroxyl value of polyol component (i) S １ : Weight of the solid content of the polyurethane resin In the above formula (2), polyol component (1), polyol component (2), polyol component (3)... polyol component (i) are all compounds included in the above polyol components (for example, one or more compounds selected from the group consisting of polyester polyol compounds, polyether polyol compounds, and polyol compound (1)). That is, when i types of polyol components are used as the reaction raw material (1) for the polyurethane resin, the numerator of the above formula (2) is the sum of the amount of each of the i types of polyol components and the hydroxyl value of each polyol component. The denominator of the above formula (2) is S, which is the weight of the solid content of the obtained polyurethane resin. １The value is obtained by multiplying by 56100. Furthermore, the polyurethane group concentration in this specification can be measured as follows. A polyurethane resin is obtained by solvent extraction from the masterbatch composition or ink composition of this embodiment. Then, the urethane bond concentration can be calculated by performing the following two analytical methods on a sample of the masterbatch composition, ink composition, or solvent-extracted polyurethane resin. In this specification, the calculation is performed using the charge ratio from the above formula (2). Analytical method 1: Perform NMR analysis and calculate the urethane group concentration from the integral value of the peak derived from the urethane bond. Analytical method 2: Perform NMR, GPC, and mass spectrometry to obtain information on the molecular weight, chemical structure, and content ratio of isocyanate compounds, polyol components, and amine compounds that constitute the polyurethane resin. Calculate the urethane group concentration from this composition information.

[0087] The amine value of the polyurethane resin in this embodiment is preferably in the range of 0.1 to 5.0 mgKOH / g, more preferably in the range of 0.2 to 4.5 mgKOH / g, and even more preferably in the range of 0.3 to 4.0 mgKOH / g. The method for calculating the above amine value is as described in the Examples section below, and is measured in accordance with JIS Test Method K 0070-1992.

[0088] The polyurethane resin of this embodiment may consist only of a resin having a substructure represented by general formula (I), or it may be a mixture containing a resin having a substructure represented by general formula (I). In this embodiment, the lower limit of the content of the resin having a substructure represented by general formula (I) relative to the total polyurethane resin (solids) (100% by mass) is preferably 0% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 32% by mass or more, 34% by mass or more, or 36% by mass or more. On the other hand, the upper limit of the content of the resin having a substructure represented by general formula (I) is preferably 100% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 78% by mass or less, or 74% by mass or less. The preferred range for the content of the polyurethane resin having a substructure represented by general formula (I) is, in order of preference, 0% to 100% by mass, 10% to 95% by mass, 20% to 90% by mass, and 32% to 80% by mass, relative to the total polyurethane resin (resin solids) (100% by mass). When the content of the resin having a substructure represented by general formula (I) is greater than 0% by mass and 100% by mass or less, a tough ink film, good adhesion, and PEEL strength can be obtained. The above upper and lower limits can be combined as appropriate. In this embodiment, the lower limit of the content of the resin (solids) having a substructure represented by general formula (I) relative to the total solids (100% by mass) of the ink composition is preferably 0% by mass or more, greater than 0% by mass, 1% by mass or more, 3% by mass or more, 5% by mass or more, 8% by mass or more, 12% by mass or more, or 15% by mass or more. On the other hand, the upper limit of the content of the resin having a substructure represented by general formula (I) is preferably 100% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 64% by mass or less, or 61% by mass or less. The range of the content of the polyurethane resin (solids) having a substructure represented by general formula (I) is preferably 0% by mass to 100% by mass, 1% by mass to 80% by mass, and 3% by mass to 64% by mass, in that order, relative to the total solids content (100% by mass) of the ink composition. The above upper and lower limits can be combined as appropriate.

[0089] <Method for Manufacturing Polyurethane Resin> The method for manufacturing the polyurethane resin in this embodiment is not particularly limited and may be manufactured by any method. The manufacturing of the polyurethane resin may be carried out in a solvent (a so-called prepolymer solvent) as needed, and a basic catalyst may also be used as needed.

[0090] The solvent is preferably an organic solvent, and examples of such solvents include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These solvents can be used individually or in combination of two or more. Furthermore, the amount of solvent used is preferably in the range of 0.1 to 5 times the total mass of the reaction raw materials (1) in order to achieve good reaction efficiency.

[0091] Examples of the basic catalysts include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc.; trioctylmethylammonium chloride, trio Examples include quaternary ammonium salts such as ctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistanoxane; organometallic compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. Furthermore, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used as the basic catalyst. These basic catalysts can be used individually or in combination of two or more.Furthermore, when using the basic catalyst, it may be used in the form of an aqueous solution of about 10% to 55% by mass, or in solid form.

[0092] <(meth)acrylic resin> The masterbatch composition of this embodiment preferably contains (meth)acrylic resin when blocking resistance is important. The masterbatch composition contains (meth)acrylic resin, which improves blocking resistance. The (meth)acrylic resin of this embodiment is not particularly limited as long as it is a polymer that mainly contains (meth)acrylic acid monomer units. The (meth)acrylic acid monomer units may be one or more monomer units selected from the group consisting of (meth)acrylic acid monomer units and (meth)acrylic acid ester monomer units. In this specification, "(meth)acrylic acid ester monomer units" refers to constituent units derived from (meth)acrylic acid ester monomers when (meth)acrylic acid ester monomers are (co)polymerized or graft polymerized, i.e., repeating units derived from (meth)acrylic acid ester monomers. Similarly, in this specification, "(meth)acrylic acid monomer unit" refers to a constituent unit derived from a (meth)acrylic acid monomer when a (meth)acrylic acid monomer is (co)polymerized or graft polymerized, i.e., a repeating unit derived from a (meth)acrylic acid ester monomer. Therefore, the (meth)acrylic resin of this embodiment includes (homo)polymers composed of one or two types of (meth)acrylic acid monomer units, (homo)polymers composed of one or more types of (meth)acrylic acid ester monomer units, and copolymers composed of one or two types of (meth)acrylic acid monomer units and one or more types of (meth)acrylic acid ester monomer units. Note that "(homo)polymer" includes both homopolymers composed of one type of monomer unit and polymers composed of two or more types of monomer units. Furthermore, the (homo)polymer and the copolymer may be random polymers, block polymers, or alternating polymers.

[0093] The term "main component" refers to a composition in which the monomer units of the main component have a content ratio of 50% by mass or more (for example, 65% by mass or more, more preferably 80% by mass or more) within the total monomer units. There is no particular upper limit to the blending ratio of monomers of the main component, but it is preferable to set it to 99.6% by mass or less (for example, less than 100% by mass, or substantially 100% by mass).

[0094] Suitable (meth)acrylic resins in this embodiment include (single) polymers composed of one or more (meth)acrylic acid ester monomer units, and copolymers composed of one or more (meth)acrylic acid monomer units and one or more (meth)acrylic acid ester monomer units. In the (meth)acrylic resin of this embodiment, the content of (meth)acrylic acid ester monomer units relative to the total amount (100% by mass) of the (meth)acrylic resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 15 to 85% by mass. When the content of (meth)acrylic acid ester monomer units contained in the (meth)acrylic resin is 15 to 85% by mass, the effect of improving blocking resistance is achieved.

[0095] In the (meth)acrylic resin of this embodiment, the content of (meth)acrylic acid monomer units relative to the total amount (100% by mass) of the (meth)acrylic resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 15 to 85% by mass. When the content of (meth)acrylic acid monomer units contained in the (meth)acrylic resin is 5 to 95% by mass, the effect of improving blocking resistance is achieved.

[0096] In this embodiment, examples of (meth)acrylic acid monomers that are precursors to (meth)acrylic acid monomer units include acrylic acid monomers and methacrylic acid monomers. Examples of (meth)acrylic acid ester monomers that are precursors to the (meth)acrylic acid ester monomer units include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, iso-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like. Here, "(meth)acrylate" refers to both acrylate and methacrylate. The polymerization method is not particularly limited, and products obtained by known bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc., can be used.

[0097] The (meth)acrylic resin of this embodiment preferably has a weight-average molecular weight (Mw) of 5,000 to 200,000, and more preferably in the range of 10,000 to 100,000.

[0098] The acid value of the (meth)acrylic resin in this embodiment is preferably 0.1 mg KOH / g or more and 100 mg KOH / g or less, more preferably 0.1 mg KOH / g or more and 90 mg KOH / g or less, and even more preferably 0.1 mg KOH / g or more and 80 mg KOH / g or less. By controlling the acid value of the (meth)acrylic resin within the above range, it becomes easier to control the acid value of the masterbatch composition or ink composition within a predetermined range, making it easier to obtain an ink composition that exhibits better storage stability and maintains better color development and low viscosity for a longer period of time.

[0099] In this embodiment, the content of (meth)acrylic resin (solids) is preferably 0 to 95% by mass with respect to the total solids content (100% by mass) of the masterbatch composition. Furthermore, if the masterbatch composition contains (meth)acrylic resin, the content of the (meth)acrylic resin is more preferably greater than 0% by mass and 90% by mass, even more preferably 10 to 90% by mass, even more preferably 10 to 85% by mass, even more preferably 10 to 80% by mass, and particularly preferably 15 to 75% by mass. Setting the total (meth)acrylic resin content of the masterbatch composition within the above range is preferable from the viewpoint of blocking resistance. In this embodiment, the content of (meth)acrylic resin (solids) is preferably 0 to 95% by mass with respect to the total solids content (100% by mass) of the ink composition. Furthermore, if the ink composition contains (meth)acrylic resin, the content of the (meth)acrylic resin is more preferably 0 to 90% by mass, even more preferably 10 to 90% by mass, even more preferably 10 to 85% by mass, even more preferably 10 to 80% by mass, and particularly preferably 15 to 75% by mass. Setting the total (meth)acrylic resin content of the ink composition within the above range is preferable from the viewpoint of blocking resistance.

[0100] (Organic Solvents) Various organic solvents can be used as the organic solvent in the masterbatch composition or ink composition of this embodiment. Preferably, one or more selected from the group consisting of aromatic organic solvents, ketone organic solvents, ester organic solvents, alcohol organic solvents, and glycol ether organic solvents is used. Examples of aromatic organic solvents include toluene and xylene. Examples of ketone organic solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of ester organic solvents include ethyl acetate, n-propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. The alcohol-based organic solvent is preferably an aliphatic alcohol with a boiling point of less than 160°C, for example, an alcohol having 1 to 15 carbon atoms. Specifically, examples include n-propanol, isopropanol, n-butanol, propylene glycol monomethyl ether, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, 2-methyl-2-butanol, isobutanol, 2-pentanol, and the like. The glycol ether-based organic solvent is preferably a glycol ether solvent with a boiling point of 160°C or less. For example, at least one selected from the group consisting of ethylene glycol ethers and propylene glycol ethers is included. As the ethylene glycol ethers, ethylene glycol monoalkyl ether is preferred, and as the propylene glycol ethers, propylene glycol monoalkyl ether is preferred. The alkyl ether group in the ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether preferably has 1 to 4 carbon atoms. Preferably, the ethylene glycol monoalkyl ether is ethylene glycol monopropyl ether or ethylene glycol mono(iso)propyl ether, and preferably the propylene glycol monoalkyl ether is propylene glycol monomethyl ether.The glycol ether-based organic solvent may be esterified, and examples include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These glycol ether-based organic solvents may be used individually or in combination of two or more. It is more preferable to use ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether in combination. Specific examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, and propylene glycol mono-n-propyl ether. The above organic solvents can be used individually or as a mixture of two or more of the exemplified organic solvents. In recent years, from the viewpoint of the working environment, it is preferable not to use aromatic organic solvents such as toluene and xylene, or ketone-based organic solvents.

