Resin, resin dispersion, and resin composition

Abstract

Provided is a resin which has high storage stability even when contained in a resin composition, and which is capable of forming a coating film of the resin composition having solvent resistance on the coated surface thereof by being contained in the resin composition. The resin contains a copolymer containing the following monomer A and monomer B as structural units. Monomer A: a monomer having at least one ring structure selected from the group consisting of an alicyclic structure, a heterocyclic structure, and an aromatic ring structure; monomer B: a monomer having an acidic group or a basic group.

Description

Technical Field

[0001] The present invention relates to resins, resin dispersions and resin compositions. Background Art

[0002] As resin compositions, various compositions such as compositions for forming a recording layer on the surface of a substrate (recording medium) etc. by dissolving or dispersing various coloring materials in a solvent, and overcoat inks for forming an overcoat layer on the surface of a recorded object are known to contain a resin in order to impart abrasion resistance to the surface of the substrate.

[0003] Among such resins, resin dispersions containing a dispersible resin dispersed in water or water and a water-soluble organic solvent are known. For example, Patent Document 1 describes a technique related to an acrylic resin emulsion obtained by emulsion polymerization of an amino group-containing acrylic monomer and a monomer mainly composed of an alkyl (meth)acrylate in the presence of a cationic or nonionic emulsifier, wherein the amino group-containing acrylic monomer is partially or completely neutralized with an organic acid.

[0004] Patent Document 1 describes that the acrylic resin emulsion has excellent water resistance.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2002-322218 Summary of the invention

[0008] Problems to be solved by the invention

[0009] In addition, the resin composition applied to the surface of various substrates contains a liquid medium (including a solvent and a liquid dispersion medium). Then, the resin composition is attached to the surface of the substrate (recording medium), the recorded object, etc., the liquid medium contained in the resin composition volatilizes, and the resin and other components are fixed on their surfaces to form layers with respective functions such as a recording layer, a primer layer, and an overcoat layer. On the other hand, from the viewpoint of productivity, it is preferred to dry at as low a temperature as possible to form layers with respective functions.

[0010] However, studies by the present inventors have revealed that if a resin composition attached to a surface of a substrate (recording medium) is dried at low temperature, film-forming properties become insufficient, which affects the solvent resistance of the obtained recorded material.

[0011] In addition, when the resin contained in the resin composition aggregates in the resin composition, the properties of the resin composition may change, such as a change in viscosity of the resin composition. Thus, the resin composition is preferably a resin composition with high storage stability.

[0012] An object of the present invention is to provide a resin which has high storage stability even when contained in a resin composition and which can form a coating film of the resin composition having solvent resistance on the coated surface thereof by containing the resin in the resin composition.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies to solve the above problems and have found that a resin containing a copolymer including a specific monomer as a structural unit can solve the above problems, thereby completing the present invention. Specifically, the present invention provides the following solutions.

[0015] (1) A resin comprising a copolymer comprising the following monomer A and monomer B as structural units.

[0016] Monomer A: A monomer having at least one ring structure selected from an alicyclic structure, a heterocyclic structure, and an aromatic ring structure

[0017] Monomer B: Monomer with acidic or basic groups

[0018] (2) A resin dispersion comprising the resin according to claim 1 as a polymer fine particle dispersion.

[0019] (3) The resin dispersion according to (2), wherein the resin contained in the polymer fine particle dispersion is an emulsion polymer.

[0020] (4) The resin dispersion according to (2) or (3), wherein the content of unreacted monomers derived from the copolymer is 0.1% by mass or less in the total amount of the resin dispersion.

[0021] (5) The resin dispersion according to any one of (2) to (4), wherein the monomer A has a side chain portion SP value calculated from the chemical structure defined by R2 in the following formula (1) of 8.0 to 11.0.

[0022] CH2=C(R1)-R2 ···Formula (1)

[0023] (R1 is hydrogen or methyl)

[0024] (6) The resin dispersion according to any one of (2) to (5), wherein the partition coefficient (LogP) of the monomer A in water / 1-octanol is 1.9 to 4.8.

[0025] (7) The resin dispersion according to any one of (2) to (6), wherein Tg of the resin is 0° C. or higher and 120° C. or lower.

[0026] (8) The resin dispersion according to any one of (2) to (7), wherein the monomer A is contained in a ratio of 50% or more in the total amount of the copolymer.

[0027] The monomer B is contained in a ratio of 0.1% to 10% in the total amount of the copolymer.

[0028] (9) A resin composition comprising the resin dispersion according to any one of (2) to (8).

[0029] Effects of the Invention

[0030] The resin of the present invention has high storage stability even when contained in a resin composition, and by containing the resin in a resin composition, a coating film of the resin composition having solvent resistance can be formed on the surface to which the resin is applied. DETAILED DESCRIPTION

[0031] Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all and can be implemented with appropriate modifications within the scope of the purpose of the present invention.

[0032] 《1. Resin》

[0033] The resin of the present embodiment is characterized by containing a copolymer including the following monomer A and monomer B as structural units.

[0034] Monomer A: A monomer having at least one ring structure selected from an alicyclic structure, a heterocyclic structure, and an aromatic ring structure

[0035] Monomer B: Monomer with acidic or basic groups

[0036] A resin composition containing a copolymer including such a monomer as a structural unit has high storage stability, and by containing the copolymer in the resin composition, a coating film of the resin composition having solvent resistance can be formed on the surface to be coated.

[0037] In this specification, for convenience, a constituent monomer refers to a monomer before the reaction that constitutes a polymer, and is explained as a polymerizable compound having a reactive group such as an ethylenically unsaturated multiple bond. However, in fact, when a monomer is included as a structural unit, it is not included in the state of a monomer before the reaction, but is included in the form of a monomer after polymerization that constitutes a copolymer after one of the multiple bonds is polymerized and disappears.

[0038] In addition, the monomer may be any polymerizable compound of a monomer having a reactive group such as an ethylenically unsaturated multiple bond, and even a monomer having a large molecular weight such as an oligomer is referred to as a monomer in the present specification.

[0039] Hereinafter, the monomer A, the monomer B, and other monomers constituting the copolymer will be described.

[0040] (Monomer A)

[0041] The monomer A refers to a monomer having at least one ring structure selected from an alicyclic structure, a heterocyclic structure, and an aromatic ring structure.

[0042] By having such a ring structure in the side chain part of the monomer, the film-forming property of the resin composition is improved even when drying at a low temperature, and a coating film of the resin composition having solvent resistance can be formed.

[0043] Examples of the alicyclic structure include cycloalkanes (e.g., cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane) which are monocyclic compounds consisting of three or more carbon-carbon single bonds, and cycloalkanes (e.g., dicyclopentane, norbornane, and adamantane) which are polycyclic compounds.

[0044] The heterocyclic structure refers to a cyclic compound containing carbon and one or more other elements (for example, at least one selected from oxygen, nitrogen, sulfur, phosphorus, boron, and silicon) in the ring.

[0045] The aromatic ring structure refers to a cyclic hydrocarbon showing aromaticity, such as a benzene ring and a naphthalene ring.

[0046] In addition, in these monomers A, the SP value calculated for the chemical structure portion defined by R2 in the following formula (1), that is, the side chain portion SP value is preferably 12.0 or less.

[0047] CH2=C(R1)-R2 ···Formula (1)

[0048] (R1 is hydrogen or methyl)

[0049] Here, the side chain part SP value refers to the SP value (solubility parameter) of the "-R2" part of formula (1). In the same way as the SP value, the functional groups constituting "-R2" are decomposed, and the total value of ΔEoh (cal / mol) is defined as A, and the total value of ΔV (cm 3 / mol) is defined as the √(A / B) value at B. It should be noted that ΔEoh and ΔV are values ​​inherent to each substituent, and refer to the values ​​of Fedors. For example, in the case of butyl acrylate (or butyl methacrylate), "-R2" is "-COO-(CH2)3-CH3", so when calculating using ΔEoh and ΔV in Table 1 below, the side chain part SP value = √((1125+1180×3+4300) / (33.5+16.1×3+18.0)) = 9.48.

[0050] [Table 1]

[0051]

[0052] By setting the SP value of the side chain portion of the monomer A to be within a predetermined range, the solvent resistance (particularly, ethanol resistance) of the obtained recorded object can be improved.

[0053] According to the research conducted by the present inventors, the physical properties of a coating film containing a polymer are often greatly affected by the side chain portion of the polymer rather than by the main chain of the polymer contained in the coating film. It is believed that by including a monomer as a structural unit in which the SP value of the "-R2" portion of formula (1), i.e., the SP value of the side chain portion, is controlled within a predetermined range, the physical properties of the coating film can be affected, and a coating film that exerts the effect of the present invention can be formed.

[0054] And, usually SP value is called solubility parameter, and the difference of SP value of known 2 kinds of components is smaller, and then solubility is higher.Because the SP value of ethanol is 12.7, therefore the more away from this value, then as coating film, the solvent resistance to ethanol is higher.On the other hand, when utilizing polymer microparticle dispersion to form coating film, microparticles are welded by water-soluble solvent each other, and resin chain diffuses, thus forms firm coating film.Therefore, solubility in water-soluble solvent is also needed to a certain extent.Therefore, think that by being set to above scope by SP value, thereby diffuse to a certain extent and become firm coating film relative to water-soluble solvent, on the other hand, become the coating film that is difficult to swell relative to solvents such as ethanol, can improve solvent resistance.

[0055] It should be noted that the side chain part SP value is preferably 8.0 or more, more preferably 8.5 or more, and further preferably 9.5 or more. The side chain part SP value is preferably 11.0 or less, more preferably 10.5 or less, and further preferably 10.0 or less. Thereby, the solvent resistance (especially ethanol resistance) of the obtained recorded material can be improved. The side chain part SP value is preferably 8.0 or more and 11.0 or less, more preferably 8.5 or more and 10.5 or less, and further preferably 9.5 or more and 10.0 or less.

[0056] In addition, in these monomers A, when the molar volume of the "-R2" part of the structural part of formula (1) is defined as the molar volume of the side chain part, the molar volume of the side chain part is not particularly limited, but is preferably 170 or less. Here, the molar volume of the side chain part refers to the molar volume of the "-R2" part of formula (1), and refers to the calculation of the ΔV (cm) of the constituent functional groups by using the Fedors value as a reference in the same way as the calculation of the side chain SP value. 3 By setting the molar volume of the side chain portion to 170 or less, the "-R2" portion of the monomer A does not become too large, and thus a coating film having higher adhesion to various substrates (recording media) can be formed.

[0057] In addition, the distribution coefficient (LogP) of the monomer A in water / 1-octanol is preferably greater than 1.0. By including a "distribution coefficient (LogP) in water / 1-octanol" that is greater than or equal to a prescribed value (i.e., a relatively hydrophobic monomer) as a structural unit, a copolymer that is not easily swollen in solvents such as ethanol is obtained. Therefore, if the distribution coefficient (LogP) of monomer A in water / 1-octanol is within a prescribed range, a coating film of a resin composition having greater solvent resistance can be formed. In addition, in the case where the resin of the present embodiment is contained in a resin dispersion in the form of a polymer particle dispersion (especially a resin emulsion), by making the "distribution coefficient (LogP) in water / 1-octanol" greater than or equal to a prescribed value, it can react effectively in the polymer particle dispersion (especially micelles) and can reduce the content of unreacted monomers. Furthermore, by making the "distribution coefficient in water / 1-octanol (LogP)" below a specified value, the hydrophobicity of the monomer A can be reduced, and free radicals from the polymerization initiator can easily enter the polymer fine particle dispersion (particularly micelles), allowing the reaction to proceed efficiently, thereby reducing the content of unreacted monomers.

[0058] It should be noted that the partition coefficient (LogP) of monomer A in water / 1-octanol is preferably 1.5 or more, more preferably 2.0 or more, and further preferably 2.5 or more. The partition coefficient (LogP) of monomer B in water / 1-octanol is preferably 4.8 or less, more preferably 4.0 or less, and further preferably 3.5 or less. The partition coefficient (LogP) of monomer A in water / 1-octanol is preferably 1.5 or more and 4.8 or less, more preferably 2.0 or more and 4.0 or less, and further preferably 2.5 or more and 3.5 or less.

[0059] The Tg of the homopolymer of the monomer A is preferably 0°C or higher, more preferably 10°C or higher, and further preferably 15°C or higher. By setting the Tg of the homopolymer of the monomer A to be 0°C or higher, the friction resistance of the obtained recorded material can be improved. The Tg of the homopolymer of the monomer A is preferably 120°C or lower, and more preferably 115°C or lower. Thus, even when dried at a low temperature, sufficient film formation can be achieved, and the solvent resistance of the obtained recorded material can be further improved. The Tg of the homopolymer of the monomer A is preferably 0°C or higher and 120°C or lower, more preferably 10°C or higher and 115°C or lower, and further preferably 15°C or higher and 115°C or lower.

[0060] Examples of monomer A include cyclohexyl acrylate (side chain SP value: 9.96, LogP: 2.760±0.226, Tg: 19°C, molar volume: 113.5 cm 3 / mol), cyclohexyl methacrylate (side chain SP value: 9.96, LogP: 3.179±0.252, Tg: 83℃, molar volume: 113.5cm 3 / mol), phenyl acrylate (side chain SP value: 10.75, LogP: 1.940±0.404, Tg: 57℃, molar volume: 105.4cm 3 / mol), phenyl methacrylate (side chain SP value: 10.75, LogP: 2.359±0.429, Tg: 110℃, molar volume: 105.4cm 3 / mol), benzyl acrylate (side chain SP value: 10.49, LogP: 2.109±0.230, Tg: 6℃, molar volume: 121.5cm 3 / mol), benzyl methacrylate (side chain SP value: 10.49, LogP: 2.527±0.255, Tg: 54°C, molar volume: 121.5cm 3 / mol), isobornyl acrylate (side chain SP value: 9.42, LogP: 4.029±0.273, Tg: 97℃, molar volume: 158.4cm 3 / mol), isobornyl methacrylate (side chain SP value: 9.42, LogP: 4.447±0.301, Tg: 180℃, molar volume: 158.4cm 3 / mol), phenoxyethyl acrylate (side chain SP value: 10.42, LogP: 2.371±0.246, Tg: -22℃, molar volume: 141.4cm 3 / mol), phenoxyethyl methacrylate (side chain SP value: 10.42, LogP: 2.790±0.268, Tg: -3℃, molar volume: 141.4cm 3 / mol), dicyclopentyl acrylate (side chain SP value: 10.31, LogP: 3.957±0.244, Tg: 120℃, molar volume: 141.5cm 3 / mol), dicyclopentyl methacrylate (side chain SP value: 10.31, LogP: 4.375±0.266, Tg: 175℃, molar volume: 141.5cm 3 / mol), styrene (side chain part SP value: 9.50, LogP: 2.821±0.191, Tg: 100℃, molar volume: 87.4cm 3 / mol), 4-acryloylmorpholine (side chain part SP value: 12.95, LogP: -0.689±0.441, Tg: 145℃, molar volume: 76.5cm 3 / mol), tetrahydrofurfuryl methacrylate (side chain SP value: 10.37, LogP: 1.399±0.340, Tg: 60℃, molar volume: 101.2cm 3 / mol), cyclic trimethylolpropane formal acrylate (side chain SP value: 9.96, LogP: 1.032±0.361, Tg: 27℃), n-butyl cyclohexyl acrylate (side chain SP value: 9.35, LogP: 5.243±0.255), 3,3,5-trimethylcyclohexyl acrylate (side chain SP value: 9.12, LogP: 4.212±0.254, Tg: 52℃, molar volume: 161.6cm 3 / mol), 4-tert-butylcyclohexyl acrylate (side chain SP value: 9.08, LogP: 4.570±0.243, Tg: 81℃, molar volume: 177.7cm 3 / mol), 4-chlorophenyl acrylate (side chain SP value: 11.63, LogP: 2.743±0.418, Tg: 60℃), hydroxycyclohexyl methacrylate (side chain SP value: 13.02, LogP: 1.230±0.281, Tg: 93℃, molar volume: 106.4cm3 / mol), cyclooctyl methacrylate (side chain SP value: 9.67, LogP: 4.233±0.253), cycloheptyl methacrylate (side chain SP value: 9.80, LogP: 3.706±0.252), naphthyl methacrylate (side chain SP value: 9.86, LogP: 4.831±0.260, Tg: 143℃), cyclopentyl methacrylate (side chain SP value: 9.86, LogP: 4.831±0.260, Tg: 143℃), Ester (side chain part SP value: 10.18, LogP: 2.652±0.252), cyclobutyl methacrylate (side chain part SP value: 10.63, LogP: 2.125±0.252), cyclopropyl methacrylate (side chain part SP value: 11.07, LogP: 1.598±0.252), tert-butyl cyclohexyl methacrylate (side chain part SP value: 9.08, LogP: 4.570±0.243, Tg: 81°C), vinyl cyclohexane (side chain part SP value: 8.54, LogP: 3.799±0.193, Tg: 134°C), tert-butyl-4-ethynyl cyclohexane (side chain part SP: 8.04, LogP: 5.609±0.219), etc. Among them, monomer A is preferably an acrylate monomer or a methacrylate monomer. These monomers A may be used alone or in combination. It should be noted that the "side chain part SP value" in the brackets refers to the SP value calculated for the chemical structure part defined by R2 in formula (1), the "LogP" in the brackets refers to the partition coefficient (LogP) in water / 1-octanol, and the "Tg" in the brackets refers to the Tg of the homopolymer of the monomer.

[0061] It should be noted that the monomer A may include a monomer having two or more ethylenically unsaturated bonds, and the monomer A is preferably composed of a monomer having only one ethylenically unsaturated bond. Thus, the brittleness of the coating film caused by the increase in the crosslinking points of the resin is alleviated, and the solvent resistance and stretchability of the obtained recorded material can be further improved.

[0062] The content of monomer A as a constituent monomer is not particularly limited, and the lower limit of the content of monomer A is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more in the total amount of the copolymer. Thus, the content of monomer A having a ring structure increases, so the film-forming property of the resin composition is more effectively improved, and a coating film of the resin composition having a higher solvent resistance can be formed.

[0063] (Monomer B)

[0064] Monomer B refers to a monomer having an acidic group or a basic group. By including a monomer having an acidic group or a basic group, the storage stability of the resin composition can be made high. In particular, when dispersed in a resin dispersion or a resin composition as a polymer particle dispersion, the dispersion stability of the polymer particle dispersion is improved by imparting electrostatic repulsion to the polymer particle dispersion, so the dispersion stability of the resin can be improved. It should be noted that the acidic group or the basic group of monomer B can remain intact, or can be neutralized and become a state of a neutralized salt.

[0065] Examples of the acidic group possessed by the monomer B include a carboxyl group, a sulfo group, and a phosphoric acid group. Among them, a carboxyl group is preferred.

[0066] Examples of the basic group possessed by the monomer B include amino groups (—NH 2 , —NHR, and —NRR′), etc. Among them, a tertiary amino group (—NRR′) is preferred.

[0067] Specific examples of monomer B include acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, mono-2-(methacryloyloxy)ethyl phthalate, mono-hydroxyethyl phthalate, ω-carboxyl-polycaprolactone (n≈2) monoacrylate, 4-carboxystyrene, 6-acrylamidocanoic acid, 2-(dimethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, dimethylaminopropyl acrylamide, 2-aminoethyl methacrylate, 2-aminoethyl methacrylamide, N-(3-aminopropyl) methacrylamide, 2-(diisopropylamino)ethyl methacrylate, and N-(2-dimethylaminoethyl) methacrylamide. These monomers B can be used alone or in combination. It should be noted that these monomers B can remain as they are or in the state of neutralized salts.

[0068] The content of the monomer B as a constituent monomer is not particularly limited, but the lower limit of the content of the monomer B is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more in the total amount of the copolymer. Thus, the storage stability of the resin dispersion or resin composition containing the copolymer can be more effectively improved.

[0069] The upper limit of the content of monomer B is preferably below 20.0% by mass, more preferably below 15.0% by mass, and further preferably below 10.0% by mass in the total amount of the copolymer. Thus, the content of monomer A in the copolymer can be relatively increased, so that, as a result, a coating film of a resin composition having more solvent resistance can be formed.

[0070] The content of the monomer B is preferably in the range of 0.1 mass % to 20.0 mass % in the total amount of the copolymer, more preferably 0.5 mass % to 15.0 mass %, further preferably 1.0 mass % to 10.0 mass %.

[0071] (Other monomers)

[0072] The copolymer contained in the resin composition of the present embodiment may or may not contain other monomers different from the monomer A and the monomer B as structural units. As other monomers, methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isodecyl (meth)acrylate, trifluoroethyl (meth)acrylate), dimethylacrylamide, diethylacrylamide, hydroxyethylacrylamide, isopropylacrylamide, etc. can be cited. These other monomers can be used alone or in combination of multiple monomers.

[0073] For example, for a polymer containing a monomer containing a carbonyl group as a structural unit in the resin structure, a compound having a functional group that can react with the carbonyl group is added as a crosslinking agent, thereby introducing a crosslinking structure into the resin containing the polymer. Therefore, by using a resin composition containing such a polymer containing a monomer containing a carbonyl group as a structural unit, the friction resistance of the obtained coating film can be improved.

[0074] Among such monomers containing a carbonyl group, examples of the carbonyl group-containing monofunctional ethylenically unsaturated monomer include 2-(acryloylamino)-2-methyl-4-pentanone (side chain portion SP value: 12.04, LogP: 0.037±0.287), acrolein (side chain portion SP value: 15.47, LogP: 0.263±0.283), N-vinylformamide (side chain portion SP value: 19.72, LogP: 0.525±0.215), methyl vinyl ketone (side chain portion SP value: 10.91, LogP: 0.142±0.249), and ethyl vinyl ketone (side chain portion SP value: 10.34, LogP: 0.652±0.249), 2-(acetoacetoxy)ethyl acrylate (side chain SP value: 11.73, LogP: 0.331±0.356), 2-(acetoacetoxy)ethyl methacrylate (side chain SP value: 11.73, LogP: 0.750±0.385), 2-(acetoacetoxy)propyl acrylate (side chain SP value: 11.43, LogP: 0.635±0.350), 2-(acetoacetoxy)propyl acrylate (side chain SP value: 11.43, LogP: 1.054±0.378), etc. However, the "water / 1-octanol partition coefficient (LogP)" of these monomers is 0 to 1.1, and they are relatively hydrophilic monomers. Thus, if the resin composition contains a polymer containing a monomer containing a carbonyl group as a structural unit, there is a tendency that the solvent resistance of the obtained coating film is relatively reduced. Therefore, the resin of the present embodiment may contain a polymer containing a monomer containing a carbonyl group as a structural unit, but unless a crosslinking agent is particularly added to introduce a crosslinking structure into the resin containing the polymer, it is preferred not to contain a polymer containing a monomer containing a carbonyl group as a structural unit.

[0075] It should be noted that the other monomers may include monomers having two or more ethylenically unsaturated bonds, and the other monomers are preferably composed of monomers having only one ethylenically unsaturated bond. Thus, the brittleness of the coating film caused by the increase in crosslinking points of the resin is alleviated, and the solvent resistance and stretchability of the obtained recorded material can be further improved.

[0076] The content of other monomers is not particularly limited, but the upper limit of the content of other monomers is preferably 45% by mass or less, more preferably 35% by mass or less, and further preferably 20% by mass or less, based on the total amount of the copolymer.

[0077] [Copolymer]

[0078] The resin of this embodiment contains a copolymer including monomer A and monomer B as structural units. Even if such a copolymer is contained in the resin composition, the storage stability is high, and by containing such a copolymer in the resin composition, a coating film of the resin composition having solvent resistance can be formed on the coated surface.

[0079] The polymer may be dissolved in a resin composition or a resin dispersion, but preferably at least a part of it is contained as a polymer particle dispersion. A polymer particle dispersion refers to a resin having dispersibility such as a resin emulsion in which a resin is dispersed in a resin composition in the form of resin particles by electrostatic repulsion, or a colloidal dispersion containing a partially dissolved resin. By containing a polymer particle dispersion as a binder resin, dispersion stability, ejection stability, etc. can be made into preferred properties.

[0080] The copolymer can be obtained by polymerizing monomers by a conventionally known free radical polymerization method such as emulsion polymerization method, suspension polymerization method, etc. Among them, the copolymer is preferably an emulsion polymer.

[0081] When a copolymer is obtained by polymerizing a monomer by emulsion polymerization, other components such as an emulsifier, a polymerization initiator, a polymerization regulator, a crosslinking agent, a neutralizer, and a film-forming aid may be used as appropriate.

[0082] When a copolymer is obtained by polymerizing a monomer by emulsion polymerization, for example, there can be mentioned a method of mixing the components and heating them up, a method of mixing a part of the components and heating them up, and then adding the remaining monomer components to polymerize, and a method of mixing components other than the monomers and heating them up, and then adding the monomer components to polymerize.

[0083] As emulsifiers, anionic, cationic and nonionic surfactants can be cited. Among them, it is preferred to use a non-reactive emulsifier that does not have multiple bonds in the structure (that is, the resin contained as the polymer particle dispersion contains a non-reactive emulsifier). By dispersing the copolymer obtained by using the non-reactive emulsifier as a polymer particle dispersion in a resin composition or a resin dispersion, the dispersion stability of the copolymer can be improved, and as a result, the storage stability can be further improved.