[0101] The above organic solvent preferably contains the above ester-based organic solvent and alcohol-based organic solvent, and it is preferable to set the mass ratio so that ester-based organic solvent:alcohol-based organic solvent = 30:70 to 95:5. When the mass ratio of the organic solvent is within this range, an ink with excellent printability and blocking resistance can be obtained. The mass ratio is more preferably 40:60 to 90:10, and even more preferably 60:40 to 85:15. The content of the organic solvent in this embodiment is preferably 40 to 90% by mass of the entire masterbatch composition, more preferably 43 to 89% by mass, more preferably 45 to 85% by mass, and even more preferably 50 to 85% by mass. The content of the organic solvent in this embodiment is preferably 40 to 98% by mass of the entire ink composition, more preferably 45 to 90% by mass, more preferably 46 to 88% by mass, and even more preferably 49 to 85% by mass.

[0102] The masterbatch composition or ink composition of this embodiment may contain water as a volatile component along with the organic solvent. The water content is preferably less than 10% by mass of the total amount of the masterbatch composition. Similarly, the water content is preferably less than 10% by mass of the total amount of the ink composition. The addition of water allows for control of the ink's drying properties, and in gravure printing in particular, it enables the clean reproduction of the characteristic gradient areas with low ink transfer. Furthermore, the water content is particularly preferably in the range of 0.1 to 5% by mass of the total amount of the masterbatch composition. Similarly, a water content in the range of 0.5 to 5% by mass of the total amount of the ink composition is particularly preferable because it results in good printability. In addition, such water addition can reduce the amount of organic solvent used. Water may be added to the organic solvent beforehand to form a water-containing mixed solvent, or a specific amount of water may be added separately.

[0103] <Water> The masterbatch composition or ink composition of this embodiment may contain water as needed. If the masterbatch composition or ink composition contains water, the water content is preferably 0.1 to 10% by mass of the total masterbatch composition or ink composition. By containing a predetermined amount of water, the pigment dispersibility by the polyurethane resin or binder resin of the masterbatch composition or ink composition is improved, and printability such as highlight transferability, plate coverability, and trapping properties is improved.

[0104] When the masterbatch composition or ink composition of this embodiment contains water, the mixing ratio of water to the alcohol-based organic solvent and / or glycol ether-based organic solvent (mass of water:mass of alcohol-based organic solvent and / or glycol ether-based organic solvent) is preferably 95:5 to 5:95, more preferably 90:10 to 10:90, and even more preferably 80:20 to 20:80. When the masterbatch composition or ink composition of this embodiment contains water, the total content of water, the alcohol-based organic solvent and the glycol ether-based organic solvent is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, even more preferably 3 to 10% by mass, and particularly preferably 3 to 8% by mass, relative to the total amount of the masterbatch composition or ink composition.

[0105] <Other Binder Resins> In addition to polyurethane resin and / or (meth)acrylic resin, other binder resins that can be used in combination in the ink technology may be added as needed to the masterbatch composition or ink composition of this embodiment. The other binder resin may be a dispersion resin. Examples of other binder resins that can be used in combination with polyurethane resin and / or (meth)acrylic resin include vinyl acetate resin (e.g., including ethylene-vinyl acetate copolymer resin), vinyl acetate resin, chlorine-based resin (meaning a resin containing chlorine atoms, e.g., including vinyl chloride resin and vinyl chloride-vinyl acetate copolymer resin), polyamide resin, polyester resin, alkyd resin, rosin-based resin, maleic acid resin (e.g., including rosin-modified maleic acid resin), polyvinyl butyral-based resin, cellulose-based resin, ketone resin, epoxy resin, cycloplastic rubber, petroleum resin, etc. In particular, the ink composition of this embodiment may contain at least one binder resin selected from vinyl acetate resin, chlorine-based resin, polyester resin, polyamide resin, rosin-based resin, maleic acid resin (including rosin-modified maleic acid resin), polyvinyl butyral-based resin, and cellulose-based resin, which can improve blocking resistance and resolubility. In another embodiment, the ink composition of this embodiment contains a binder resin, a colorant, an organic solvent, and an additive, and the binder resin contains polyurethane resin and / or (meth)acrylic resin in an amount of more than 0% by mass and 100% by mass relative to the total amount of the binder resin, and preferably further contains at least one binder resin selected from the group consisting of chlorine-based resin, polyvinyl butyral-based resin, maleic acid resin, cellulose-based resin, polyester resin, and polyamide resin, if necessary. Furthermore, it is preferable from the viewpoint of reducing environmental impact that the ink composition of this disclosure does not contain chlorine-based resin. The other binder resins mentioned above can be used individually or in mixtures of two or more. The content of the aforementioned other binder resin is preferably 0 to 30% by mass relative to the entire ink composition.

[0106] On the other hand, in the masterbatch composition of this embodiment, it is preferable that it does not contain any acidic resins other than (meth)acrylic resin and acidic resin, from the viewpoint of the overall stability of the composition (for example, suppression of hydrolysis of other binder resins (e.g., resins having ester bonds) due to changes in pH, or a decrease in the dispersibility of pigments, etc.). For this reason, the masterbatch composition of this embodiment preferably contains at least one resin selected from vinyl acetate resin, chlorine-based resin, polyester resin, polyamide resin, polyvinyl butyral-based resin, and cellulose-based resin as a binder resin, and more preferably contains at least one resin selected from chlorine-based resin, polyester resin, polyvinyl butyral-based resin, and cellulose-based resin as a binder resin. In this specification, an acidic resin refers to a resin having a carboxylic acid group (-COOH) or an anhydride group thereof, other than a (meth)acrylic resin. More specifically, the acidic resin may have an acid value of 0.5 mg KOH / g or more and 500 mg KOH / g or less, a weight-average molecular weight (Mw) of 10,000 to 50,000, and may be a resin having a carboxylic acid group (-COOH) or its anhydride group. Specifically, the acidic resin is preferably one or more selected from the group consisting of alkyd resins, rosin-based resins, and maleic acid resins. In another embodiment, the masterbatch composition of this embodiment contains a binder resin, a colorant, and an organic solvent, and the binder resin contains more than 0% by mass and 100% by mass of polyurethane resin and / or (meth)acrylic resin relative to the total binder resin, and optionally further contains at least one resin selected from the group consisting of chlorine-based resins, polyvinyl butyral-based resins, and cellulose-based resins. The above other binder resins can be used alone or in a mixture of two or more. The content (solids) of the other binder resin is preferably 0.5 to 50% by mass, more preferably 1 to 45% by mass, more preferably 2 to 40% by mass, and even more preferably 3 to 40% by mass, based on the total solids (100% by mass) of the masterbatch composition. The polyester resin and the polyamide resin are not particularly limited, and known resins can be used.

[0107] <<Polyvinyl Butyral Resin>> The masterbatch composition or ink composition of this embodiment preferably further contains a polyvinyl butyral resin as a binder resin. The polyvinyl butyral resin has binding and dispersing properties as a binder resin, and since its constituent elements are only carbon atoms, hydrogen atoms, and oxygen atoms, it has the effect of reducing the environmental burden compared to vinyl chloride-vinyl acetate copolymer resins. Furthermore, in masterbatch compositions or ink compositions containing colorants such as pigments, when the pigment is dispersed by kneading with a polyvinyl butyral resin, a suitable group from among butyral groups, polyvinyl alcohol residues, or vinyl acetate residues is adsorbed onto the pigment, and steric hindrance occurs due to the bulky butyral groups. Therefore, using a polyurethane resin or acrylic resin in combination with a polyvinyl butyral resin can exhibit superior dispersion stability. As the polyvinyl butyral resin of this embodiment, there are no particular limitations, and any known resin can be used. Generally, as a polyvinyl butyral resin, a reaction product obtained by acetalizing polyvinyl alcohol with an aldehyde compound such as butyraldehyde using a known reaction can be used. The polyvinyl butyral resin of this embodiment has the following general formula (II): (In the above general formula (II), n4 and n5 are each independent integers of 1 or more, R ６ It is preferable that the substructure is represented by ) where R represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. In the above general formula (II), ６ R preferably represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, aryl groups, or aralkyl groups, and may be linear, branched, or cyclic. Among these, alkyl groups are preferred. Among these, R ６ A propyl group or an isopropyl group is more preferable. As mentioned above, the polyvinyl butyral resin of this embodiment is a resin that uses polyvinyl alcohol and an aldehyde compound as reaction raw materials. In this case, the aldehyde compound is R６ When expressed as -C(=O)H, R in the general formula (4) above ６ This is a hydrocarbon group derived from an aldehyde compound used in the synthesis of polyvinyl butyral resins.

[0108] The preferred polyvinyl butyral resin of this embodiment is preferably a resin having a substructure represented by the above general formula (II), a substructure represented by the following general formula (III), and a substructure represented by the following general formula (IV). (In the above general formula (III), n6 are each independent integers greater than or equal to 1, and R ７ (This represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) (In the above general formula (IV), n7 are each independent integers greater than or equal to 1.)

[0109] In the above general formula (III), R ７ R preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ７ For example, hydrogen atoms, methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, or tert-butyl groups are more preferred. Furthermore, when the polyvinyl butyral resin of this embodiment is represented as a resin having a substructure represented by the above general formula (II), a substructure represented by the following general formula (III), and a substructure represented by the above general formula (IV), the content of the substructure represented by the above general formula (III) relative to the total amount of the polyvinyl butyral resin is preferably 12% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. By setting the content of the substructure represented by the above general formula (III) in the polyvinyl butyral resin within the above range, an ink layer with an excellent balance of fluidity and dispersibility can be obtained.

[0110] The weight-average molecular weight of the polyvinyl butyral resin in this embodiment is preferably 5,000 to 150,000, more preferably 6,000 to 100,000, and even more preferably 7,000 to 50,000. By setting the weight-average molecular weight of the polyvinyl butyral resin within the above range, excellent curability is achieved, and both the strength of the coating film and appropriate flexibility can be obtained. Furthermore, polyvinyl butyral resins with a weight-average molecular weight of 5,000 to 150,000 are readily available, and by using such a polyvinyl butyral resin, an ink layer with an excellent balance of fluidity and dispersibility can be obtained.

[0111] The glass transition temperature (hereinafter sometimes referred to as Tg) of the polyvinyl butyral resin in this embodiment is preferably in the range of 50°C to 120°C, more preferably in the range of 55°C to 115°C, and more preferably in the range of 60°C to 110°C. In the present invention, the glass transition temperature is obtained by measurement using a differential scanning calorimeter.

[0112] The hydroxyl value of the polyvinyl butyral resin in this embodiment is preferably in the range of 10 to 40% by mass, and more preferably in the range of 15% to 30% by mass. By setting the amount of hydroxyl groups in the polyvinyl butyral resin within the above range, an ink layer with an excellent balance of fluidity and dispersibility can be obtained. The amount of hydroxyl groups refers to the amount of the substructure represented by the above general formula (IV) relative to the total amount of the polyvinyl butyral resin.