[0084] Examples of the non-reactive emulsifier include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium tetradecyl sulfate and other alkyl sulfates, ammonium lauryl sulfate, sodium diphenyl ether sulfonate, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, and the like. Specific examples include "ADEKA Pluronic L-31", "ADEKA Pluronic P-85", "ADEKA Pluronic F-108", "ADEKA TOL LB-83", "ADEKA TOL SO-145", "ADEKA HOPE YES-25", "ADEKA MINE 4MAC-30", "ADEKA MINE 4MT-50", "ADEKA COL TS-230E", "ADEKA COL PS-810E" (all manufactured by ADEKA Corporation), "EMULGEN 120", "EMULGEN 147", "EMULGEN 109P", "EMULGEN 210P", "EMULGEN 306P", "EMULGEN 409PV", "EMULGEN 420", "EMULGEN 709", "EMULGEN 1108", "EMULGEN 1118S-70", "EMULGEN 1150S-60", "EMULGEN 1135S-70", "EMULGEN 4085", "EMULGEN 2020G-HA", "EMULGEN A-60", "EMULGEN A-90", "EMULGEN A-500", "EMULGEN LS-110", "EMULGEN G2E-4", "EMAL 2FG", "EMAL 20CM", "EMAL 270J", "LATEMUL AD-25", "LATEMUL E-1000A", "ACETAMIN 24", "QUARTAMIN 60W", "SANISOL C", "EMANON 1112" (all manufactured by Kao Corporation) and the like. These may be used alone or in combination of two or more.

[0085] Specific examples of the reactive emulsifier include "ADEKA REASOAP SE-20N", "ADEKA REASOAP SE-10N", "ADEKA REASOAP PP-70", "ADEKA REASOAP PP-710", "ADEKA REASOAP SR-10", "ADEKA REASOAP SR-20" [all manufactured by ADEKA Corporation], "ELEMINOL JS-2", "ELEMINOL RS-30" [all manufactured by Sanyo Chemical Industries, Ltd.], "LATEMUL S-180A", "LATEMUL S-180", "LATEMUL PD-104" [all manufactured by Kao Corporation], "AQUALON BC-05", "AQUALON BC-10", "AQUALON BC-20", "AQUALON HS-05", "AQUALON HS-10", "AQUALON HS-20", "NEW FRONTIER Commercially available products include ADEKA REASOAP NE-10, ADEKA REASOAP NE-20, ADEKA REASOAP NE-30, ADEKA REASOAP NE-40, ADEKA REASOAP ER-10, ADEKA REASOAP ER-20, ADEKA REASOAP ER-30, ADEKA REASOAP ER-40, ADEKA REASOAP ER-10, ADEKA REASOAP ER-20, ADEKA REASOAP ER-30, ADEKA REASOAP ER-40, ADEKA REASOAP ER-40, ADEKA REASOAP 10, ADEKA REASOAP 20, ADEKA REASOAP 30, ADEKA REASOAP ...40, ADEKA REASOAP 10, ADEKA REASOAP 20, AQUALON RN-20, AQUALON RN-30, AQUALON RN-50, ADEKA REASOAP 50, ADEKA REASOAP 50

[0086] The amount of the emulsifier used can be appropriately adjusted, and is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more, relative to 100 parts by mass of the monomer, in terms of solid content conversion. The amount of the emulsifier used is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less, relative to 100 parts by mass of the monomer, in terms of solid content conversion. The amount of the emulsifier used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and further preferably 1 part by mass or more and 10 parts by mass or less.

[0087] Examples of the polymerization initiator include alkyl peroxides, tert-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, tert-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, diisobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and organic peroxides such as tert-butyl peroxyisobutyrate; 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2- methylbutyronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, ammonium (amine) salt of 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis(2-methylamide oxime) dihydrochloride, 2,2'-azobis(2-methylbutyramide oxime) dihydrochloride tetrahydrate, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]-propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], various redox catalysts (in this case, as the oxidizing agent, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, methane hydroperoxide, etc. can be used, and as the reducing agent, sodium sulfite, acidic sodium sulfite, Rongalite, ascorbic acid, etc. can be used.) and the like. These polymerization initiators can be used alone or in combination of two or more.

[0088] The amount of polymerization initiator used is appropriately adjusted, and relative to 100 parts by mass of monomer, it is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and more preferably 0.05 parts by mass or more. The amount of polymerization initiator used is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 1 part by mass or less relative to 100 parts by mass of monomer. The amount of polymerization initiator used is preferably 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.03 parts by mass or more and 3 parts by mass or less, and more preferably 0.05 parts by mass or more and 1 part by mass or less relative to 100 parts by mass of monomer.

[0089] Examples of the polymerization regulator include alcohols such as methanol, ethanol, propanol, and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, furfural, and benzaldehyde; and mercaptans such as n-dodecyl mercaptan, thioglycolic acid, octyl thioglycolate, and thioglycerol. These may be used alone or in combination of two or more.

[0090] The amount of polymerization regulator used is appropriately adjusted, preferably 0.01 mass parts or more, more preferably 0.05 mass parts or more, and more preferably 0.1 mass parts or more relative to 100 mass parts of monomers. The amount of polymerization regulator used is preferably 10 mass parts or less relative to 100 mass parts of monomers, more preferably 5 mass parts or less, and more preferably 3 mass parts or less. The amount of polymerization regulator used is preferably 0.01 mass parts or more and 10 mass parts or less relative to 100 mass parts of monomers, more preferably 0.05 mass parts or more and 5 mass parts or less, and more preferably 0.1 mass parts or more and 3 mass parts or less.

[0091] A crosslinking agent may be used, but preferably no crosslinking agent is used (ie, the resin does not contain a crosslinking agent). By including a copolymer that does not contain a crosslinking agent in a resin composition or a resin dispersion, storage stability can be improved.

[0092] When a cross-linking agent is contained, examples of the plasticizer include, in addition to aliphatic dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide, carbonate polyhydrazide, aliphatic, alicyclic, and aromatic bisaminourea, aromatic dicarboxylic acid dihydrazide, polyhydrazide of polyacrylic acid, dihydrazide of aromatic hydrocarbons, hydrazine-pyridine derivatives, and dihydrazides of unsaturated dicarboxylic acids such as maleic acid dihydrazide.

[0093] The neutralizing agent is used to neutralize, for example, an acidic group or a basic group derived from the monomer B. In the case where the copolymer contains a monomer B having an acidic group or a basic group as a structural unit, by neutralizing the acidic group or the basic group derived from the monomer B (that is, by the copolymer containing the monomer B having a neutralized acidic group or a basic group as a structural unit), a resin composition that more effectively exhibits the effect of the present invention is obtained.

[0094] Examples of the acid for neutralizing the basic group derived from the monomer B include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, propionic acid, benzoic acid, succinic acid, butyric acid, fumaric acid, p-toluenesulfonic acid, citric acid, and oxalic acid. Among them, benzoic acid is preferably used from the viewpoint of solvent resistance during low-temperature drying.

[0095] Examples of the base for neutralizing the acidic group derived from the monomer B include inorganic bases such as alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, isopropylamine, propanolamine, 2-methyl-2-aminopropanol, diethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, dimethylamine, triethylamine, dibutylamine, N,N-diethylethanolamine, N,N-dibutylaminoethanol, N- Amines such as (β-aminoethyl)ethanolamine, N-methylethanolamine, 2-ethylaminoethanol, mono-n-butylethanolamine, mono-n-butyldiethanolamine, n-tert-butyldiethanolamine, 3-methyl-2-oxazolidinone, n-(2-hydroxyethyl)morpholine, aminomethylpropylene glycol, aminoethylpropylene glycol, 2-(dimethylaminomethyl)-2-propanol, tris(hydroxymethyl)aminomethane, DL-2-amino-1-butanol, 3-amino-4-octanol, and triethanolamine tris(2-hydroxyethyl)amine. Among them, ammonia and N,N-dimethylethanolamine are preferably used from the viewpoint of solvent resistance during low-temperature drying.

[0096] The Tg of the resin of the present embodiment can be controlled by appropriately changing the types and contents of at least two monomers, namely, the monomer A and the monomer B, which comprise the copolymer containing the monomer A and the monomer B as structural units obtained in this way.

[0097] The Tg of the resin containing the copolymer is preferably 0° C. or higher and 120° C. or lower. By setting the Tg of the resin to 0° C. or higher, the friction resistance of the obtained recorded material is improved. By setting the Tg of the resin to 120° C. or lower, the film-forming property of the resin composition is improved even when dried at low temperatures, and a coating film of the resin composition having solvent resistance can be formed. In addition, the stretchability of the coating film of the resin composition can be improved.

[0098] It should be noted that the Tg of the resin containing the copolymer is more preferably 20°C or more, more preferably 30°C or more, and more preferably 40°C or more. The Tg of the resin containing the copolymer is more preferably 100°C or less, more preferably 90°C or less, and more preferably 80°C or less. The Tg of the resin containing the copolymer is preferably 0°C or more and 120°C or less, more preferably 20°C or more and 100°C or less, more preferably 30°C or more and 90°C or less, and more preferably 40°C or more and 80°C or less.

[0099] In addition, it is preferred to reduce the content of the unreacted monomers from the copolymer as much as possible. Due to the unreacted monomers from the copolymer, the coating film of the resin composition is sometimes relatively viscous. By reducing the content of the unreacted monomers from the copolymer, the anti-blocking property is improved, and the resin composition that more effectively exerts the effect of the present invention is formed.

[0100] Specifically, the content of unreacted monomers derived from the copolymer is preferably 0.15% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.08% by mass or less in the total amount of the resin (in the total amount of the resin dispersion). The anti-blocking property of the recorded material obtained by using the resin composition containing such a copolymer is improved.

[0101] It should be noted that the content of the unreacted monomer derived from the copolymer can be controlled by selecting a monomer A having a water / 1-octanol partition coefficient (LogP) within a predetermined range.

[0102] The arrangement of monomers contained in the copolymer comprising monomer A and monomer B as structural units can be a random copolymer in which the arrangement of monomers is disordered, or a block copolymer in which the same monomer is long and continuous, or a graft copolymer in which the monomers are arranged in a branched shape, preferably a random copolymer. By making the random copolymer comprising monomer A and monomer B as structural units disperse as a polymer particle dispersion, the dispersion stability of the copolymer can be improved. For example, in a resin composition containing the copolymer and spraying the resin composition onto the surface of a substrate by an inkjet method, the spraying stability can be improved.

[0103] The type of resin containing the copolymer containing monomer A and monomer B as structural units is not particularly limited, and for example, a resin containing one or more resins or copolymer resins selected from acrylic resins (including copolymers such as styrene-acrylic resins), polyurethane resins, polyester resins, vinyl chloride resins, vinyl acetate resins, polyether resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, acrylamide resins, epoxy resins, polycarbonate resins, silicone resins, and polystyrene resins, or a resin containing a mixture thereof can be used. Among them, acrylic resins are preferably contained.

[0104] In the case of containing a resin as a polymer particle dispersion, from the viewpoint of dispersion stability in the resin composition, the average particle size of the polymer particle dispersion is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more. From the viewpoint of dispersion stability and film-forming properties in the resin composition, the average particle size of the polymer particle dispersion is preferably 500 nm or less, more preferably 350 nm or less, and further preferably 200 nm or less. The average particle size of the polymer particle dispersion is preferably 10 nm or more and 500 nm or less, more preferably 20 nm or more and 350 nm or less, and further preferably 30 nm or more and 200 nm or less. It should be noted that the average particle size of the polymer particle dispersion can be measured using a thick particle size analyzer (Japanese: thick particle size analyzer) (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000) at a measurement temperature of 25 ° C.

[0105] From the viewpoint of film water resistance and stretchability, the weight average molecular weight of the polymer microparticle dispersion is preferably 5000 or more, more preferably 10000 or more, and further preferably 100000 or more. From the viewpoint of the storage stability of the resin composition, it is preferably 2000000 or less, more preferably 1750000 or less, and further preferably 1500000 or less. The weight average molecular weight of the polymer microparticle dispersion is preferably 5000 or more and 2000000 or less, more preferably 10000 or more and 1750000 or less, and further preferably 100000 or more and 1500000 or less. It should be noted that in the present embodiment, the molecular weight of the resin represents the weight average molecular weight Mw, which is a value measured by GPC (gel permeation chromatography), and can be measured by "HLC-8320GPC" manufactured by Tosoh Corporation with a polystyrene standard as the standard for the calibration curve.

[0106] 《2. Resin dispersion》

[0107] The resin dispersion of the present embodiment is a resin dispersion containing the following resin as a polymer particle dispersion, and the resin contains a copolymer containing the above-mentioned specific monomer as a structural unit. It should be noted that in this specification, the resin dispersion is mainly applied to the surface of a substrate (recording medium), etc., to form a recording layer, a primer layer, an outer coating layer, etc., which have their own functions, and is therefore different from a resin composition. The resin dispersion of the present embodiment is used to manufacture a resin composition for forming a coating film with a desired function, and the resin containing the copolymer containing the above-mentioned specific monomer as a structural unit is dispersed in a liquid dispersion medium such as water as a polymer particle dispersion. For example, by mixing the resin dispersion of the present embodiment and other components contained in the resin composition (such as colorants, cationic compounds, leveling agents, etc.), a resin composition can be manufactured.

[0108] Thus, by dispersing the copolymer containing the above-mentioned specific monomer as a structural unit in a liquid dispersion medium to prepare a resin dispersion, and further adding other components to the dispersion to produce a resin composition, the storage stability (dispersion stability) of the resin composition can be improved.

[0109] As the liquid dispersion medium, for example, water or a water-soluble organic solvent can be used. As the water or the water-soluble organic solvent, the water or the water-soluble organic solvent contained in the resin composition described below can be used.

[0110] 《3. Resin composition》

[0111] The resin composition of the present embodiment contains the above-mentioned resin dispersion. Since the resin composition contains a copolymer containing the above-mentioned specific monomer as a structural unit, the storage stability is high. In addition, by applying the resin composition on the surface of a substrate (recording medium), a recorded object, etc., a coating film of the resin composition having solvent resistance can be formed. It should be noted that in this specification, "resin composition" refers to a composition containing a resin or a resin dispersion (also referred to as a resin-containing composition or a resin-containing ink composition), and is used to include a composition that becomes a liquid (ink-like) by containing water or a water-soluble solvent described later as an arbitrary component.

[0112] It should be noted that the resin composition of the present embodiment may be a coloring ink containing a colorant. In this specification, "colorant" includes dyes and pigments, and is used as a concept including dyes or pigments contained in coloring inks that form images such as yellow, magenta, cyan, black, and their intermediate colors and light colors, white dyes or white pigments contained in white inks, and bright pigments contained in metallic inks.

[0113] The coloring ink may be yellow, magenta, cyan, black, or any intermediate or light color thereof, and may be a white ink containing a white colorant, or may be a metallic ink containing a bright pigment.

[0114] In addition, the resin composition of the present embodiment may be a receiving solution (Japanese: receiving solution) containing a cationic compound applied to the substrate before the colored ink is applied to the substrate. In addition, it may be a transparent ink without a colorant, a primer for forming a primer on the surface of a substrate, etc., an overcoat ink for forming an overcoat on the surface of a recorded object, etc., or a resin composition called a coating or a coating agent.

[0115] Hereinafter, each component contained in the resin composition of this embodiment will be described. Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate changes within the scope of the purpose of the present invention.

[0116] [Resin]

[0117] The resin used may be a resin containing a copolymer including the above-mentioned specific monomer as a structural unit.

[0118] In addition, the resin composition of the present embodiment may further contain a resin different from the copolymer containing monomer A and monomer B as structural units. As the resin, specifically, a resin containing one or more resins or copolymer resins selected from acrylic resins (including copolymers such as styrene-acrylic resins) different from the above copolymers, polyurethane resins, polyester resins, vinyl chloride resins, vinyl acetate resins, polyether resins, vinyl chloride-vinyl acetate copolymer resins, polyethylene resins, acrylamide resins, epoxy resins, polycarbonate resins, silicone resins, and polystyrene resins, or a resin containing a mixture thereof can be used.

[0119] Examples of commercially available polymer fine particle dispersions (resin emulsions) include ACRIT WEM-031U, WEM-200U, WEM-321, WEM-3000, WEM-202U, and WEM-3008 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic-urethane resin emulsions), ACRIT UW-550CS, UW-223SX, AKW107, and RKW-500 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic resin emulsions), LUBRIJET N240 (manufactured by Lubrizol, acrylic resin emulsions), SUPERFLEX 150, 210, 470, 500M, 620, 650, E2000, E4800, and R5002 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., urethane resin emulsions), and VINYBLAN 701FE35, 701FE50, 701FE65, 700, 701, 711, 737, 747 (Nissin Chemical Co., Ltd., vinyl chloride-acrylic resin emulsion), VINYBLAN 2706, 2685 (Nissin Chemical Co., Ltd., acrylic resin emulsion), Mowinyl 743N, 6520, 6600, 6820, 7470, 7720 (Japan Coating Resin, acrylic resin emulsion), PRIMAL AC-261P, AC-818 (Dow Chemical, acrylic resin emulsion), JE-1056 (Starlight PMC, acrylic resin emulsion), NeoCryl XK-190 (DSM Coating Resin, acrylic resin emulsion), NeoCryl A2091, A2092, A639, A655, A662 (styrene-acrylic resin emulsion manufactured by DSM Coating Resin Co., Ltd.), QE-1042, KE-1062 (styrene-acrylic resin emulsion manufactured by Starlight PMC Co., Ltd.), JONCRYL7199, PDX-7630A (styrene-acrylic resin emulsion manufactured by BASF Japan Co., Ltd.), CHALINE R170BX (silicone-acrylic resin emulsion manufactured by Nissin Chemical Industry Co., Ltd.), TAKELAC W-6010 (urethane resin emulsion manufactured by Mitsui Chemicals Co., Ltd.), elitel KA-5071S (polyester resin emulsion manufactured by Unitika Co., Ltd.), Polyzol AP-1350 (acrylic resin emulsion manufactured by Showa Denko Co., Ltd.), etc., but are not limited to these.

[0120] The content of resin is not particularly limited, and the lower limit of the content of resin is preferably 0.05% by mass or more in the total amount of the resin composition, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit of the content of resin is preferably 20% by mass or less in the total amount of the resin composition, more preferably 17.5% by mass or less, and further preferably 15% by mass or less. The range of the content of resin is preferably 0.05% by mass or more and 20% by mass or less in the total amount of the resin composition, more preferably 0.1% by mass or more and 17.5% by mass or less, further preferably 0.5% by mass or more and 15% by mass or less, and further preferably 1% by mass or more and 15% by mass or less.

[0121] [water]

[0122] The resin composition of the present embodiment contains water. As water, various ions are not contained, and deionized water is preferably used. As the content of water, as long as each component can be dispersed or dissolved, there is no particular limitation, and the lower limit of the content of water is preferably in the range of more than 30 mass % in the total amount of the resin composition, more preferably in the range of more than 45 mass %, and more preferably in the range of more than 50 mass %. The upper limit of the content of water is preferably in the range of less than 85 mass % in the total amount of the resin composition, more preferably in the range of less than 80 mass %, and more preferably in the range of less than 75 mass %. The range of the content of water is preferably in the range of more than 30 mass % and less than 85 mass % in the total amount of the resin composition, more preferably in the range of more than 45 mass % and less than 80 mass %, and more preferably in the range of more than 50 mass % and less than 75 mass %.

[0123] [Water-soluble solvent]

[0124] The resin composition of the present embodiment may contain a water-soluble solvent. The solvent can disperse or dissolve colorants, etc. It should be noted that, in this specification, "water-soluble solvent" mainly refers to a water-soluble organic solvent. In addition, the water-soluble solvent does not necessarily have to be a solvent for dissolving all the components contained, and can also be a dispersion medium for dispersing at least a portion of the components contained.

[0125] Examples of the water-soluble solvent include alkyl alcohols having 1 to 5 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, and n-pentanol; monohydric alcohols, such as 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, and 3-methoxy-n-butanol; formamide, acetamide, propionamide, butyramide, isobutylamide, valeramide, N-methylformamide, N-methylacetamide, N-methylpropionamide, N-methylbutyramide, and N-methylisothiazolinone. Butylamide, N-methylvaleramide, N-ethylformamide, N-ethylacetamide, N-ethylpropionamide, N-ethylbutyramide, N-ethylisobutylamide, N-ethylvaleramide, N-propylformamide, N-propylacetamide, N-propylpropionamide, N-propylbutyramide, N-propylisobutylamide, N-propylvaleramide, N-isopropylformamide, N-isopropylacetamide, N-isopropylpropionamide, N-isopropylbutyramide, N-isopropylisobutylamide, N-isopropylvaleramide, N-butylformamide, N-butylacetamide, N-Butyl propionamide, N-butyl butanamide, N-butyl isobutylamide, N-butyl valeramide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyl propanamide, N,N-dimethyl butanamide, N,N-dimethyl isobutylamide, N,N-dimethyl valeramide, N,N-diethyl formamide, N,N-diethyl acetamide, N,N-diethyl propanamide, N,N-diethyl butanamide, N,N-diethyl isobutylamide, N,N-diethyl valeramide, N,N-dipropyl formamide, N,N- Dipropylacetamide, N,N-dipropylpropionamide, N,N-dipropylbutanamide, N,N-dipropylisobutylamide, N,N-dipropylvaleramide, N,N-diisopropylformamide, N,N-diisopropylacetamide, N,N-diisopropylpropionamide, N,N-diisopropylbutanamide, N,N-diisopropylisobutylamide, N,N-diisopropylvaleramide, N,N-dibutylformamide, N,N-dibutylacetamide, N,N-dibutylpropionamide, N,N-dibutylbutanamide, N,N-dibutylisobutylamide, N,N-Dibutylvaleramide, N-ethyl-N-methylformamide, N-ethyl-N-methylacetamide, N-ethyl-N-methylpropionamide, N-ethyl-N-methylbutyramide, N-ethyl-N-methylisobutylamide, N-ethyl-N-methylvaleramide, N-methyl-N-propylformamide, N-methyl-N-propylacetamide, N-methyl-N-propylpropionamide, N-methyl-N-propylbutyramide, N-methyl-N-propylisobutylamide, N-methyl-N-propylvaleramide, N-ethyl-N-propylformamide , N-methyl-N-(1-methylethyl)formamide, N-hydroxypropyl-N-methylacetamide, N-ethyl-N-propylacetamide, N-ethyl-N-propylpropionamide, N-ethyl-N-propylbutanamide, N-ethyl-N-propylisobutylamide, N-ethyl-N-propylvaleramide, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, N-vinylmethyloxazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 3-methoxypropionamide, 3 Amides such as N,N-dibutyl-3-methoxypropionamide, N,N-dibutyl-3-butoxypropionamide, N,N-dimethyl-3-butoxypropionamide; ketones or ketone alcohols such as acetone, diacetone alcohol, Texanol; ethers such as tetrahydrofuran, dioxane (including 1,4-dioxane, etc.); oxyethylene or oxypropylene copolymers such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, isobutylene glycol, triethylene glycol, tripropylene glycol , tetraethylene glycol, 1,3-propylene glycol, 2-methyl-1,2-propylene glycol, 2-methyl-1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol and other glycols; glycerol, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol and other triols: meso-erythritol, pentaerythritol and other tetrahydric alcohols; ethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl) ether, diethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl) ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, propylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, dipropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, tripropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether and other monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl Dialkyl ethers of polyols such as methyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol ethyl methyl ether; ethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, diethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, propylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate ) ether acetate, dipropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, tripropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate and other acetates; γ-butyrolactone, α-methylene-γ-butyrolactone, ε-caprolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, δ-valerolactone, δ-caprolactone, δ-heptanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecalactone, γ,Lactones such as γ-dimethyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-crotonolactone (Japanese: γ-crotrolactone), α-methylene-γ-butyrolactone, β-methyl-γ-butyrolactone, 6-methylvalerolactone, 2,3-butylene carbonate, ethylene carbonate, propylene carbonate, etc. Carbonates such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, octyl acetate, etc. Acetic acid esters such as lactate, lactic acid Lactic acid esters such as ethyl lactate, butyl lactate, propyl lactate, ethylhexyl lactate, amyl lactate, isoamyl lactate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, etc., monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyl Alkanolamines such as 1,2-diethanolamine; saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, isododecane; unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene; cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin; cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene; aromatic hydrocarbons such as benzene, toluene, xylene; N-methyl-2-pyrrolidone, 2-pyrrolidone , β-lactam, δ-lactam, ε-caprolactam, N-methyl-ε-caprolactam, 2-hydroxyethylpyrrolidone, N-2-hydroxyethyl-2-pyrrolidone, 3-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and other nitrogen-containing heterocyclic compounds; cyclic compounds such as sulfolane, N-methylmorpholine, N-ethylmorpholine, N-formylmorpholine, N-hydroxyethylmorpholine, 2-hydroxyethylmorpholine, 4-acetylmorpholine and other morpholines, terpene solvents, etc. They can be used alone or in combination of two or more. Among them, it is preferred to select a water-soluble solvent in such a way that the resin composition has the desired static surface tension. For example, it is preferred to contain at least one alkanediol-based water-soluble solvent. ,

[0126] As the content of the water-soluble solvent, as long as each component can be dispersed or dissolved, there is no particular limitation. The lower limit of the content of the water-soluble solvent is preferably in the range of 5% by mass or more in the total amount of the resin composition, more preferably in the range of 10% by mass or more, and more preferably in the range of 12% by mass or more. The upper limit of the content of the water-soluble solvent is preferably in the range of 50% by mass or less in the total amount of the resin composition, more preferably in the range of 45% by mass or less, and more preferably in the range of 40% by mass or less. The range of the content of the water-soluble solvent is preferably in the range of 5% by mass or more and 50% by mass or less in the total amount of the water-based ink, more preferably in the range of 10% by mass or more and 45% by mass or less, and more preferably in the range of 12% by mass or more and 40% by mass or less.