[0113] The amount of acetyl groups in the polyvinyl butyral resin is preferably 8% by mass or less, and more preferably 5% by mass or less. By setting the amount of acetyl groups in the polyvinyl butyral resin within the above range, an ink layer with an excellent balance of fluidity and dispersibility can be obtained. The amount of acetyl groups refers to the amount of R in the substructure represented by the general formula (III) above. ７ When the substructure is a methyl group, it is called an acetyl group, and the amount of that acetyl group is the content relative to the total amount of polyvinyl butyral resin.

[0114] The content (solids) of polyvinyl butyral resin is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and most preferably 3 to 20% by mass, relative to the total solids (100% by mass) of the masterbatch composition. By setting the content of polyvinyl butyral resin to 3 to 20% by mass, the effect of improving pigment dispersibility can be achieved. The content (solids) of polyvinyl butyral resin is preferably 0.1 to 5% by mass, more preferably 0.1 to 4.0% by mass, and most preferably 0.2 to 3.0% by mass, relative to the total solids (100% by mass) of the ink composition. Adding a total of 0.1% by mass or more of polyvinyl butyral resin tends to maintain the adhesion and transferability of the ink film, while keeping the total at 5% by mass or less can maintain the lamination strength of the ink. Furthermore, the lower limit of the solid content mass ratio in the ink composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and most preferably 0.3% by mass or more. Also, the upper limit of the solid content mass ratio in the ink is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0115] <<Maleic Acid Resin>> In this embodiment, a rosin-modified maleic acid resin is preferred. The rosin-modified maleic acid resin is an alkyd resin obtained by reacting a polyhydric alcohol such as glycerin, pentaerythritol, or ethylene glycol with an adduct formed by the Diels-Alder reaction of rosin and maleic acid. The acid value is determined by the ratio of the polyhydric alcohol reacted with the rosin-maleic acid adduct and the degree of esterification. In addition to polyhydric alcohols, polybasic acids may also be used to form a structure in which a long-chain alkyd resin is bonded to a rosin skeleton.

[0116] Examples of polyhydric alcohols used to react with the rosin and maleic acid adduct include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol. Polybasic acids used as raw materials for alkyd resins along with these polyhydric alcohols include phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, and sebacic acid.

[0117] Furthermore, for example, a compound having a carbon-carbon unsaturated double bond, such as maleic acid, may be used as a raw material for the above-mentioned alkyd resin, and a styrene monomer may be reacted with it to produce a rosin-modified styrene-maleic acid resin, which is also included in rosin-modified maleic acid resins.

[0118] The maleic acid resin content (solids) is preferably 0.1 to 15% by mass, more preferably 0.2 to 15% by mass, and most preferably 0.3 to 15% by mass, relative to the total solids content (100% by mass) of the masterbatch composition. By setting the maleic acid resin content to a range of 0.3 to 15% by mass, an effect of improving deinking properties can be achieved. The maleic acid resin content (solids) is preferably 0.1 to 5% by mass, more preferably 0.1 to 4.0% by mass, and most preferably 0.2 to 3.0% by mass, relative to the total solids content (100% by mass) of the ink composition. By setting the maleic acid resin content to a range of 0.3 to 3.0% by mass, an effect of good adhesion to aluminum foil and metal vapor-deposited films can be achieved.

[0119] <<Cellulose-based resins>> Examples of the above-mentioned cellulose-based resins include cellulose ester resins such as cellulose acetate propionate, cellulose acetate butyrate, and other cellulose ester resins; nitrocellulose (also called nitrated cotton); hydroxyalkylcellulose; and carboxyalkylcellulose. The cellulose ester resin preferably has an alkyl group, and examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and hexyl groups, and the alkyl group may also have substituents. Among the above-mentioned cellulose-based resins, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferred, and cellulose acetate propionate and cellulose acetate butyrate are particularly preferred. The molecular weight of the cellulose-based resin is preferably 5,000 to 200,000 by weight average molecular weight, and more preferably 10,000 to 50,000. Furthermore, it is more preferable that the glass transition temperature is 120°C to 180°C. The combined use of polyurethane resin in this embodiment is expected to improve blocking resistance, scratch resistance, or other properties of the ink film. Nitrocellulose (nitrated cotton) is preferably obtained as a nitrate ester by reacting natural cellulose with nitric acid, in which three hydroxyl groups in the six-membered ring of the anhydrous glucopyranose group in natural cellulose are replaced with nitrate groups.

[0120] The content (solids) of cellulose-based resin is preferably 0.1 to 20% by mass, more preferably 0.1 to 18% by mass, and most preferably 0.1 to 15% by mass, based on the total solids (100% by mass) of the masterbatch composition. By setting the content of cellulose-based resin in the range of 0.1 to 15% by mass, an anti-blocking effect can be achieved. The content (solids) of cellulose-based resin is preferably 0.1 to 5% by mass, more preferably 0.1 to 4.0% by mass, and most preferably 0.2 to 3.0% by mass, based on the total solids (100% by mass) of the ink composition. By setting the content of cellulose-based resin in the range of 0.3 to 3.0% by mass, an anti-blocking effect can be achieved.

[0121] <Chlorine-based resin> The masterbatch composition of this embodiment preferably contains less than 40% by mass of a chlorine-based resin (or chlorine-containing resin), for example, vinyl chloride-vinyl acetate copolymer resin (solids), relative to the total masterbatch composition (solids), more preferably 0% by mass or more and less than 35% by mass, even more preferably 1% by mass or more and 35% by mass or less, and even more preferably 1% by mass or more and 30% by mass or less. Similarly, the content of vinyl chloride-vinyl acetate copolymer resin (solids) having hydroxyl groups is preferably less than 40% by mass, more preferably 0% by mass or more and less than 35% by mass, even more preferably 1% by mass or more and 35% by mass or less, and even more preferably 1% by mass or more and 30% by mass or less, relative to the total masterbatch composition (solids).

[0122] In the ink composition of this embodiment, the content of chlorine-based resin (or chlorine-containing resin), for example, vinyl chloride-vinyl acetate copolymer resin (solids), is preferably less than 4.5% by mass, more preferably less than 2.5% by mass, even more preferably less than 1.2% by mass, and even more preferably less than 0.5% by mass, relative to the total ink composition (solids). Similarly, the content of vinyl chloride-vinyl acetate copolymer resin (solids) having hydroxyl groups is preferably less than 4.5% by mass, more preferably less than 2.5% by mass, even more preferably less than 1.2% by mass, and even more preferably less than 0.5% by mass, relative to the total ink composition (solids). This makes it possible to provide an environmentally friendly ink that is chlorine-free, thus reducing the environmental burden. In general, inks currently used in lamination processes widely employ a combination of polyurethane resin and / or (meth)acrylic resin and chlorine-based resins such as vinyl chloride-vinyl acetate copolymer resin as a binder resin that can achieve both excellent dispersibility and high film properties. In particular, the combination of chlorine-based resins and polyurethane resins is very effective in achieving good printability and various physical properties required for laminating inks (adhesion to substrate, lamination strength, and boil-retort suitability). However, when prioritizing the provision of environmentally friendly inks, it becomes necessary to exclude chlorine-based resins such as vinyl chloride-vinyl acetate copolymer resins. However, if the amount of chlorine-based resins such as vinyl chloride-vinyl acetate copolymer resins used is less than a predetermined amount or substantially not used, a decrease in extrusion lamination strength becomes a problem. However, in this disclosure, it has been confirmed that even with a chlorine-based resin-free binder resin composition, including vinyl chloride-vinyl acetate copolymer, the necessary extrusion lamination strength can be imparted to the ink. This embodiment is a masterbatch composition containing at least a colorant, a binder resin containing polyurethane resin and / or (meth)acrylic resin, and an organic solvent, wherein the chlorine content of the binder resin is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass. This allows us to provide environmentally friendly inks, such as chlorine-free inks that do not contain chlorine, when reducing environmental impact is a priority.The vinyl chloride-vinyl acetate copolymer resin described above is a copolymer of vinyl chloride monomer and vinyl acetate monomer. Therefore, the vinyl chloride-vinyl acetate copolymer resin contains vinyl chloride monomer units and vinyl acetate monomer units. In addition, the vinyl chloride-vinyl acetate copolymer resin may contain monomer units other than vinyl chloride monomer units and vinyl acetate monomer units (other monomer units) as needed. The other monomers are not particularly limited as long as they can be copolymerized with vinyl chloride and vinyl acetate.

[0123] [Ink Composition] The ink composition of this embodiment may be an ink composition prepared using a masterbatch composition. More specifically, the ink composition of this embodiment contains a masterbatch composition and additives blended into the masterbatch composition. Preferably, the additive is one or more selected from the group consisting of acidic resins, curing agents, antiblocking agents, antistatic agents, film reinforcing agents, and defoaming agents. By using a masterbatch composition, an ink composition can be provided that exhibits excellent storage stability and maintains excellent color development and low viscosity for a long period of time. Therefore, the ink composition of this embodiment contains a colorant, a polyurethane resin and / or a (meth)acrylic resin, an organic solvent, an additive, and an optional additive component. Furthermore, the ink composition of this embodiment preferably contains a total amount of colorant, polyurethane resin (solids) and / or (meth)acrylic resin (solids), organic solvent, additives, and any additional components of 80% to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass, relative to the total ink composition (100% by mass).

[0124] The ink composition of this embodiment preferably contains a total content of colorant, binder resin (solids), organic solvent, additives, and optional additive components of 80% to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass, relative to the total ink composition (100% by mass). Furthermore, the binder resin (solids) preferably contains polyurethane resin (solids) and / or (meth)acrylic resin (solids) in an amount of 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass, relative to the total binder resin (solids), and preferably contains at least one resin (solids) selected from vinyl acetate resin, chlorine-based resin, polyester resin, polyamide resin, polyvinyl butylated resin, and cellulose-based resin in an amount of 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass. The overall acid value of the ink composition of this embodiment is preferably 0 mg KOH / g or more and 30 mg KOH / g or less, more preferably greater than 0 mg KOH / g and 20 mg KOH / g or less, even more preferably 0.88 mg KOH / g or more and 18 mg KOH / g or less, even more preferably 1.2 mg KOH / g or more and 15 mg KOH / g or less, and even more preferably 1.5 mg KOH / g or more and 10 mg KOH / g or less. Within the above range, excellent color development and low viscosity can be maintained for a long period of time.

[0125] (Additives) The ink composition of this embodiment contains additives. The additive may be one or more selected from the group consisting of acidic resins, curing agents, antiblocking agents, antistatic agents, film reinforcing agents, and defoaming agents. The content (solids) of the additives in this embodiment is preferably more than 0% by mass and 15% by mass or less, more preferably 0.01 to 10% by mass, and most preferably 0.1 to 8% by mass, based on the total solids content (100% by mass) of the ink composition. Since the ink composition of this embodiment is prepared via a masterbatch composition, a so-called metastable solution can be formed in which a relatively unreactive substance (polyurethane resin and / or (meth)acrylic resin) and the colorant associate before the highly reactive additive and colorant coexist. Therefore, it is believed that an ink composition is prepared that exhibits excellent storage stability and maintains excellent color development and low viscosity for a long period of time. <Acidic Resin> The ink composition of this embodiment preferably contains an acidic resin. By including the acidic resin, the property of easily removing ink components or varnish components from the printed substrate (deinking) is improved. As described above, the acidic resin in this specification refers to a resin with an acid value of 0.5 to 500 mgKOH / g and a weight-average molecular weight (Mw) of 10,000 to 50,000. The content (solids) of the above acidic resin is preferably 0 to 15% by mass, more preferably 0.01 to 13% by mass, and most preferably 0.1 to 12% by mass, relative to the total solids (100% by mass) of the ink composition. By setting the acidic resin content to a range of 0.1 to 10% by mass, a deinking effect can be achieved. The acidic resin in this embodiment is preferably one or more selected from the group consisting of alkyd resin, epoxy resin (1), rosin-based resin, and maleic acid resin, and more preferably one or more selected from the group consisting of epoxy resin (1) and maleic acid resin.

[0126] - Alkyd Resin - The alkyd resin of this embodiment may be a condensed polymer of a polybasic acid and a polyhydric alcohol, or a condensed polymer obtained by condensing a polyhydric alcohol and a polybasic acid together with animal and vegetable oils and / or their fatty acids. Examples of the polybasic acid include isophthalic acid, terephthalic acid, adipic acid, trimellitic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexenedicarboxylic acid, 1,4-cyclohexenedicarboxylic acid, hexahydrophthalic anhydride, 5-sodiosulfoisophthalic acid, fumaric acid, benzoic acid, tert-butylbenzoic acid, tetrahydrophthalic anhydride, maleic anhydride, succinic acid, succinic anhydride, fumaric acid, sebacic acid, azelaic acid, tetrabromophthalic anhydride, methylhymic anhydride, tetrachlorophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methylcyclohexenedicarboxylic acid anhydride, and the like. These can be used alone or in combination of two or more, along with phthalic acid or phthalic anhydride, which are essential components.

[0127] The above polyhydric alcohol is not particularly limited as long as it is a compound that forms an ester with the above polybasic acid, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, spiroglycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol, 1,3,3-methyl Examples include lupentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, ethylene oxide-modified compounds of difunctional phenols such as bisphenol A, propylene oxide-modified compounds of difunctional phenols such as bisphenol A, ethylene oxide-propylene oxide copolymer-modified compounds of bisphenol A, copolymer polyether polyols of ethylene oxide and propylene oxide, polycarbonate diols, adamantanediol, polyether diols, polyester diols, and polycaprolactone diols. These can be used individually or in combination of two or more.

[0128] The weight-average molecular weight (Mw) of the alkyd resin in this embodiment is preferably 1,000 to 100,000, more preferably 5,000 to 50,000. The acid value of the alkyd resin in this embodiment is preferably 0.5 mg KOH / g to 500 mg KOH / g, more preferably 0.5 mg KOH / g to 450 mg KOH / g, and even more preferably 1 mg KOH / g to 400 mg KOH / g.

[0129] -Epoxy Resin (1)- Examples of epoxy resin (1) in this embodiment include known epoxy resins such as epoxy (meth)acrylate resin and bisphenol-type epoxy resin. The epoxy (meth)acrylate resin is a resin containing a cardanol skeleton, a bisphenol skeleton, and a (meth)acrylate moiety. Examples of the bisphenol-type chemical structure or bisphenol skeleton include bisphenol A skeleton, bisphenol F skeleton, bisphenol P skeleton, and bisphenol Z skeleton. Examples of the epoxy compounds include bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin; novolac-type epoxy resins such as orthocresol novolac type epoxy resin, phenol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol A novolac type epoxy resin, brominated phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, bisphenol S novolac type epoxy resin, alkoxy group-containing novolac type epoxy resin, and brominated phenol novolac type epoxy resin; and other phenol aralkyl type epoxy resins (commonly known as epoxidized Zyloc resins). Examples include diglycidyl ether of resorcinol, diglycidyl ether of hydroquinone, diglycidyl ether of catechol, bifunctional epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, sulfur-containing epoxy resins, and stilbene-type epoxy resins, as well as alicyclic epoxy resins such as hydrogenated bisphenol A-type epoxy resins; triglycidyl cisocyanurate, triphenylmethane-type epoxy resins, tetraphenylethane-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl-modified novolac-type epoxy resins (epoxidized polyhydric phenol resins in which phenol nuclei are linked by bismethylene groups), alkoxy-group-containing novolac-type epoxy resins, and tetrabromobisphenol A-type epoxy resins. Furthermore, the epoxy compounds may be used individually or in combination of two or more types.

[0130] The weight-average molecular weight (Mw) of the epoxy resin (1) in this embodiment may be, for example, 1,000 to 50,000, preferably 1,000 to 30,000. The acid value of the epoxy resin (1) in this embodiment is preferably 10 mg KOH / g to 700 mg KOH / g, more preferably 10 mg KOH / g to 600 mg KOH / g, and even more preferably 10 mg KOH / g to 500 mg KOH / g.

[0131] -Rosin-based resin- The rosin-based resin in this embodiment can be any resin that uses rosin as a reaction raw material. The rosin contains a mixture of abietic acid, palastic acid, isopimal acid, and levopimal acid, etc. A rosin-modified resin is preferred as the rosin-based resin. Examples of rosin-modified resins include condensate polymers obtained by condensation polymerization of the above polyhydric alcohols or the above polybasic acids, and adducts obtained by adding resol, which is a phenol condensate, to the benzene ring contained in the rosin skeleton. Specifically, examples include rosin ester resins, fumarated rosin resins, rosin-modified fumaric acid resins, rosin-modified phenol resins, rosin-modified alkyd resins, etc.

[0132] The weight-average molecular weight (Mw) of the rosin-based resin in this embodiment may be, for example, 1,000 to 200,000, preferably 1,500 to 150,000. The acid value of the rosin-based resin in this embodiment is preferably 1 mg KOH / g to 700 mg KOH / g, more preferably 5 mg KOH / g to 600 mg KOH / g, and even more preferably 5 mg KOH / g to 500 mg KOH / g.

[0133] -Maleic acid resin- Examples of maleic acid resins in this embodiment include rosin-modified maleic acid resin, styrene-maleic acid resin, polyolefin-maleic acid resin, vinyl chloride-vinyl acetate-maleic acid copolymer resin, etc. Furthermore, the contents described in the <<Maleic acid resin>> section above shall be used as reference for the maleic acid resin.

[0134] The weight-average molecular weight (Mw) of the maleic acid resin in this embodiment may be, for example, 100 to 20,000, preferably 500 to 10,000. The acid value of the maleic acid resin in this embodiment is preferably 50 mg KOH / g to 800 mg KOH / g, more preferably 60 mg KOH / g to 700 mg KOH / g, and even more preferably 70 mg KOH / g to 600 mg KOH / g.

[0135] <Curing Agent> The ink composition of this embodiment preferably contains a curing agent. By including the curing agent, the adhesion and lamination strength of the ink can be improved. The curing agent refers to a compound that has the function of curing a binder resin containing a polyurethane resin and / or a (meth)acrylic resin. Examples of the curing agent include a compound having a plurality of epoxy groups, a compound having a plurality of carbodiimide groups, a polyamine compound having a plurality of amino groups, and a polyisocyanate compound (1) having a plurality of isocyanate groups. The compound having a plurality of epoxy groups is preferably an epoxy resin, and for example, bisphenol A type epoxy resin, novolac type epoxy resin, polyfunctional epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin can be used.

[0136] The compounds having the aforementioned plurality of carbodiimide groups include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); and poly(phenylenecarbodiimide). Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(naphthylenecarbodiimide), poly(trylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. These may be used individually or in combination of two or more types.

[0137] The polyamine compounds include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl) Examples include propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone.

[0138] Examples of the polyisocyanate compound (1) include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, and lysine triisocyanate. Furthermore, examples of the polyisocyanate compound (1) include polyisocyanate compounds (1) obtained by the reaction of the above polyisocyanate compound with a compound having at least two active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group, and water, as well as 3 to 5-mers of the polyisocyanate compound (1).

[0139] The amount of the curing agent is not particularly limited, but it is preferable that the total amount of the curing agent in this embodiment be 0 to 15% by mass, preferably 0.01 to 13% by mass, preferably 0.1 to 12% by mass, and preferably 0.12 to 11% by mass. If the total amount of the blocking inhibitor is 0.01% by mass or more and 15% by mass or less relative to the total amount of the ink composition, good adhesion and lamination strength tend to be expected.

[0140] <Blocking Inhibitor> The ink composition of this embodiment preferably contains a blocking inhibitor. By including the blocking inhibitor, the blocking resistance can be improved. Various waxes or fine particles can be used as the blocking inhibitor. Commonly used blocking inhibitors such as inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be used as the fine particles.

[0141] Examples of the inorganic fine particles include silica, zirconia, barium sulfate, calcium carbonate, and titanium dioxide. Examples of organic fine particles include resin beads using known urethane resins, acrylic resins, and melamine resins. Examples of organic-inorganic composite fine particles include acrylic-silicone and silicone fine particles. Among these, it is preferable to use inorganic fine particles, and it is preferable to use silica. More specifically, it is preferable to use synthetic amorphous silica.

[0142] Furthermore, it is also preferable to use wax as the blocking inhibitor. Examples of waxes include carnauba wax, polyolefin wax, paraffin wax, Fischer-Tropsch wax, beeswax, microcrystalline wax, polyethylene oxide wax, and amide wax. These may be used alone or in combination. Among these, the use of polyolefin wax and / or amide wax is preferred.

[0143] The amount of the anti-blocking agent is not particularly limited, but it is preferable that the total amount of the anti-blocking agent in the ink composition of this embodiment contains 0 to 10% by mass, preferably 0.01 to 8% by mass, preferably 0.1 to 7% by mass, and preferably 0.12 to 5% by mass. If the total amount of the anti-blocking agent is 0.01% by mass or more relative to the total amount of the ink composition, blocking properties tend to be maintained, and if the total amount of the anti-blocking agent is 10% by mass or less relative to the total amount of the ink composition, adhesion and lamination strength tend to be maintained.

[0144] <Antistatic Agent> The ink composition of this embodiment preferably contains an antistatic agent. By including such an antistatic agent, it is effective in preventing electrostatic damage or suppressing electrostatic problems during printing, such as whiskers and lightning streaks. Examples of antistatic agents include nonionic types such as sorbitan type, ether type, ester type, sorbitol type, and glucose type; cationic types such as quaternary ammonium salt type, quaternary ammonium resin type, imidazoline type, Arcover type, and Solomin A type; anionic types such as alkyl sulfate type, alkyl phosphate type, phosphate ester salt type, and sulfate ester salt type; and amphoteric surfactant types such as betaine type, amino acid type, and aminosulfate ester type.