[0127] [Color]

[0128] The resin composition of the present embodiment may contain a colorant. It is not an essential configuration for the resin composition of the present embodiment to contain a colorant, but by containing a colorant, a colored ink that forms a desired image pattern, a white ink that becomes a base layer, a metallic ink, etc. can be made. The colorant may be a dye or a pigment.

[0129] In the resin composition of the present embodiment, the pigment that can be used is not particularly limited, and organic pigments or inorganic pigments used in the previous resin composition (coloring ink) can be cited. They can be used alone or in combination of two or more. It should be noted that the resin composition of the present embodiment may not contain a colorant. In the case of using a pigment in the resin composition of the present embodiment, the dispersion stability of the pigment can be improved by using a dispersant or a dispersing aid (pigment derivative). In addition, the resin can also be used by containing a pigment or a dye.

[0130] As pigments, inorganic pigments or organic pigments used in conventional resin compositions (coloring inks) can be cited. They can be used alone or in combination of two or more. As specific organic pigments, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine organic pigments, quinacridone organic pigments, perylene organic pigments, perindole organic pigments, azomethine organic pigments, anthraquinone organic pigments (anthrone organic pigments), xanthene organic pigments, diketopyrrolopyrrole organic pigments, dioxazine organic pigments, nickel azo pigments, isoindolinone organic pigments, pyranthrone organic pigments, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindolinone organic pigments, quinacridone solid solution pigments, perylene solid solution pigments and other organic solid solution pigments can be cited, and as other pigments, color lake pigments, carbon black, etc. can be cited.

[0131] If organic pigments are listed by color index (CI) number, CI Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, CI Pigment Red 5, 7, 9, 12, 48, 48:2, 48:3, 49, 52, 53, 57, 57:1, 97, 112, 122, 123, 146, 149, 150, 1 68, 176, 177, 180, 184, 185, 192, 202, 206, 208, 209, 213, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 269, 291, CI Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 16, 22, 60, 64, CI Pigment Green 7, 36, 58, 59, 62, 63, CI Pigment Brown 23, 25, 26, CI Pigment Black 7, etc.

[0132] Specific examples of dyes that can be used in the resin composition of the present embodiment include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, crotonate dyes, merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes such as indigo, fulgide dyes, nickel complex dyes, and azulene dyes.

[0133] Specific examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, aluminum oxide, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and inorganic solid solution pigments.

[0134] The average dispersed particle size of the pigment is not particularly limited as long as the desired color development can be performed. Although different according to the type of pigment, from the viewpoint of good dispersion stability of the pigment and sufficient tinting power, the lower limit of the average dispersed particle size of the pigment is preferably in the range of more than 10nm, more preferably in the range of more than 20nm, and more preferably in the range of more than 30nm. The upper limit of the average dispersed particle size of the pigment is preferably in the range of less than 500nm, more preferably in the range of less than 400nm, and more preferably in the range of less than 300nm. If the average dispersed particle size is less than 500nm, even in the case of the resin composition of the present embodiment of inkjet ejection, it is not easy to cause the nozzle of the nozzle to be blocked, and a homogeneous image with high reproducibility can be obtained. If the average dispersed particle size is more than 10nm, the light resistance of the obtained record can be made good. The range of the average dispersed particle size of the pigment is preferably in the range of more than 10nm and less than 500nm, more preferably in the range of more than 20nm and less than 400nm, and more preferably in the range of more than 30nm and less than 350nm. It should be noted that, in the present embodiment, the average dispersed particle size of the pigment is an average particle size (D50) measured at 25°C using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000). It should be noted that, in the present specification, "volume-based cumulative 50% particle size (D50)" refers to the particle size at which the cumulative volume calculated from the small particle size side becomes 50%. "Volume-based cumulative 50% particle size (D50)" is sometimes also referred to as "volume average particle size D50" or "median particle size (median particle size)".

[0135] The resin composition of the present embodiment may contain a bright pigment as a pigment. Examples of the bright pigment include single metals such as aluminum, silver, gold, nickel, chromium, tin, zinc, indium, titanium, and copper; metal compounds; bright pigments containing metals as at least one of alloys and mixtures thereof, mica, fish scale foil, bismuth oxychloride, silicon dioxide, metal oxides, metal compounds, and pearlescent pigments having pearl luster or interference luster such as laminates thereof.

[0136] When the resin composition of the present embodiment contains a bright pigment, the bright pigment is preferably in a plate shape (also referred to as a fine plate shape, a scale shape, etc.) This can impart a more suitable metallic luster to the substrate.

[0137] In the case where the resin composition of the present embodiment contains a colorant (including dyes, pigments, bright pigments), the content of the colorant is not particularly limited, and is preferably 0.05% by mass or more in the total amount of the resin composition, more preferably 0.08% by mass or more, and further preferably 0.1% by mass or more. In the case where the resin composition of the present embodiment contains a colorant, the content of the colorant is preferably 20.0% by mass or less in the total amount of the resin composition, more preferably 17.0% by mass or less, and further preferably 15.0% by mass or less. The content of the colorant is preferably 0.05% by mass or more and 20.0% by mass or less in the total amount of the resin composition, more preferably 0.08% by mass or more and 17.0% by mass or less, and further preferably 0.1% by mass or more and 15.0% by mass or less. By making the content of the colorant be within the range of 0.05% by mass or less or 20% by mass, the balance of the dispersion stability and the tinting power of the colorant can be excellent.

[0138] [Pigment dispersant]

[0139] The resin composition of the present embodiment may contain a pigment dispersant together with the pigment. Here, the pigment dispersant refers to a resin or a surfactant having a function of improving the dispersibility of the pigment in the resin composition by adhering to a part of the surface of the pigment.

[0140] The pigment dispersant that can be used in the resin composition of the present embodiment is not particularly limited. For example, cationic, anionic, nonionic, amphoteric, silicone (silicon)-based, fluorine-based and other surfactants can be used. Among the surfactants, the polymer surfactant (polymer dispersant) exemplified below is preferred.

[0141] As the pigment dispersant that can be used in the resin composition of the present embodiment, a water-soluble polymer dispersant can be preferably used. As the water-soluble polymer dispersant, for example, a dispersant having a polyester-based, polyacrylic acid-based, polyurethane-based, polyamine-based, polycaprolactone-based main chain and a side chain having polar groups such as amino, carboxyl, sulfonic, and hydroxyl groups can be cited. For example, there can be mentioned (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene and unsaturated carboxylic acid esters such as acrylic acid esters; (partial) amine salts, (partial) ammonium salts, (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates, and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reaction of poly(lower alkylene imine) with free carboxyl-containing polyesters, and their bases); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from the three compounds of polyesters having free carboxyl groups, polyamides, or co-condensates of esters and amides (polyesteramides)), etc. Among them, from the viewpoint of dispersion stability of the resin composition and image clarity of printed materials, a water-soluble polymer dispersant containing a (meth)acrylic resin is preferred.

[0142] Specific examples of the water-soluble polymer dispersant include SMA1440, SMA2625, SMA17352, SMA3840, SMA1000, SMA2000, SMA3000 manufactured by Cray Valley, JONCRYL 67, JONCRYL 678, JONCRYL 586, JONCRYL 611, JONCRYL 680, JONCRYL 682, JONCRYL 690, JONCRYL 819, JONCRYL-JDX5050, EFKA4550, EFKA4560, EFKA4585, EFKA5220, EFKA6230 manufactured by BASF Japan, and Dispex UltraPX4575, SOLSPERSE20000, SOLSPERSE27000, SOLSPERSE40000, SOLSPERSE41000, SOLSPERSE41090, SOLSPERSE43000, SOLSPERSE44000, manufactured by Lubrizol Corporation SOLSPERSE45000, SOLSPERSE46000, SOLSPERSE47000, SOLSPERSE53095, SOLSPERSE54000, SOLSPERSE64000, SOLSPERSE65000, SOLSPERSE66000, SOLSPERSE J400, SOLSPERSE W100, SOLSPERSE W200, SOLSPERSE W320, SOLSPERSEWV400, ANTI-TERRA-250 manufactured by BYK-Chemie, BYKJET-9150, BYKJET-9151, BYKJET-9152, BYKJET-9170, DISPERBYK-102, DISPERBYK-168, DISPERBYK-180, DISPERBYK-184, DISPERBYK-185, DISPERBYK-187, DISPERBYK-190, DISPERBYK-191, DISPERBYK-193, DISPERBYK-194N, DISPERBYK-198, DISPERBYK-199, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2013, DISPERBYK-2014, DISPERBYK-2015, DISPERBYK-2018, DISPERBYK-2019, DISPERBYK-2055, DISPERBYK-2060, DISPERBYK-2061, DISPERBYK-2081, DISPERBYK-2096, TEGO DISPERS650, TEGO DISPERS651, TEGO DISPERS652, TEGO DISPERS655, TEGO DISPERS660C, TEGO DISPERS670, TEGO DISPERS715W, TEGODISPERS740W, TEGO DISPERS741W, TEGO DISPERS750W, TEGO DISPERS752W, TEGODISPERS755W, TEGO DISPERS757W, TEGO DISPERS760W, TEGO DISPERS761W, TEGODISPERS765W, ZETASPERSE170, ZETASPERSE179, ZETASPERSE182, ZETASPERSE3100, ZETASPERSE3400, ZETASPERSE3700, ZETASPERSE3800, SN Dispersant2010, SN Dispersant 2060, SN Dispersant 4215, SN Dispersant 5027, SN Dispersant5029, SN Dispersant 5034, SN Dispersant 5468, NOPCALL 5200, Nopcosant K, NopcosantR, Nopcos Perth44-C, Nopcos Perth 6100, Nopcos Perth 6150, etc. These pigment dispersants can be suitably used in the resin composition of this embodiment.

[0143] [Cationic or anionic compounds]

[0144] The resin composition of the present embodiment may contain a cationic compound. It is not a necessary structure for the resin composition of the present embodiment to contain a cationic or anionic compound, but by containing a cationic or anionic compound, the resin composition of the present embodiment can be made into a receiving solution (pretreatment solution). Usually, the colorant contained in the coloring ink is anionic, and before the coloring ink is applied to the substrate, a receiving solution (pretreatment solution) containing a cationic compound is applied to the substrate, thereby enabling the colorant to be condensed by the cationic compound, and the bleeding of the coloring ink can be suppressed. In addition, when the colorant contained in the coloring ink is cationic, by applying a receiving solution (pretreatment solution) containing anionic compounds on the substrate before applying the coloring ink on the substrate, the colorant can be condensed by the anionic compound, and the bleeding of the coloring ink can be suppressed.

[0145] Examples of the cationic compound include cationic resins and polyvalent metal salts (polyvalent metal ions).

[0146] Cationic resins can be synthesized by known methods, or commercial products can be used. Examples of commercial products include APC-810, 815; D-6010, 6020, 6030, 6040, 6050, 6060, 6080, 6310, DEC-50, 53, 56, 65; FL-14, 42, 44LF, 61, 2099, 2250, 2273, 2350, 2550, 2565, 2599, 2650, 2665, 2670, 2680, 2760, 2771, 2780, 2790, 2800, 2810, 2820, 2830, 2840, 2850, 2860, 2871, 2880, 2890, 2910, 2930, 2940, 2950, ​​2960, 2970, 2980, 29 ... 850, 2949, 3050, 3150, 4340, 4420, 4440, 4450, 4520, 4530, 4535, 4540, 4620, 4820; FQP-1264; RSL-18-22, 4071H, 4400, 8391, 8391H, HD70C, HF70D; WS-72 (made by SNF), ARAFIX 100, 251S, 255, 255LOX (Arakawa Chemical Co., Ltd.), DK-6810, 6853, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (Starlight PMC Co., Ltd.), Senka F-300; PAPYOGEN P-105, P-113, P-271, P-316; PITCHNOL QG5A; MILLIOGEN P-20; Unisense FPA100L, FPA101L, FPA102L, FPA1000L, FPA1001L, FPA100LU, FPA102LU, FPA1000LU; Unisense FCA1000L, FCA1001L, FCA1002L, FCA1003L, FCA5000L; UnisenseKCA100L, KCA100LU, KCA1000LU, KCA1001LU; Unisense Unisense FPV1000L, FPV1000LU; UnisenseFCV1000L; Unisense ZCA1000L, ZCA1001L, ZCA1002L, ZCA5000L;Unisense KPV100LU, KPV1000LU (Senka), Paralock 410K101, 410K111, 420K308, 420K300, 460K313, 460K318, 470K308, 480K300, 490K300, 490K309, 500K30E, 500K40E, 59D, 920AP500, 975AP500, PD700, PD714L, PD714S, P600 (Asada Chemical Co., Ltd.), Sumirez Resin 650 (30), 675A, 6615, SLX-1 (Taoka Chemical Industry Co., Ltd.), EP-1137; MZ-477, 480; NS-310X, 625XC (Takamatsu Oil Co., Ltd.), PAA-D11-HCL, D19-HCL, D41-HCL, D19A; PAA-HCL-03, 05, 3L, 10L; PAA-1112CL, 21CL, AC5050A, N5050CL, SA; PAS-A-1, 5; PAS-H-1L, 5L, 10L; PAS-J-81, 81L; PAS-M-1, 1A, 1L; PAS-21, 21CL, 22SA-40, 24, 92, 92A, 880, 2201CL, 2401 (Nittobo Medical Co., Ltd.), PP-17 (Meisei Chemical Co., Ltd.); Catio Master PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (Yokkaichi Synthetic Co., Ltd.), Jet Fix 36N, 38A, 5052 (Satota Chemical Co., Ltd.), Mowinyl 3500, 6910, 6940, 6950, 6951, 7820 (Japan Coating Resin Co., Ltd.), CTW-113S, WEM-505C, WBR-2122C (Taisei Fine Chemical Co., Ltd.), AP-1350, AE-803, AE-821, AM-3500 (Resonac Co., Ltd.), HYDRAN CP-7050, CP-7520 (DIC Co., Ltd.), etc. ;

[0147] It should be noted that the cationic resin may be present in a state of being dissolved in the resin composition or in a state of being dispersed as a polymer fine particle dispersion.

[0148] As the metal salt, there can be mentioned a polyvalent metal salt containing an ion and an anion of a polyvalent metal having a valence of at least 2. As the polyvalent metal ion, for example, there can be mentioned calcium ion, magnesium ion, aluminum ion, titanium ion, iron (II) ion, iron (III) ion, cobalt ion, nickel ion, copper ion, zinc ion, barium ion, strontium ion, etc. Among them, from the aspect of large interaction with the colorant in the resin composition, suppression of bleeding, uneven effect, it is preferred to contain one or more selected from calcium ion, magnesium ion, nickel ion, zinc ion, aluminum ion.

[0149] The anion may be an anion of an inorganic substance or an anion of an organic substance. Specific examples of anions of organic substances include anions of acetic acid, benzoic acid, salicylic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, dimethylolpropionic acid, pantothenic acid, succinic acid, maleic acid, glutaric acid, suberic acid, trimellitic acid, and methylmalonic acid. Specific examples of anions of inorganic substances include chloride ions, bromide ions, nitrate ions, sulfate ions, and the like.

[0150] As the content of cationic or anionic compounds, it is not particularly limited, and the lower limit of the content of cationic or anionic compounds is preferably in the range of 0.1% by mass or more in the total amount of the resin composition, more preferably in the range of 0.8% by mass or more, and further preferably in the range of 1.0% by mass or more. By making the content of cationic or anionic compounds in the total amount of the resin composition in the range of 0.5% by mass or more, the colorant can be fixed more effectively, and the bleeding of the coloring ink can be more effectively suppressed. The upper limit of the content of cationic or anionic compounds is preferably in the range of 15% by mass or less in the total amount of the resin composition, more preferably in the range of 8% by mass or less, and further preferably in the range of 7% by mass or less. By making the content of cationic or anionic compounds in the range of 15% by mass or less in the total amount of the resin composition, the storage stability and ejection stability of the resin composition are improved. The content of the cationic or anionic compound is preferably in the range of 0.1% by mass to 15% by mass, more preferably in the range of 0.8% by mass to 8% by mass, and even more preferably in the range of 1.0% by mass to 7% by mass, based on the total amount of the aqueous ink composition.

[0151] [Leveling agent]

[0152] The resin composition of the present embodiment may contain a leveling agent as a surfactant different from the emulsifier and pigment dispersant contained in the above-mentioned copolymer. By containing a leveling agent, the surface tension of the resin composition can be controlled within an appropriate range. The leveling agent is not particularly limited, and from the aspect of excellent adjustability of the surface tension, anionic surfactants, nonionic surfactants, silicone (silicon) surfactants, fluorine-based surfactants, acetylene glycol surfactants, etc. are preferably used.

[0153] Specific examples include EMAL, LATEMUL, PELEX, NEOPELEX, DEMOL (all anionic surfactants; manufactured by Kao Corporation), Sannol, Lipolan, Lipon, Lipal (all anionic surfactants; manufactured by Lion Corporation), NOIGEN, Epan, Solgen (all nonionic surfactants; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), EMULGEN, AMIET, Emasol (all nonionic surfactants; manufactured by Kao Corporation), NAROACTY, Emulmin, Sannonic (all nonionic surfactants; manufactured by Sanyo Chemical Industries, Ltd.), Surfynol 104, 82, 420, 440, 465, 485, TG, 2502, SE-F, 107L, Dynol 360, Dynol 604, Dynol 607 (all acetylene glycol surfactants; manufactured by Evonik), Dynol 960 (a complex of acetylene glycol and silicone surfactants; manufactured by Evonik), Surfynol AD01 (an alkanediol surfactant; manufactured by Evonik), OLFINE E1004, E1010, PD004, EXP4300 (all acetylene glycol surfactants; manufactured by Nissin Chemical Industries, Ltd.), Megaface (a fluorine-based surfactant; manufactured by DIC Corporation), Surflon (a fluorine-based surfactant; manufactured by AGC Corporation), SEMICHEMICAL), BYK302, 306, 307, 331, 333, 345, 346, 347, 348, 349, 3420, 3450, 3451, 3455, 3456 (all silicone surfactants; BYK-Chemie), KP-110, 112, 323, 341, 6004 (all silicone surfactants; Shin-Etsu Chemical Co., Ltd.), SILFACE SAG002, SILFACE SAG005, SILFACE SAG008, SILFACE SAG014, SILFACE SAG503A, SILFACE SJM-002, SILFACE SJM-003 (all silicone surfactants;Nissin Chemical Industry Co., Ltd.), TEGO FLOW 425, TEGO Glide 100, 110, 130, 410, 432, 440, 450, 482, 490, 492, 494, 496, ZG400, TEGO Twin 4000, TEGO Twin 4100, TEGOTwin 4200, TEGO Wet 240, KL245, 250, 260, 265, 270, 280 (all silicone surfactants; Evonik), TEGO Wet 500, 505, 510, 520 (all nonionic surfactants; Evonik), etc. ;

[0154] The content of the leveling agent is not particularly limited, and the lower limit of the content of the leveling agent is preferably in the range of 0.30 mass % or more in the total amount of the resin composition, more preferably in the range of 0.40 mass % or more, and further preferably in the range of 0.50 mass % or more. The upper limit of the content of the leveling agent is preferably in the range of 5.0 mass % or less in the total amount of the resin composition, more preferably in the range of 4.0 mass % or less, and further preferably in the range of 3.0 mass % or less. The range of the content of the leveling agent is preferably in the range of 0.30 mass % or more and 5.0 mass % or less in the total amount of the aqueous ink composition, more preferably in the range of 0.40 mass % or more and 4.0 mass % or less, and further preferably in the range of 0.50 mass % or more and 3.0 mass % or less.

[0155] [Other ingredients]

[0156] The resin composition of the present embodiment may further contain conventionally known additives as required, such as wax, viscosity modifier, pH modifier, antioxidant, preservative, mildewproofing agent, antibacterial agent, antiviral agent, ultraviolet absorber, light stabilizer, etc.

[0157] <Method for preparing resin composition>

[0158] The method for preparing the resin composition of the present embodiment is not particularly limited, and examples thereof include a method of adding a self-dispersible pigment, a resin, a surfactant, and other components as required to a water-soluble solvent; a method of adding a pigment and a dispersant to a water-soluble solvent for dispersion, and then adding a resin (resin dispersion), a surfactant, and other components as required; a method of adding a pigment, a resin, a surfactant, and other components as required to a water-soluble solvent and then dispersing the pigment, etc.

[0159] The method of applying the resin composition of the present embodiment to the surface of the substrate is not particularly limited, and for example, an inkjet method, a gravure method, a flexographic method, a spray method, a screen method, a coater method, etc. can be cited. Among them, the inkjet method is preferred. If it is an inkjet method, the desired image on the electronic can be ejected to any part of the substrate to form the desired image.

[0160] The surface tension of the resin composition of the present embodiment is not particularly limited. The upper limit of the surface tension of the resin composition of the present embodiment at 25°C is preferably 40.0 mN / m or less, more preferably 35.0 mN / m or less, and further preferably 32.0 mN / m or less. The lower limit of the surface tension of the resin composition of the present embodiment at 25°C is preferably 17.0 mN / m or more, more preferably 18.0 mN / m or more, and further preferably 19.0 mN / m or more. The range of the surface tension of the resin composition of the present embodiment at 25°C is preferably 17.0 mN / m or more and 40.0 mN / m or less, more preferably 18.0 mN / m or more and 35.0 mN / m or less, and further preferably 19.0 mN / m or more and 32.0 mN / m or less.

[0161] "4. Ink set (Japanese: インクセット)"

[0162] The resin composition may be a colored ink, a metallic ink, etc., a receiving solution containing a cationic compound, a transparent ink without a colorant, a primer, or an overcoat ink. The ink set of this embodiment may also be an ink set composed of these ink compositions.

[0163] For the ink set of this embodiment, at least one composition contained in the ink set can be a resin composition containing a copolymer containing the above-mentioned at least two monomers as structural units. For example, in an ink set containing composition A and composition B, composition A can be a resin composition containing a copolymer containing the above-mentioned at least two monomers as structural units, and composition B can be a composition different from the resin composition containing the copolymer containing the above-mentioned at least two monomers as structural units. In addition, both composition A and composition B can be a resin composition containing a copolymer containing the above-mentioned at least two monomers as structural units. The same is true for an ink set containing three or more compositions.

[0164] As the ink set of this embodiment, for example, there can be mentioned an ink set containing a coloring ink composition containing a colorant and a receiving solution (pretreatment liquid) containing a cationic compound; an ink set containing a coloring ink composition containing a colorant, a receiving solution (pretreatment liquid) containing a cationic compound, and an overcoating ink; and an ink set containing a coloring ink composition containing a colorant and an overcoating ink.

[0165] In addition, it is also possible to use an ink set in which a coloring ink composition containing a coloring material is combined with each other. For example, it is also possible to use an ink set in which a plurality of compositions such as coloring ink compositions of yellow, magenta, cyan, black, and intermediate colors thereof (e.g., orange ink, green ink, blue ink, red ink), and light colors (e.g., light magenta ink, light cyan ink, and light black ink) are combined. In addition, it is also possible to use an ink set containing a white ink composition containing a white coloring material, and a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition; and an ink set containing a white ink composition containing a white coloring material, and a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition, and intermediate color ink compositions and light color ink compositions of yellow, magenta, cyan, and black. In addition, it can also be an ink set containing a metallic ink containing a bright pigment, and a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition; an ink set containing a metallic ink containing a bright pigment, and a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition, as well as an intermediate color ink composition and a light color ink composition of yellow, magenta, cyan, and black.

[0166] 《5. Recording Method》

[0167] The recording method of the present embodiment is a recording method in which the above-mentioned resin composition containing a copolymer including at least two monomers as structural units is applied onto a substrate.

[0168] If the resin composition contains a copolymer including at least two monomers as structural units, the storage stability is high, and therefore the resin composition can be applied to a substrate while maintaining the high storage stability.

[0169] The method of applying the above-mentioned resin composition containing the copolymer comprising at least two monomers as structural units to the surface of the substrate is not particularly limited, and for example, an inkjet method, a gravure method, a flexographic method, a spraying method, a screen method, a coater method, etc. can be cited. Among them, the inkjet method is preferred. If it is an inkjet method, it can be sprayed to any position on the substrate.

[0170] The recording method of the present embodiment may include a drying step of drying the resin composition applied on the surface of the substrate. This allows the heating temperature during printing to be adjusted, and the productivity of the recorded material to be improved.