[0145] Specific examples of antistatic agents include anionic surfactants such as carboxylic acid-based, sulfonic acid-based, and phosphoric acid-based surfactants; cationic surfactants such as quaternary ammonium-based surfactants; amphoteric surfactants such as alkyl betaine-based, alkylimidazoline-based, and alkylalanine-based surfactants; nonionic surfactants such as alkylene oxide polymers, alkylene oxide copolymers, and aliphatic alcohol-alkylene oxide adducts; inorganic conductive substances such as carbon and various metal powders such as gold, platinum, silver, copper, aluminum, nickel, titanium, and molybdenum; and conductive polymers such as polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyphenylenevinylene, polyvinylcarbazole, or polyether ester amide resins composed of aminocarboxylic acid, dicarboxylic acid, and polyethylene glycol. The preferred antistatic agent in this embodiment is preferably one that has a linear alkyl group and a quaternary ammonium base, and the number of carbon atoms in the alkyl chain is preferably 10 to 25.

[0146] The amount of the antistatic agent is not particularly limited, but it is preferable that the total amount of the ink composition in this embodiment contains 0 to 10% by mass of the antistatic agent, preferably 0.01 to 8% by mass, preferably 0.1 to 7% by mass, and preferably 0.12 to 5% by mass. If the total amount of the antistatic agent is 0.01% by mass or more and 10% by mass or less of the total amount of the ink composition, it tends to show an effect of preventing electrostatic damage.

[0147] <Coating Reinforcement Agent> The ink composition of this embodiment preferably contains a coating reinforcement agent. The inclusion of the coating reinforcement agent tends to improve the abrasion resistance of the ink. Examples of the coating reinforcement agent include hydrocarbon waxes (including particulate form). Examples of hydrocarbon waxes include polyolefin waxes and paraffin waxes. The average particle size of the particulate hydrocarbon wax is preferably 0.5 to 12 μm, more preferably 1 to 10 μm, and even more preferably 1.5 to 4 μm. The average particle size of the hydrocarbon wax refers to the D50 value in the dynamic light scattering method.

[0148] The amount of the coating reinforcing agent is not particularly limited, but it is preferable that the total amount of the coating reinforcing agent in the ink composition of this embodiment be 0 to 10% by mass, preferably 0.01 to 8% by mass, preferably 0.1 to 7% by mass, and preferably 0.12 to 5% by mass. If the total amount of the coating reinforcing agent is 0.01% by mass or more and 10% by mass or less relative to the total amount of the ink composition, the ink tends to show an effect of improved abrasion resistance.

[0149] <Defoaming Agent> The ink composition of this embodiment preferably contains a defoaming agent. By containing the defoaming agent, it exhibits an antifoaming effect. As the defoaming agent, a known defoaming agent can be used, and so-called antifoaming polymers are preferred. Examples of the defoaming agent include one or more selected from silicone-based defoaming agents (hydrophobic polydimethylsiloxane-based defoaming agents, defoaming agents combining polysiloxane containing long-chain alkyl groups or aralkyl groups with polyoxyalkylene chain-containing polysiloxane, defoaming agents mainly composed of polysylcarbensiloxane consisting of silcarben units and siloxane units, etc.), hydrophobic silica-based defoaming agents, polyether-based defoaming agents, acetylene glycol-based defoaming agents, acrylic polymer-based defoaming agents, oil-based defoaming agents, metal soap-based defoaming agents, or amide wax-based defoaming agents. The amount of the defoaming agent is not particularly limited, but it is preferable that the total amount of the defoaming agent in the ink composition of this embodiment be 0 to 10% by mass, preferably 0.01 to 8% by mass, preferably 0.1 to 7% by mass, and preferably 0.12 to 5% by mass. If the total amount of the defoaming agent is 0.01% by mass or more and 10% by mass or less relative to the total amount of the ink composition, a defoaming effect tends to be expected.

[0150] (Preferred Embodiment of Ink Composition) When the ink composition of this embodiment essentially contains polyurethane resin, a preferred ink composition contains a colorant, polyurethane resin, polyvinyl butyral resin, an organic solvent, and an additive, and the total content of the colorant, polyurethane resin, polyvinyl butyral resin, organic solvent, and additive is preferably 98% by mass or more and 100% by mass or less, and more preferably 98.3% by mass or more and 99.8% by mass or less, based on the total amount (100% by mass) of the ink composition. Furthermore, it is preferable that the ink composition further contains cellulose acetate propionate resin. When cellulose acetate propionate resin is included, the content of the cellulose acetate propionate resin is preferably 0.2% by mass or more and 1% by mass or less, based on the total amount (100% by mass) of the ink composition. The additive is preferably one selected from the group consisting of maleic acid resin, styrene maleic anhydride, epoxy resin (1), polyisocyanate compound (1), antistatic agent, defoaming agent, antiblocking agent, and film reinforcing agent. In this embodiment, a preferred ink composition is preferably, for example, one containing 6% to 15% by mass of a colorant, 6% to 12% by mass of a polyurethane resin, 1.5% to 5% by mass of a polyvinyl butyral resin, 70% to 80% by mass of an organic solvent, and 1% to 6% by mass of an additive, based on the total amount (100% by mass) of the ink composition. When the additive is maleic acid resin, styrene maleic anhydride, epoxy resin (1), antistatic agent, or defoaming agent, the content of the additive is preferably 1.5% to 3% by mass, based on the total amount (100% by mass) of the ink composition. On the other hand, when the additive is a polyisocyanate compound (1), the content of the additive is preferably 3% to 6% by mass relative to the total amount (100% by mass) of the ink composition. When the additive is an anti-blocking agent, the content of the additive is preferably 1.5% to 3% by mass (0.1% to 0.3% by mass in terms of solid content) relative to the total amount (100% by mass) of the ink composition.Furthermore, if the additive is a film reinforcing agent, the content of the additive is preferably 1.5% to 3% by mass (0.2% to 0.8% by mass in terms of solid content) of the total amount (100% by mass) of the ink composition.

[0151] In the case where the ink composition of this embodiment essentially contains (meth)acrylic resin, a preferred ink composition contains a colorant, (meth)acrylic resin, polyvinyl butyral resin, organic solvent, and additives, and the total content of the colorant, (meth)acrylic resin, polyvinyl butyral resin, organic solvent, and additives is preferably 98% by mass or more and 100% by mass or less, more preferably 98.3% by mass or more and 99.8% by mass or less, based on the total amount (100% by mass) of the ink composition. Furthermore, it is preferable that the ink composition further contains cellulose acetate propionate resin. When cellulose acetate propionate resin is included, the content of the cellulose acetate propionate resin is preferably 0.2% by mass or more and 1% by mass or less, based on the total amount (100% by mass) of the ink composition. The additive is preferably one selected from the group consisting of maleic acid resin, styrene maleic anhydride, epoxy resin (1), polyisocyanate compound (1), antistatic agent, defoaming agent, antiblocking agent, and film reinforcing agent. In this embodiment, a preferred ink composition is preferably, for example, one containing 6% to 15% by mass of a colorant, 6% to 12% by mass of a (meth)acrylic resin, 1.5% to 5% by mass of a polyvinyl butyral resin, 70% to 80% by mass of an organic solvent, and 1% to 6% by mass of an additive, based on the total amount (100% by mass) of the ink composition. When the additive is maleic acid resin, styrene maleic anhydride, epoxy resin (1), antistatic agent, or defoaming agent, the content of the additive is preferably 1.5% to 3% by mass, based on the total amount (100% by mass) of the ink composition. On the other hand, when the additive is a polyisocyanate compound (1), the content of the additive is preferably 3% to 6% by mass relative to the total amount (100% by mass) of the ink composition. When the additive is an anti-blocking agent, the content of the additive is preferably 1.5% to 3% by mass (0.1% to 0.3% by mass in terms of solid content) relative to the total amount (100% by mass) of the ink composition.Furthermore, if the additive is a film reinforcing agent, the content of the additive is preferably 1.5% to 3% by mass (0.2% to 0.8% by mass in terms of solid content) of the total amount (100% by mass) of the ink composition.

[0152] [Method for Manufacturing Masterbatch Composition and Method for Manufacturing Ink Composition] (Method for Manufacturing Masterbatch Composition (or Masterbatch Preparation Process)) The masterbatch composition of this embodiment can be manufactured by dissolving and / or dispersing a polyurethane resin and / or (meth)acrylic resin, a colorant such as a pigment, in an organic solvent. Specifically, a pigment dispersion can be manufactured by dispersing a pigment in an organic solvent with a binder resin, and a masterbatch can be manufactured by blending the obtained pigment dispersion with the above-mentioned other binder resins and / or the above-mentioned optional additive components as needed. The dispersion of the colorant (e.g., pigment) may use a polyurethane resin and / or (meth)acrylic resin, or other resins, or a dispersant, but it is preferable to disperse it using one or more resins selected from the group consisting of polyurethane resin, (meth)acrylic resin, polyvinyl butyral resin, chlorine resin, polyamide resin, polyester resin, and cellulose resin, with polyvinyl butyral resin or chlorine resin being more preferable. This makes it easier to form a so-called metastable state, resulting in a masterbatch that can be used to prepare an ink composition exhibiting superior storage stability and maintaining excellent color development and low viscosity for a long period of time.

[0153] The particle size distribution of the pigment in the above-mentioned pigment dispersion can be adjusted by appropriately adjusting the size of the grinding media in the disperser, the packing rate of the grinding media, the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, etc. As the disperser, commonly used types such as roller mills, ball mills, pebble mills, attritors, and sand mills can be used. If air bubbles or unexpectedly large particles are included in the ink, it is preferable to remove them by filtration or the like, as this will degrade the quality of the printed material. Conventional known filters can be used.

[0154] The viscosity of the masterbatch composition produced by the above method is preferably in the range of 10 mPa·s or more from the viewpoint of preventing sedimentation of colorants such as pigments and dispersing them appropriately, and 1000 mPa·s or less from the viewpoint of workability during masterbatch production and printing. The above viscosity is measured at 25°C using a Tokimec Type B viscometer. The viscosity of the masterbatch composition can be adjusted by appropriately selecting the type and amount of raw materials used, such as binder resin (e.g., polyvinyl butyral resin), colorants or pigments, organic solvents, etc. The viscosity of the masterbatch composition can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the masterbatch composition.

[0155] The masterbatch composition of this embodiment has five basic process colors—yellow, red, blue, black, and white—depending on the type of pigment used, and three extra-process gamut colors—red (orange), grass (green), and purple. Furthermore, transparent yellow, peony, vermilion, brown, gold, silver, pearl, and a nearly transparent medium for adjusting color density (including extender pigments as needed) are prepared as base colors. The ink for boil retort processing is selected appropriately considering the migration properties and heat resistance of the pigments.

[0156] (Method for Manufacturing Ink Composition) The method for manufacturing the ink composition of this embodiment comprises a masterbatch preparation step of preparing a masterbatch composition containing a colorant, a polyurethane resin and / or a (meth)acrylic resin, and an organic solvent, and an additive step of adding the additives to the masterbatch composition. If necessary, the method for manufacturing the ink composition of this embodiment may also include an additive preparation step of preparing the additives. The masterbatch preparation step is carried out by reference to the contents described in the (Method for Manufacturing Masterbatch Composition) section above. Furthermore, after the masterbatch preparation step, from the viewpoint of maintaining storage stability, color development, and low viscosity for a long period of time, it is preferable to let the masterbatch composition obtained in the masterbatch preparation step, which is the method for manufacturing the masterbatch composition described above, stand for 1 to 24 hours.