[0171] As a method for drying the resin composition applied to the surface of the substrate, for example, it may be a method of drying it using a heating mechanism such as a preheater, a platen heater, or a post-heater provided in the device, it may be an air supply mechanism for blowing hot air, air of normal temperature, etc. to the surface of the recorded object, or it may be a radiation irradiation mechanism for heating the surface of the recorded object using infrared rays, etc. In addition, a plurality of these heating mechanisms may be combined.

[0172] In particular, the resin composition containing a copolymer containing at least two monomers as structural units can be sufficiently coated even when dried at a relatively low temperature, and the obtained recorded material has high solvent resistance. Therefore, by drying at a low temperature, recorded materials can be produced with high productivity while reducing energy load and load on the device.

[0173] Specifically, in the recording method of the present embodiment, it is preferred to dry the recorded object so that the surface temperature reaches 120°C or lower, more preferably 100°C or lower, and even more preferably 80°C or lower. In addition, in the recording method of the present embodiment, it is preferred to dry the recorded object so that the surface temperature reaches 30°C or higher, more preferably 35°C or higher, and even more preferably 40°C or higher. In the recording method of the present embodiment, it is preferred to dry the recorded object so that the surface temperature reaches 30°C or higher and 120°C or lower, more preferably 35°C or higher and 100°C or lower, and even more preferably 40°C or higher and 80°C or lower.

[0174] In the case of a recording method in which the inkjet method is applied to a substrate, the resin composition containing a copolymer comprising at least two monomers as structural units may be discharged by any of piezoelectric, thermal, and electrostatic methods.

[0175] 《6. Method for producing recorded matter》

[0176] The above-mentioned recording method can also be defined as a method for producing a recorded object, comprising applying the above-mentioned resin composition containing a copolymer including at least two monomers as structural units onto a substrate.

[0177] 7. Records

[0178] The various layers constituting the recorded object manufactured by the method for manufacturing a recorded object according to the above embodiment will be described. Specifically, the recorded object is formed by applying the above resin composition containing a copolymer including at least two monomers as structural units, or the resin composition contained in the above ink set, onto a substrate. The medium (recording medium) and the layers of the resin composition constituting the recorded object will be described below.

[0179] The substrate (recording medium) contained in the recorded matter of this embodiment is not particularly limited, and may be a non-absorbent substrate such as a resin substrate, a metal plate, or glass; an absorptive substrate such as paper or cloth; or a substrate with a surface coating such as a substrate having a receiving layer. Various substrates can be used.

[0180] Examples of non-absorbent substrates include resin substrates such as polyester resins, polypropylene synthetic paper, polypropylene resins, polyethylene resins, acrylic resins, styrene resins, polycarbonate resins, ABS resins, vinyl chloride resins, polyimide resins, metals, metal foil coated paper, glass, synthetic rubber, natural rubber, and the like.

[0181] The resin composition containing a polymer containing a specific monomer as a structural unit can form a coating film having high adhesion to an olefin resin, and therefore, the substrate (recording medium) is preferably an olefin resin. Among them, the surface of the olefin resin subjected to surface treatments such as corona treatment, flame treatment, plasma treatment, flame treatment, ultraviolet irradiation treatment, and chromic acid treatment has particularly high adhesion. It should be noted that the olefin resin may be unstretched or may be a stretched olefin resin such as uniaxial stretching or biaxial stretching.

[0182] Examples of the absorbent substrate include wood pulp paper, medium-quality paper, high-quality paper, synthetic paper, cotton, chemical fiber fabrics, silk, linen, cloth, nonwoven fabrics, and leather.

[0183] Examples of the substrate on which the surface is coated include coated paper, art paper, cast-coated paper, lightweight coated paper, and lightly coated paper.

[0184] [Coating film of resin composition]

[0185] The coating of the resin composition refers to a layer formed by the volatilization of the solvent (water, water-soluble organic solvent) contained in the above-mentioned resin composition containing a copolymer containing at least two monomers as structural units. For example, when the resin composition contains a colorant, it becomes a decorative layer or a base layer thereof that forms a desired image. It should be noted that in this specification, the shape of the "coating" is not limited to, for example, a flat plate or a layer, and may have concave-convex, may have holes formed in a part, and may also be formed with a coating on a part of the surface. In addition, for convenience, a coating in a state where the coating of the resin composition is absorbed by the absorbent substrate and substantially becomes a part of the substrate is also recorded as the coating of the resin composition.

[0186] When the resin composition containing a copolymer including at least two monomers as structural units is made into a receiving solution containing a cationic compound, the resin composition containing a copolymer including at least two monomers as structural units (receiving solution) may be applied on a substrate, and the resin composition containing a copolymer including at least two monomers as structural units (colored ink) may be applied thereon. Alternatively, the resin composition containing a copolymer including at least two monomers as structural units (receiving solution) may be applied on a substrate, and a composition (colored ink) different from the resin composition containing a copolymer including at least two monomers as structural units (colored ink) may be applied thereon.

[0187] In addition, when the resin composition containing a copolymer including at least two monomers as structural units is made into an overcoat ink, it becomes an overcoat layer formed on the surface of the recorded object. It should be noted that, in this case, the composition forming the recording layer of the recorded object may be the resin composition containing a copolymer including at least two monomers as structural units, or may be a composition different from the resin composition containing a copolymer including at least two monomers as structural units.

[0188] 8. Installation

[0189] The apparatus of this embodiment can include a printer using the resin composition containing a copolymer including at least two monomers as structural units, or the resin composition contained in the ink set, etc. The apparatus of this embodiment is not particularly limited, and examples thereof include various coating machines such as an inkjet recording device, a gravure printing machine, a flexographic printing machine, a spray printing machine, a screen printing machine, a blade coater, and a die coater.

[0190] The device of this embodiment is preferably an inkjet recording device equipped with a container filled with the resin composition or the resin composition contained in the ink set. By using an inkjet recording device, it is possible to discharge to any position on the substrate.

[0191] It should be noted that a storage container is mounted in the device for supplying the resin composition or the resin composition contained in the ink set. These storage containers are not particularly limited, and examples thereof include containers such as ink bottles, bags, bags in boxes, and drums. In addition, these containers may be further stored in ink cartridges, etc. The material of the storage container is not particularly limited, and may be a conventionally known resin, or may be a material containing a metal material as a part thereof (e.g., an aluminum bag having an aluminum vapor-deposited layer).

[0192] In addition, the apparatus preferably includes a drying mechanism for drying the resin composition after the resin composition is ejected, thereby adjusting the surface temperature of the recorded matter during printing and effectively removing the volatile components contained in each resin composition.

[0193] The drying mechanism is not particularly limited as long as it can dry the recording medium, and is preferably any one of a preheater, a platen heater, a postheater, a radiation irradiation, and an air supply mechanism (hot air, air at room temperature, etc.). In addition, a plurality of these heating mechanisms may be combined.

[0194] Furthermore, when the device is an inkjet recording device, the ejection method in each ejection section may be any of a piezoelectric method, a thermal method, an electrostatic method, and the like.

[0195] Example

[0196] Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited to these descriptions at all.

[0197] 1. Synthesis of resin (resin dispersion)

[0198] [Example 1] Synthesis of Resin Dispersion 1

[0199] A mixture containing 88.7 parts of cyclohexyl methacrylate, 9.8 parts of n-butyl methacrylate, and 1.50 parts of methacrylic acid was added to an aqueous solution prepared by dissolving 2.0 parts of EMULGEN A-90 (manufactured by Kao Corporation; nonionic surfactant, solid content 100%) and 6.2 parts of EMAL 20CM (manufactured by Kao Corporation; anionic surfactant, solid content 25%) in 41.0 parts of water (deionized water), and stirred to prepare an emulsified monomer composition.

[0200] Next, 185.0 parts of water (deionized water) and 4.1 parts of "EMAL 20CM (manufactured by Kao Corporation; anionic surfactant, solid content 25%)" were added to a glass reaction container equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction tube, and a dropping funnel, stirred to dissolve, and heated to 73°C. 5% by mass of the above-mentioned emulsified monomer was added thereto and stirred, and 1.4 parts of 3% potassium persulfate were added to the reaction container to carry out an initial polymerization reaction. Then, the temperature was raised to 80°C, and 6.7 parts of 3% potassium persulfate and the remaining emulsified monomer composition were added dropwise over 4 hours while maintaining the temperature to carry out a polymerization reaction. After the addition was completed, the pH was adjusted to 8 using a 10% ammonia aqueous solution, and the reaction was aged for 1 hour. Then, it was cooled to room temperature, thereby obtaining a milky white resin dispersion. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersion 1 are shown in the following table.

[0201] [Examples 2 to 4] Synthesis of Resin Dispersions 2 to 4

[0202] Resin dispersions 2 to 4 were obtained in the same manner as in Example 1 except that the blending amounts of cyclohexyl methacrylate and n-butyl methacrylate were changed as shown in Table 2 below. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersions 2 to 4 are shown in Table 2 below.

[0203] [Examples 5 to 7] Synthesis of Resin Dispersions 5 to 7

[0204] In Example 1, except that n-butyl methacrylate was changed to cyclohexyl acrylate, and the blending amounts of cyclohexyl methacrylate and cyclohexyl acrylate were changed as shown in the following table, the same operation as in Example 1 was carried out to obtain resin dispersions 5 to 7. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersions 5 to 7 are shown in the following table.

[0205] [Examples 8-9] Synthesis of Resin Dispersions 8-9

[0206] In Example 1, except that n-butyl methacrylate was not used and the blending amounts of cyclohexyl methacrylate and cyclohexyl acrylate were changed as shown in the following table, the same operation as in Example 1 was carried out to obtain resin dispersions 8 to 9. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersions 8 to 9 are shown in the following table.

[0207] [Example 10] Synthesis of Solution Resin 1 (Solution Polymerization)

[0208] 100.0 parts by mass of diethylene glycol ethyl methyl ether was added to a reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. After the temperature was raised to 95°C under a nitrogen atmosphere, a solution of 98.5 parts by mass of cyclohexyl methacrylate, 1.5 parts by mass of methacrylic acid, and 1.60 parts by mass of PERBUTYL O (manufactured by NOF Corporation) was continuously added dropwise thereto over 2 hours. Then, the temperature was maintained at 95°C, and 0.50 parts by mass of PERBUTYL O (manufactured by NOF Corporation) was added 4 times every 30 minutes after the end of the dropwise addition. Then, the mixture was aged for 3.5 hours, and 77.5 parts by mass of diethylene glycol ethyl methyl ether was added for dilution. After dilution, the mixture was cooled to room temperature, thereby obtaining a solution of resin 1. The weight average molecular weight, solid content, viscosity, and other coating properties of the obtained resin 1 are shown in the following table. The solid content of the solution resin 1 was measured by heating in an oven at 150°C for 2 hours.

[0209] [Example 11] Synthesis of Resin Dispersion 10 (Suspension Polymerization)

[0210] 188.3 g of water (deionized water) in which 26.0 g of sodium hydroxide was dissolved was added to 941.3 g of water (deionized water) in which 36.9 g of magnesium chloride was dissolved, and the mixture was stirred for 20 minutes. A mixture containing 78.8 parts of cyclohexyl methacrylate, 19.7 parts of n-butyl methacrylate, 1.5 parts of methacrylic acid, and 5.81 g of PERBUTYL O (manufactured by NOF Corporation) was added thereto, and the mixture was stirred with a homogenizer to prepare a monomer composition.

[0211] Next, the monomer composition was added to a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, and the temperature was raised to 80°C while stirring. Then, the polymerization reaction was carried out for 6 hours while the temperature was maintained at 80°C. After the reaction was completed, the pH was adjusted to 8 using hydrochloric acid, and the reaction was aged for 1 hour. Then, it was cooled to room temperature, thereby obtaining a milky white resin dispersion. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersion 10 are shown in the following table.

[0212] [Examples 12 to 19] Synthesis of Resin Dispersions 11 to 18

[0213] In Example 1, the amounts of cyclohexyl methacrylate, n-butyl methacrylate, surfactant, and polymerization initiator were changed as shown in the following table, and the aging time after the completion of the monomer dropwise addition was changed to 10 minutes (resin dispersion 18), 20 minutes (resin dispersion 17), 30 minutes (resin dispersion 16), and 45 minutes (resin dispersion 15). Resin dispersions 11 to 18 were obtained in the same manner as in Example 1. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersions 11 to 18 are shown in the following table.

[0214] [Examples 20 to 26] Synthesis of Resin Dispersions 19 to 25

[0215] In Example 1, except that the type and compounding amount of the monomers were changed as shown in the following table, the same operation as in Example 1 was carried out to obtain resin dispersions 19 to 25. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersions 19 to 25 are shown in the following table.