[0157] Furthermore, the method for producing the ink composition of this embodiment includes, if necessary, an additive preparation step for preparing additives. In the additive preparation step, the additives may be dissolved in the organic solvent if necessary, and it is preferable to prepare a solution in which the concentration of the additives is 10 to 90% by mass.

[0158] The method for producing the ink composition of this embodiment includes a step of adding the additive to the masterbatch composition obtained in the masterbatch preparation step. That is, a predetermined amount of the additive is mixed with the masterbatch composition obtained in the masterbatch preparation step. As for the mixing method, after blending the masterbatch composition and the additive, the mixture is kneaded in a bead mill or a three-roll mill, etc., to adjust the viscosity and obtain the ink composition. The viscosity of the ink composition produced by the above method is preferably in the range of 10 mPa·s or more from the viewpoint of preventing the settling of colorants such as pigments and dispersing them appropriately, and 1000 mPa·s or less from the viewpoint of workability efficiency during ink production and printing. The above viscosity is the viscosity measured at 25°C with a Tokimec Type B viscometer. The viscosity of the ink composition can be adjusted by appropriately selecting the type and amount of raw materials used, for example, binder resin (for example, polyvinyl butyral resin), colorants or pigments, organic solvents, etc. The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.

[0159] (Printed Materials) The ink composition of this embodiment can be printed to produce printed materials. Printing can be done using known printing methods such as gravure printing and flexographic printing, but gravure printing is particularly preferred. Known cylinders such as engraved type and etching type are used for gravure printing. The layer in which a desired pattern is formed by the ink composition of this embodiment is called the printed layer. The printed layer may be a single layer or there may be multiple printed layers. If there are multiple printed layers, the ink composition used for each printed layer may be the same, or may have the same composition but different pigments, or may have different compositions. For example, if there are multiple printed layers, the printed material may have a first printed layer formed from a colored ink composition, a second white printed layer formed from white ink, and a third white printed layer in this order. The first printed layer can form a pattern using pigments, and the second white printed layer and the third printed layer formed from white ink can be used as backgrounds for the pattern. If the second or third printing layer is an overprint varnish, it does not need to contain coloring agents such as pigments.

[0160] The base ink is diluted with a diluent solvent to a viscosity and concentration suitable for gravure or flexographic printing, and supplied to each printing unit, either alone or in mixtures, for printing.

[0161] (Laminated Laminate) The present disclosure may be a laminated laminate having a substrate and a printed layer on which an ink composition is printed on at least a portion of the surface of the substrate. The printed layer on the surface of the substrate may be in direct or indirect contact with the surface of the substrate. Preferred configurations of the laminated laminate of this embodiment include, for example, the following (1) to (4): (1) Substrate / adhesive layer / printed layer / substrate (2) Substrate / adhesive layer / substrate / printed layer / adhesive layer / substrate (3) Substrate / adhesive layer / first printed layer / second printed layer / substrate (4) Substrate / adhesive layer / barrier layer / printed layer / adhesive layer / substrate (5) Substrate / printed layer / adhesive layer / substrate However, the laminated laminate of this embodiment is not limited to (1) to (4) above and may include additional substrates. If multiple substrates are included, the substrates may be the same or different. Furthermore, the substrate may be a sealable sealant film or a multilayer film containing a sealant layer made of a heat sealant, and the sealable layer is referred to as the sealant layer. In addition, multiple adhesive layers may have the same composition or different compositions. Furthermore, an anchor coat layer may be sandwiched between the adhesive layers to improve the adhesive strength.

[0162] The ink composition of this embodiment is useful for a wide variety of films, from general-purpose films to various high-performance films, as a substrate for printing. There are no particular limitations on the usable plastic films, and examples include films made of polyamide resins such as Ny6, nylon 66, and nylon 46; polyester resins such as polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; biodegradable resins represented by polyhydroxycarboxylic acids such as polylactic acid, aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate); thermoplastic resins such as polyolefin resins such as polypropylene (PP) and polyethylene, polyimide resins, polyarylate resins, or mixtures thereof; various high-performance films coated with inorganic or organic barrier coating materials on the surface; and laminates thereof. Among these, films made of polyester, polyamide, polyethylene, and polypropylene can be preferably used. These films may be unstretched or stretched films, and their manufacturing methods are not limited. The film may be a multilayer film produced by co-extruding the resins of each layer, or a multilayer sealant film having a sealant layer on the outermost layer of the multilayer film. The thickness of the base film is not particularly limited, but is usually in the range of 1 to 500 μm.

[0163] The above-mentioned substrate may be formed from biomass polyolefin. This biomass polyolefin refers to a polyolefin resin using plant-derived olefins as raw material monomers. These raw material monomers may include petroleum-derived monomers and do not necessarily contain 100% plant-derived monomers. Commercially available biomass polyolefins can also be used. Examples of commercially available products include SGM9450F, SLL118, SLL118 / 21, SLL218, SLL318, SLH118, SLH218, and SLH0820 from Braschem.

[0164] Furthermore, the substrate used in the laminated structure of this embodiment may be a substrate having a vapor-deposited layer made of inorganic material and / or inorganic oxide on the resin film described above. By using a substrate with such vapor-deposited layer, barrier properties can be imparted to the laminated structure of this embodiment. The vapor-deposited layer can be formed using known inorganic material or inorganic oxide by known methods, and its composition and formation method are not particularly limited. In addition, the laminated structure may have two or more vapor-deposited layers, which may have the same composition or different compositions.

[0165] As the above-mentioned vapor-deposited layer, for example, a vapor-deposited film of an inorganic substance or inorganic oxide such as silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), or yttrium (Y) can be used. Furthermore, vapor-deposited films of inorganic oxides such as silicon oxide and aluminum oxide are transparent.

[0166] The inorganic oxides mentioned above are denoted as MOx (where M represents an inorganic element), such as SiOx and AlOx. The value of x can take on the following ranges: silicon (Si) 0-2, aluminum (Al) 0-1.5, magnesium (Mg) 0-1, calcium (Ca) 0-1, potassium (K) 0-0.5, tin (Sn) 0-2, sodium (Na) 0-0.5, boron (B) 0-1.5, titanium (Ti) 0-2, lead (Pb) 0-1, zirconium (Zr) 0-2, and yttrium (Y) 0-1.5. In the above, if x = 0, it is a complete inorganic element (pure substance) and is not transparent, and if the value of x is at the upper limit of the range, it indicates that it is completely oxidized. Silicon (Si) and aluminum (Al) are preferably used as the vapor-deposited layer. For silicon (Si), an x ​​value in the range of 1.0 to 2.0 can be used, and for aluminum (Al), an x ​​value in the range of 0.5 to 1.5 can be used.

[0167] The above-mentioned vapor-deposited layer can be formed on the surface of the substrate or the like by methods such as vacuum deposition, sputtering, and ion plating (physical vapor deposition, PVD), or plasma chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition (chemical vapor deposition, CVD).

[0168] The thickness of the above-mentioned vapor-deposited layer is not particularly limited as long as the vapor-deposited layer alone can exhibit a certain gas barrier function. The preferred range of thickness varies depending on the type of metal or metal oxide to be deposited, but is preferably 0.05 to 70 nm, more preferably 0.1 to 70 nm, even more preferably 3 to 70 nm, and even more preferably 5 to 60 nm.

[0169] As the above-mentioned metal-deposited film, VM-CPP film, which is obtained by depositing a metal such as aluminum onto a CPP film, and VM-OPP film, which is obtained by depositing a metal such as aluminum onto an OPP film, can be used. As the above-mentioned transparent-deposited film, examples include films obtained by depositing silica or alumina onto an OPP film, PET film, nylon film, etc. Films with a coating applied to the deposited layer may also be used for purposes such as protecting the inorganic-deposited layer of silica or alumina.

[0170] Paper can also be used as the substrate. For example, high-quality paper, kraft paper, pure white roll paper, glassine paper, parchment paper, Manila cardboard, white cardboard, coated paper, art paper, imitation paper, thin paper, thick paper, polyethylene coated paper, various synthetic papers, and acid-resistant paper can be used for printing on packaging materials for cosmetics, beverages, pharmaceuticals, toys, and equipment. Furthermore, it is preferable that the printing surface of the substrate be treated with corona discharge to further improve adhesion to the substrate.

[0171] <Lamination Method> The lamination method for producing the laminated body of this embodiment is not particularly limited and includes methods such as dry lamination, wet lamination, non-solvent lamination, and extrusion lamination. In this case, the layer located between the substrates is called the adhesive layer.

[0172] Examples of adhesives used in the above dry lamination include solvent-type two-component curing adhesives. A "solvent-type" adhesive refers to a form used in the so-called dry lamination method, in which the adhesive is applied to a substrate, heated in an oven or the like to evaporate the organic solvent in the coating, and then bonded to another substrate. It includes a polyisocyanate composition, a polyol composition, and an organic solvent capable of dissolving (diluting) them.

[0173] In the above-mentioned two-component curing adhesive, considering the construction of a sustainable circular society, it is preferable to use plant-derived raw materials (biomass raw materials) as raw materials for the polyisocyanate composition or polyol composition. By appropriately using biomass raw materials, the environmental burden can be reduced. Examples of biomass raw materials include castor oil-based polyols such as castor oil, dehydrated castor oil, hydrogenated castor oil (a hydrogenated product of castor oil), and 5 to 50 mole alkylene oxide adducts of castor oil, as well as aliphatic polybasic acids such as succinic acid, succinic anhydride, glutaric acid, adipic acid, azelaic acid, sebacic acid, and itaconic acid, and alkyl esters of these acids, and dimer acids.

[0174] Commercially available adhesives can also be used as the above-mentioned adhesives that utilize biomass raw materials. Commercially available adhesives listed by the Japan Organic Resources Association can be used, such as DIC Dry BM (manufactured by DIC Corporation) and Takenate BM (manufactured by Mitsui Chemicals, Inc.).

[0175] The weight of the above adhesive layer after drying is 0.1 to 10 g / m². ２ Preferably, it is 1 to 6 g / m ２ It is more preferable that the amount be 2-5 g / m ２ It is even more preferable that this is the case. Furthermore, the thickness of the adhesive layer is preferably 0.1 to 10 μm, more preferably 1 to 7 μm, and even more preferably 2 to 5 μm.

[0176] Furthermore, various adhesives can be used as the adhesive layer, but it is preferable to use a pressure-sensitive adhesive. Examples of such pressure-sensitive adhesives include rubber-based adhesives obtained by dissolving polyisobutylene rubber, butyl rubber, or mixtures thereof in an organic solvent such as benzene, toluene, xylene, or hexane; or rubber-based adhesives obtained by compounding these with tackifiers such as rosin aviethylene acid ester, terpene-phenol copolymer, or terpene-indene copolymer; or acrylic-based adhesives obtained by dissolving acrylic copolymers with a glass transition temperature of 20°C or lower, such as 2-ethylhexyl acrylate / n-butyl acrylate copolymer or 2-ethylhexyl acrylate / ethyl acrylate / methyl methacrylate copolymer, in an organic solvent.

[0177] By using materials with gas barrier properties as the adhesive or anchor coating agent described later, a laminate film with particularly excellent barrier properties can be obtained. A particularly preferred adhesive with excellent gas barrier properties is 3 g / m². ２ The oxygen barrier property of the cured coating film of the adhesive applied with (solid content) is 300 cc / m². ２ / day / atm or less, or water vapor barrier property of 120 g / m² ２ This refers to products that satisfy at least one of the following conditions: / day or less. Examples of commercially available products include the "PASLIM" series such as PASLIM VM001 and PASLIM J350X manufactured by DIC Corporation, and "MAXIEVE" manufactured by Mitsubishi Gas Chemical Company.

[0178] Furthermore, the adhesive layer may also be formed from a thermoplastic resin, and the formation method may be conventionally known methods, such as the melt extrusion lamination method or the sand lamination method. The ink composition of this disclosure is preferably laminated by the extrusion lamination method or the sand lamination method in order to particularly improve the interlayer adhesion strength of the extruded laminate. Examples of thermoplastic resins that can be used for the adhesive layer include polyethylene resins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE); polypropylene resins such as propylene homopolymers, propylene-α-olefin random copolymers, and propylene-α-olefin block copolymers; norbornene polymers such as ring-opening polymers (COP) of norbornene monomers and norbornene copolymers (COC) obtained by copolymerizing norbornene monomers with olefins such as ethylene, and their hydrogenated products; cyclic polyolefin resins such as vinyl alicyclic hydrocarbon polymers and cyclic conjugated diene polymers; and ethylene Examples include polyethylene elastomers such as polyvinyl acetate copolymer (EVA) and ethylene-α-olefin copolymer, thermoplastic elastomers such as polypropylene elastomers and butene elastomers; ethylene copolymers such as ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), and ethylene-methacrylic acid copolymer (EMAA); and further, ionomers of ethylene-acrylic acid copolymer and ionomers of ethylene-methacrylic acid copolymer. In addition, to improve interlayer adhesion, acid-modified polyolefin resins obtained by modifying the above-mentioned polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid can also be used. Furthermore, resins obtained by graft polymerization or copolymerization of polyolefin resins with unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, or ester monomers can also be used. These resins can be used individually or in combination of two or more types.Furthermore, it is also preferable to use a polyethylene-based resin that uses the above-mentioned biomass-derived ethylene as the monomer unit.

[0179] When laminating adhesive layers by extrusion lamination, an anchor coat layer may be provided on the surface of the layer to be laminated by applying and drying an anchor coat agent. Examples of anchor coat agents include any resin with a heat resistance temperature of 135°C or higher, such as polybutadiene resins, known urethane resins, polyisocyanate / polyether polyols, polyethyleneimine, vinyl-modified resins, epoxy resins, polyester resins, alkyl titanates, etc., and anchor coat agents obtained by diluting the above adhesive with an organic solvent. Among these, polyethyleneimine-based anchor coat agents and anchor coat agents obtained by diluting the above adhesive with an organic solvent are preferably used. In addition, a silane coupling agent may be used in combination as an additive, and nitrated cotton may be used in combination to improve heat resistance.

[0180] (Packaging Material) The packaging material of this embodiment preferably consists of a laminate laminate including a printed layer formed from the above-mentioned ink composition, and more preferably consists of a laminate laminate including the above-mentioned ink composition. For example, it may be a packaging material in which two laminate laminates are arranged and sealed so that their respective sealant layers are in contact with each other, or a packaging material in which a continuous (one) laminate laminate is folded and arranged so that its sealant layers are in contact with each other and then sealed, or a packaging material in which the laminate laminate and a thermoplastic resin film are arranged and sealed so that the sealant layer of the laminate laminate is in contact with the thermoplastic resin film. The sealing method is not particularly limited and may be heat sealing, ultrasonic sealing, or any known method. The packaging material can be suitably used as a package. Examples of such packaging include food packaging for Western-style confectionery, snacks, bread, Japanese-style confectionery, and seasonings; medical packaging for pharmaceuticals, bandages, syringes, and other medical supplies; and packaging for sanitary products such as cleaning cloths, masks, and brushes. The printed materials, laminates, and packaging materials using these are recyclable, and the recycled plastic can be used as recycled plastic.

[0181] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples. In addition, unless otherwise specified, "%" in the compositions of the following examples means "mass percent".

[0182] The raw materials used in the examples and comparative examples are as follows: <Coloring agent> The following pigment was used as a coloring agent: Phthalocyanine-based blue pigment DIC Corporation FASTOGEN BLUE FA5380

[0183] <Binder Resins> ・Vinyl chloride-vinyl acetate copolymer resin solution (solid content concentration 15% by mass) Solvine A manufactured by Nisshin Chemical Industry Co., Ltd., non-volatile content 15%, n-propyl acetate solution ・Polyvinyl butyral resin solution (solid content concentration 15% by mass) Polyvinyl butyral resin obtained by reacting polyvinyl alcohol with butyraldehyde (weight-average molecular weight 10,000, hydroxyl group content 15% by mass, glass transition temperature 60°C, acetyl group content 8% by mass), non-volatile content 15%, isopropyl alcohol solution ・Cellulose acetate propionate resin solution (solid content concentration 20% by mass) Cellulose acetate propionate resin (CAP-482-0.5 manufactured by Eastman Chemical), non-volatile content 20%, ethyl acetate / IPA solution. • Polyurethane resin solution (solid content concentration 30% by mass) The polyurethane resin (polyurethane resin solution (solid content concentration 30% by mass)) used in this example and comparative example was synthesized by the methods described in Synthesis Examples 1 to 3 below.

[0184] <Synthesis of Polyurethane Resin> <<Synthesis Example 1>> Preparation of Polyurethane Resin Solution (PU1) 120.0 parts by mass of polyester polyol compound ((PES #2000): "TA22-981" manufactured by Resonaq Corporation), 30.0 parts by mass of polyether polyol compound ((PEG #400): "PEG #400" manufactured by NOF Corporation), and 45.0 parts by mass of isophorone diisocyanate (IPDI) were added to a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. The mixture was reacted at 85°C for 6 hours under a nitrogen stream to produce a urethane prepolymer (1). Then, 48.8 parts by mass of ethyl acetate was added to make a homogeneous solution to obtain urethane prepolymer solution (1). Next, to a mixed solution containing 12.0 parts by mass of isophorone diamine (IPDA), 0.3 parts by mass of cyclohexylamine (CHA), 289.8 parts by mass of ethyl acetate, and 145.1 parts by mass of isopropyl alcohol (IPA), the urethane prepolymer solution (1) was added and reacted at 40°C for 4 hours under a nitrogen atmosphere to obtain a polyurethane resin solution (PU1). The non-volatile content (solid content concentration) of the obtained polyurethane resin solution (PU1) was 30% by mass, the amine value of the solid content of the polyurethane resin solution (PU1) was 2.5 mg KOH / g, and the number-average molecular weight (Mn) of the solid content of the polyurethane resin solution (PU1) was 35,000. The urethane bond concentration of the solid content of the polyurethane resin solution (PU1) was 1.30 mg KOH / g.

[0185] <<Synthesis Example 2>> A polyurethane resin solution (PU2) was prepared in the same manner as in Synthesis Example 1, except that the composition of the raw materials for preparing the polyurethane resin solution (PU2) was changed as shown in Table 1 below. The non-volatile content (solid content concentration) of the obtained polyurethane resin solution (PU2) was 30% by mass, and the urethane bond concentration of the solid content of the polyurethane resin solution (PU2) was 0.56 mg KOH / g.

[0186] <<Synthesis Example 3>> A polyurethane resin solution (PU3) was prepared in the same manner as in Synthesis Example 1, except that the composition of the raw materials was changed as shown in Table 1 below. The non-volatile content (solid content concentration) of the obtained polyurethane resin solution (PU3) was 30% by mass, and the urethane bond concentration of the solid content of the polyurethane resin solution (PU3) was 0.35 mg KOH / g. The composition and physical properties of the polyurethane resin solutions (PU1) to (PU3) prepared in Synthesis Examples 1 to 3 above are shown in Table 1 below.

[0187] • (Meth)acrylic resin solution, manufactured by Mitsubishi Chemical Corporation, "Dianal BR-106", acid value 3.3 mg KOH / g, non-volatile content 30%, ethyl acetate solution.

[0188] <Additives> <<Acidic Resins>> ・Rosin maleic acid resin M1 Arakawa Chemical Industries, Ltd. Marquid #31, non-volatile content 50%, IPA solution, acid value 175-200 mg KOH / g ・Rosin maleic acid resin M2 Arakawa Chemical Industries, Ltd. Marquid #32, non-volatile content 50%, IPA solution, acid value 120-140 mg KOH / g ・Styrene maleic anhydride solution SMA1 Aurorium, Inc. "XIRAN1000", acid value 475 mg KOH / g, non-volatile content 50%, ethyl acetate solution ・Styrene maleic anhydride solution SMA2 Aurorium, Inc. "XIRAN1000", acid value 355 mg KOH / g, non-volatile content 50%, ethyl acetate solution ・Epoxy resin (1) "Epiclon B-4500", acid value 425 mg KOH / g, non-volatile content 50%, ethyl acetate solution / polyisocyanate compound (P1), manufactured by Tosoh Corporation, "Coronate HL" - Polyisocyanate compound (P2), manufactured by EVONIK, "VESTANAT T1890 / 100" - Antistatic agent, manufactured by Kyoeisha Chemical Co., Ltd., "Florence AE-2" - Antifoaming agent, manufactured by Bic Chemie Japan, "BYK-051N" - Blocking inhibitor, manufactured by Fuji Silysia Co., Ltd., "Silysia 350", non-volatile content 10%, ethyl acetate dispersion / film reinforcing agent, manufactured by Mitsui Chemicals, Inc., "High Wax 220P", non-volatile content 25%, isopropyl alcohol dispersion

[0189] The evaluation results for the examples and comparative examples were measured and evaluated as follows. <Molecular weight measurement> The number-average molecular weight and weight-average molecular weight are the values ​​measured by gel permeation chromatography (GPC) under the following conditions. Measuring device: High-speed GPC device (HLC-8220GPC manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series. 1 x TSKgel G5000 (7.8 mm I.D. × 30 cm) 1 x TSKgel G4000 (7.8 mm I.D. × 30 cm) 1 x TSKgel G3000 (7.8 mm I.D. × 30 cm) 1 x TSKgel G2000 (7.8 mm I.D. × 30 cm) Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard samples: A calibration curve was prepared using the following standard polystyrene. [Standard Polystyrene] TSKgel Standard Polystyrene A-500 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-1000 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-2500 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-5000 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-1 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-2 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-4 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-10 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-20 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-40 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-80 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-128 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-288 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-550 (manufactured by Tosoh Corporation)

[0190] <Amine Value (mgKOH / g)> The amine value of polyurethane resin is calculated in accordance with JIS Test Method K 0070-1992. Specifically, 0.5 to 2 g of the sample was accurately weighed (sample solid content: S g), and 50 mL of a methanol / methyl ethyl ketone = 60 / 40 (mass ratio) mixed solution was added and dissolved. Bromophenol blue was added to the resulting solution as an indicator, and titration was performed with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The endpoint was the point where the color of the solution changed from green to yellow, and the titration volume at this point (A mL) was used to determine the amine value using the following formula: Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g] Note that the amine value is calculated as the number of mg of potassium hydroxide equivalent to the amount of hydrochloride needed to neutralize the amine contained in 1 g of the sample.

[0191] <Acid Value (mgKOH / g)> The method for measuring the acid value in this example and comparative example is as follows: It represents the amount of potassium hydroxide required to neutralize acid groups such as carboxyl groups per gram of sample solids (solids of each resin, masterbatch composition, or ink composition), expressed in milligrams, and was measured in accordance with JIS K 5601-2-1:1999.

[0192] <Color difference change (ΔE*ab)> The color difference ΔE*ab, expressed as the distance between two points in the "L*a*b* color space" defined by the CIE (International Commission on Illumination) in 1976, was calculated using the following method. Specifically, the ΔL* of each masterbatch composition prepared in the examples was calculated. ２ / a* ２ / b* ２ And the ΔL* of the masterbatch composition containing the additive, measured by the following method. １ / a* １ / b* １ The color difference (ΔE*ab) was calculated using the values. Ink compositions prepared by adding additives to the masterbatch compositions prepared in the Examples section with the compositions shown in Tables 1-2 were printed onto OPP film (Toyobo P2161 20 μm) using a bar coater No. 4 (RD Specialties). After that, the film was placed on white paper and the ΔL* １ / a* １ / b*１ The color was measured using an eXact colorimeter manufactured by X-Rite, and the color difference (ΔE*ab) was determined according to JIS Z 8781-4. The L*, a*, and b* values ​​in the CIE L*a*b* color system were obtained by taking measurements at five points and averaging them out.

[0193] The formula used to calculate the color difference (ΔE*ab) was the "CIE 1976 L*a*b* color difference formula". (In the above formula, ΔL* ２ a* ２ and b* ２ ΔL* represents the L*, a*, and b* values ​​of the masterbatch composition, which is the composition before additives are added. １ a* １ and b* １ These represent the L*, a*, and b* values ​​of the ink composition, which is the composition obtained after the additives have been added to the masterbatch composition.

[0194] <Viscosity Change Rate> The viscosity of each masterbatch composition prepared in the examples and the viscosity of the ink composition obtained by compounding the masterbatch composition with additives in the compositions shown in Tables 1 and 2 were measured by the following method, and then calculated using the following formula. Specifically, a Zahn cup of a size (number with orifice diameter) in which the viscosity of the masterbatch composition (the composition before the addition of additives) falls within the range of 20 to 30 seconds was selected. Next, the cup portion of the Zahn cup was immersed in the masterbatch composition, slowly lifted, and the time from the moment a droplet fell from the orifice to the moment the droplet stopped falling was measured. Similarly, a Zahn cup of a size (number with orifice diameter) in which the viscosity of the ink composition (the composition with additives) falls within the range of 20 to 30 seconds was selected. Next, the cup portion of the Zahn cup was immersed in the ink composition, slowly lifted, and the time from the moment a droplet fell from the orifice to the moment the droplet stopped falling was measured. In the measurement of viscosity change rate (%) in this embodiment, if the dropping time of the masterbatch composition and its ink composition is in the range of 20 to 30 seconds, a viscosity change difference of 2 to 3 seconds between the two dropping times is considered to be within the usable range. Viscosity change rate (%) = |({η ｍｉｘ -ηｍ} / η ｍ ) | × 100 < 15 (%) (In the above formula (1), η ｍｉｘ η represents the viscosity (seconds) of the ink composition at 25°C, which is the composition after additives have been added to the masterbatch composition. ｍ This represents the viscosity (seconds) of the masterbatch composition, which is the composition before the addition of additives at 25°C. The above viscosity change rate (%) values ​​were evaluated according to the following criteria: A: Viscosity change rate (%) is less than 10%. B: Viscosity change rate (%) is less than 15% (10% or more). C: Viscosity change rate (%) is 15% or more.

[0195] <Storage Stability> Each ink composition prepared using the masterbatch compositions prepared in the Examples and Comparative Examples was placed in a glass bottle and left to stand at 25°C for one week. The degree of separation and precipitation was then evaluated. Separation was evaluated by measuring the thickness of the separated layer, and precipitation was evaluated by scraping the bottom of the bottle once with a spatula to assess the amount of precipitate. 5: No separation or precipitation was observed. 4: A small separated layer of 1 mm or less was formed, or a small amount of precipitate could be recovered on the tip of the spatula. 3: A separated layer of 3 mm or less was formed, or precipitate could be recovered to about 1 / 3 of the tip of the spatula. 2: A separated layer of 5 mm or less was formed, or precipitate could be recovered to about half of the spatula. 1: A separated layer of 5 mm or more was formed, or precipitate filled more than half of the spatula.

[0196] (Examples 1-8) <Preparation of Masterbatch Compositions> Using each compound listed in the (raw materials) section above, the masterbatch compositions (1) to (8) of Examples 1-8 were prepared by mixing and stirring in the composition ratios shown in Table 2. Then, according to the evaluation procedure above, the acid value and ΔL* of each masterbatch composition were evaluated. ２ / a* ２ / b* ２ The viscosity was also measured. The acid values ​​of the masterbatch compositions (1) to (8) were all in the range of 0 mg KOH / g to 30 mg KOH / g. Specifically, the acid values ​​of masterbatch compositions (1) to (4) were approximately 0 mg KOH / g, the acid values ​​of masterbatch compositions (5) to (6) were 29.7 mg KOH / g, and the acid value of masterbatch composition (7) was 14.9 mg KOH / g.

[0197] (Examples 9-31) <Preparation of Ink Compositions> After allowing the masterbatch compositions (1)-(8) prepared in Examples 1-8 to stand for 6 hours, the masterbatch compositions (1)-(8) and each compound listed in the (raw materials) column above were mixed and stirred in the composition ratios shown in Tables 3-1-3-2 to prepare the ink compositions (1)-(23) of Examples 8-31. Then, according to the evaluation procedure described above, the acid value and ΔL* were evaluated for each ink composition. １ / a* １ / b* １ The viscosity was measured, and the color difference ΔE and viscosity change rate (%) were calculated. Furthermore, the storage stability of each ink composition was evaluated according to the evaluation procedure described above. The results are shown in Tables 3-1 to 3-2.

[0198] (Comparative Examples 1-21) Using each compound listed in the (raw materials) section above, comparative ink compositions (1) to (21) of Comparative Examples 1-21 were prepared by performing a series of continuous mixing operations in the composition ratios shown in Table 4 without preparing a masterbatch. Then, according to the evaluation procedure described above, the acid value and ΔL* were evaluated for each comparative ink composition. １ / a* １ / b* １ The viscosity was measured, and the difference in the corresponding masterbatch composition was calculated to determine the color difference ΔE and viscosity change rate (%). Furthermore, the storage stability of each ink composition was evaluated according to the evaluation procedure described above. The results are shown in Table 4. From the experimental results in Tables 3 and 4 below, it was confirmed that the ink composition obtained from the masterbatch composition of this example exhibits excellent storage stability, excellent color development with little change in color difference, and maintains low viscosity for a long period of time. Note that the numbers for the composition ratio (parts by mass) in Tables 2 to 6 below represent the total mass of the component including the liquid when the component is a liquid containing solids.

[0199]

[0200]

[0201]

[0202]

[0203] (Examples 32-62) <Preparation of Ink Compositions> After allowing the masterbatch compositions (1) to (8) prepared in Examples 1 to 8 to stand for 6 hours, the masterbatch compositions (1) to (8) and each compound listed in the (raw materials) column above were mixed and stirred in the composition ratios shown in Tables 5-1 to 5-2 to prepare the ink compositions (24) to (54) of Examples 32 to 62. Then, according to the evaluation procedure described above, the acid value and ΔL* were evaluated for each ink composition. １ / a* １ / b* １ The viscosity was measured, and the color difference ΔE and viscosity change rate (%) were calculated. Furthermore, the storage stability of each ink composition was evaluated according to the evaluation procedure described above. The results are shown in Tables 5-1 to 5-2.

[0204] (Comparative Examples 22-48) Using each compound listed in the (raw materials) section above, comparative ink compositions (22) to (48) were prepared by performing a series of continuous mixing operations in the composition ratios shown in Tables 6-1 to 6-2 without preparing a masterbatch. Then, according to the evaluation procedure described above, the acid value and ΔL* were evaluated for each comparative ink composition. １ / a* １ / b* １ The viscosity was measured, and the difference in the corresponding masterbatch compositions was calculated to determine the color difference ΔE and viscosity change rate (%). Furthermore, the storage stability of each ink composition was evaluated according to the evaluation procedure described above. The results are shown in Tables 6-1 to 6-2. From the experimental results in Tables 5-1 to 5-2 and Tables 6-1 to 6-2 below, it was confirmed that the ink compositions obtained from the masterbatch compositions of this example exhibit excellent storage stability, excellent color development with little change in color difference, and maintain low viscosity for a long period of time.

[0205]

[0206]

[0207]

[0208]

[0209] This application claims priority to Japanese Patent Application No. 2025-047530, filed on 21 March 2025, and the entire disclosure of said application is incorporated herein by reference.

Claims

1. A masterbatch composition containing a colorant, a polyurethane resin and / or a (meth)acrylic resin, and an organic solvent.

2. A masterbatch composition for preparing an ink composition by blending an additive, wherein the additive is blended in an amount of 1 to 10 parts by mass per 100 parts by mass of the masterbatch composition, according to claim 1.

3. The masterbatch composition according to claim 2, wherein the additive contains one or more selected from the group consisting of an acidic resin, a curing agent, an antiblocking agent, an antistatic agent, a coating reinforcing agent, and an antifoaming agent.

4. The masterbatch composition according to claim 1 or 2, wherein the content of the coloring agent is 5 to 40% by mass with respect to the total amount (100% by mass) of the masterbatch composition.

5. The masterbatch composition according to claim 1 or 2, wherein the content of the polyurethane resin and / or the (meth)acrylic resin is 5 to 30% by mass with respect to the total amount (100% by mass) of the masterbatch composition.

6. The masterbatch composition according to claim 1 or 2, wherein the concentration of urethane groups in the polyurethane resin in the entire masterbatch composition is 0.3 mmol / g or more and 1.5 mmol / g or less.

7. The masterbatch composition according to claim 2, wherein the white color difference ΔE*ab calculated from L*, a*, and b* measured by the SCE method using a spectrophotometer before and after mixing with the additive is 2 or less.

8. The percentage change in viscosity of the composition before and after mixing with the additive is given by the following formula (1): Percentage change in viscosity (%) = |({η ｍｉｘ -η ｍ } / η ｍ ) | × 100 < 15 (In the above equation (1), η ｍｉｘ η represents the viscosity of the mixture of the masterbatch composition and the additive at 25°C, ｍ ) represents the viscosity of the masterbatch composition at 25°C. The masterbatch composition according to claim 2 or 7, satisfying the following conditions.

9. The masterbatch composition according to claim 1 or 2, wherein the acid value of the entire masterbatch composition is in the range of 0 mg KOH / g or more and 30 mg KOH / g or less.

10. A method for producing an ink composition, comprising: a masterbatch preparation step of preparing a masterbatch composition according to claim 1, which contains a colorant, a polyurethane resin and / or a (meth)acrylic resin, and an organic solvent; an additive preparation step of preparing an additive; and an additive step of adding the additive to the masterbatch composition.

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