[0216] [Example 27] Synthesis of Resin Dispersion 26

[0217] A mixture containing 74.1 parts of cyclohexyl methacrylate, 18.5 parts of n-butyl methacrylate, and 13.1 parts of 2-(dimethylamino)ethyl benzoate of methacrylate was added to an aqueous solution prepared by dissolving 2.0 parts of EMULGENA-90 (manufactured by Kao Corporation; nonionic surfactant, solid content 100%) and 6.2 parts of SANISOL B-50 (manufactured by Kao Corporation; cationic surfactant, solid content 50%) in 40.0 parts of water (deionized water), and stirred to prepare an emulsified monomer composition.

[0218] Next, 190.0 parts of water (deionized water) and 4.1 parts of "SANISOL B-50 (manufactured by Kao Corporation; cationic surfactant, solid content 50%)" were added to a glass reaction container equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a dropping funnel, stirred to dissolve, and heated to 73°C. 5% by mass of the above-mentioned emulsified monomer was added thereto and stirred, and 0.5 parts of a 15% aqueous solution of 2,2-azobis(2-diaminopropane) dihydrochloride was added to the reaction container to perform an initial polymerization reaction. Then, the temperature was raised to 80°C, and while maintaining the temperature, 1.2 parts of a 14% aqueous solution of 2,2-azobis(2-diaminopropane) dihydrochloride and the remaining emulsified monomer composition were added dropwise over 4 hours to perform a polymerization reaction. After the addition was completed, the reaction was aged for 1 hour. Then, it was cooled to room temperature, thereby obtaining a milky white resin dispersion. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersion 26 are shown in the following table.

[0219] [Example 28] Synthesis of Resin Dispersion 27

[0220] In Example 27, except that the blending amount of the monomers was changed as shown in the following table, the same operation as in Example 27 was carried out to obtain a resin dispersion 27. The weight average molecular weight, solid content concentration, viscosity, average particle size and theoretical glass transition temperature of the obtained resin dispersion 27 are shown in the following table.

[0221] [Example 29] Synthesis of Resin Dispersion 28

[0222] In Example 20, except that n-butyl methacrylate was changed to cyclohexyl acrylate and the blending amounts of cyclohexyl methacrylate and cyclohexyl acrylate were changed as shown in the following table, a resin dispersion 28 was obtained in the same manner as in the resin dispersion 26. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersion 28 are shown in Table 2.

[0223] [Example 30] Synthesis of Resin Dispersion 29

[0224] In Example 29, except that the blending amount of the monomers was changed as shown in the following table, the same operation as in Example 29 was carried out to obtain a resin dispersion 29. The weight average molecular weight, solid content concentration, viscosity, average particle size and theoretical glass transition temperature of the obtained resin dispersion 29 are shown in the following table.

[0225] [Comparative Examples 1 to 4] Synthesis of Resin Dispersions 30 to 33

[0226] In Example 1, except that the types and blending amounts of the monomers were changed as shown in the following table, the same operation as in Example 1 was carried out to obtain resin dispersions 30 to 33. The weight average molecular weight, solid content concentration, viscosity, average particle size, and theoretical glass transition temperature of the obtained resin dispersions 30 to 33 are shown in the following table.

[0227] 2. Evaluation of resin (resin dispersion)

[0228] The resin dispersions obtained in the above-mentioned Examples and Comparative Examples were evaluated as follows.

[0229] (Storage stability)

[0230] The storage stability of the resins (resin dispersions) of the examples and comparative examples was evaluated. Specifically, the resins (resin dispersions) of the examples and comparative examples were placed in a sealed container and placed in a hot air dryer at 60°C for 7 days. The state after placement was visually observed and evaluated according to the following criteria.

[0231] ◎: There is absolutely no change in appearance and viscosity.

[0232] ○: There is no change in appearance, but there is a slight increase or decrease in viscosity.

[0233] △: There are pitting (Japanese: ブツ) on the surface, and the viscosity increases or decreases sharply.

[0234] ×: The product is gelled or separated into a pudding-like state.

[0235] (Solid content)

[0236] The mass of the solid content was measured for the resins (resin dispersions) of Examples and Comparative Examples except Example 10. Specifically, the resins (resin dispersions) of Examples and Comparative Examples were heated in an oven at 105° C. for 1 hour, and the mass of the heated resins was measured.

[0237] (Viscosity)

[0238] The viscosity of the resin (resin dispersion) of the examples and comparative examples was measured. Specifically, the viscosity of the resin (resin dispersion) of the examples and comparative examples was measured at 25° C. using a B-type viscometer.

[0239] (Average particle size)

[0240] The average particle size of the resins (resin dispersions) of Examples and Comparative Examples was measured. Specifically, the average particle size of the resins (resin dispersions) of Examples and Comparative Examples was measured at a measurement temperature of 25° C. using a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

[0241] (Weight average molecular weight)

[0242] The weight average molecular weight of the resin (resin dispersion) of the examples and comparative examples was measured. Specifically, the weight average molecular weight of the resin (resin dispersion) of the examples and comparative examples was measured by gel permeation chromatography using polystyrene as a standard substance and THF as an eluent using a GPC measuring apparatus (manufactured by Tosoh Corporation, "HLC-8320GPC").

[0243] (Amount of unreacted monomers)

[0244] The amount of unreacted monomers in the resins (resin dispersions) of the examples and comparative examples was measured. Specifically, the amount of unreacted monomers in the resins (resin dispersions) of the examples and comparative examples was measured by gas chromatography using Nexis GC-2030 (manufactured by Shimadzu Corporation). The column used was "SH-Rtx-Wax (30m, 0.25mmID, 0.25μmdf)". A hydrogen flame ionization detector (FID) was used as a detector, and nitrogen was used as a carrier gas.

[0245] 3. Preparation of Pigment Dispersion

[0246] 2.5 g of a pigment dispersion resin ((meth) acrylic resin having a weight average molecular weight of 20,000 and an acid value of 143 mgKOH / g) and 0.6 g of N,N-dimethylaminoethanol were dissolved in 81.85 g of water (deionized water), 15 g of CI Pigment Blue 15:3 and 0.05 g of a defoaming agent (“Surfynol 104PG” manufactured by Air Products) were added, and the mixture was dispersed using zirconium oxide beads and a paint shaker to obtain a pigment dispersion.

[0247] 4. Preparation of resin composition

[0248] [Examples 1 to 20, Comparative Examples 1 to 4]

[0249] A resin composition containing 20% ​​by mass of a pigment dispersion, 25% by mass of the polymer fine particle dispersion (solid content concentration 30%), 25% by mass of 1,2-propylene glycol, 0.5% by mass of a polysiloxane compound, and 29.5% by mass of water (deionized water) was prepared.

[0250] [Examples 21 and 22]

[0251] A resin composition was prepared containing 25 mass % of the polymer fine particle dispersion (solid content concentration 30%), 9 mass % of 1,2-hexanediol, 25 mass % of 1,2-propylene glycol, 0.5 mass % of a polysiloxane compound, and 40.5 mass % of water (deionized water).

[0252] 4. Evaluation of resin composition

[0253] (Storage stability)

[0254] The storage stability of the resin composition containing the resins (resin dispersions) of the examples and comparative examples was evaluated. Specifically, the resin composition was heated in an oven at 60°C for 1 week, and the viscosity before and after heating was measured at a liquid temperature of 25°C, and the evaluation was performed based on the following evaluation criteria. The evaluation results are recorded in the following table (recorded as "storage stability" in the table).

[0255] Evaluation Benchmarks

[0256] ◎: Viscosity change rate is less than 5%

[0257] 0: Viscosity change rate exceeds 5% and is less than 7.5%

[0258] △: Viscosity change rate is 7.5% or more and less than 10%

[0259] ×: Viscosity change rate is 10% or more (outside the practical range)

[0260] (Adhesion)

[0261] The adhesion of the resin composition containing the resin of the example and the comparative example was evaluated. Specifically, the resin composition of the example and the comparative example was applied to a printed substrate (surface modified substrate: corona treated OPP, untreated substrate: untreated OPP) using a bar coater #4, and dried at 100°C for 8 minutes. After a transparent tape (trade name "Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.") was fully pressed against the applied portion, the transparent tape was peeled off. Then, the peeling of the applied surface was visually observed, and the adhesion was evaluated according to the evaluation criteria shown below.

[0262] Evaluation Benchmarks

[0263] ◎: The coated surface was not peeled off at all.

[0264] ○: The coated surface peeled off slightly.

[0265] Δ: The area of ​​the peeled coated surface is larger than the area of ​​the unpeeled and remaining coated surface.

[0266] ×: The coated surface is completely peeled off. (Out of practical range)

[0267] (Anti-adhesion)

[0268] The anti-blocking property of the resin composition containing the resin (resin dispersion) of the example and the comparative example was evaluated. Specifically, the resin composition of the example and the comparative example was applied to the printed substrate (surface modified substrate: corona treated OPP) using a bar coater #4, and after drying at 100°C for 8 minutes, the coated surface and the non-coated surface of the substrate were overlapped, and 3 kg / cm was applied at 50°C and 80% humidity. 2 The adhesive was quickly peeled off after 18 hours under a load, and the anti-blocking property was evaluated according to the following criteria.

[0269] Evaluation Benchmarks

[0270] ◎: No transfer of coating to non-coated surface and no peeling sound

[0271] ○: No transfer of coating to non-coated surface, slight peeling sound

[0272] △: No transfer of coating to non-coated surface, resistance during peeling, and peeling sound

[0273] ×: The coating transfers to the non-coated surface (outside the practical range)

[0274] (Solvent resistance)

[0275] The solvent resistance of the resin composition containing the resin (resin dispersion) of the embodiment and the comparative example was evaluated. Specifically, a printed material with a solid image of 100% printing density was produced on a printed substrate (surface modified substrate: corona treated OPP) using an inkjet recording device, and dried for 8 minutes at any temperature (60°C, 80°C, 100°C) described in the following table. The coating film on the coated surface of the ink composition immediately after printing was observed for appearance under the conditions of Gakushin type friction fastness tester II, 200g weight, and backing cloth: fine cotton cloth (Japanese: Kinjin) No. 3 immersed in an ethanol aqueous solution with a mass concentration of 50%. The appearance of the coating film (described as solvent resistance in the table) was evaluated according to the following evaluation criteria (coating film appearance index).

[0276] Evaluation Benchmarks

[0277] ◎: No appearance change after 50 times

[0278] 0: No appearance change after 25 times. Slight appearance change after 50 times.

[0279] △: No appearance change after 10 times, slight appearance change after 25 times

[0280] ×: Appearance changes after 10 times (outside the practical range)

[0281] (Stretchability)

[0282] The stretchability of the resin composition containing the resin (resin dispersion) of the embodiment and the comparative example was evaluated. Specifically, the printed substrate (polyvinyl chloride film with adhesive) was coated using a rod coater #4 and dried at 100°C for 8 minutes. Then, the substrate coated with the resin composition was cut into a 1.5 cm × 9.0 cm long rectangle and the backing paper was removed. The upper and lower parts were fixed and the entire coating was stretched at a speed of 0.1 mm / min. The coating was interrupted at a point where there were changes such as cracks, and the stretchability at this time was evaluated.

[0283] Evaluation Benchmarks

[0284] ◎: Elongation is more than 150%

[0285] ○: Elongation is 130% or more and less than 150%

[0286] △: Elongation is 120% or more and less than 130%

[0287] ×: Elongation is less than 120% (outside the practical range)

[0288] [Table 2]

[0289]

[0290] [Table 3]

[0291]

[0292] [Table 4]

[0293]

[0294] [Table 5]

[0295]

[0296] In the table, "CHMA" means cyclohexyl methacrylate.

[0297] In the table, "CHA" means cyclohexyl acrylate.

[0298] In the table, "DCPMA" means dicyclopentyl methacrylate.

[0299] In the table, "THFMA" means tetrahydrofurfuryl methacrylate.

[0300] In the table, "CPhA" means 4-chlorophenyl acrylate.

[0301] In the table, "MAA" means methacrylic acid.

[0302] In the table, "DMMA" means 2-(dimethylamino)ethyl methacrylate.

[0303] In the table, "MMA" means methyl methacrylate.

[0304] In the table, "BMA" means butyl methacrylate.

[0305] In the table, "Mw" means weight average molecular weight.

[0306] In the table, "Mn" means number average molecular weight.

[0307] In the table, "corona-treated OPP" refers to a polypropylene-based resin substrate (polyolefin-based resin substrate) whose surface has been subjected to a corona treatment.

[0308] In the table, "untreated OPP" refers to an untreated polypropylene-based resin substrate (polyolefin-based resin substrate).

[0309] In the table, "polyvinyl chloride" refers to polyvinyl chloride film with adhesive.

[0310] As is apparent from the above table, when a resin containing a copolymer including a specific monomer as a structural unit is included in a resin composition, a coating film of the resin composition having solvent resistance can be formed on the surface to be coated.

[0311] Among them, the resins of Examples 1 to 9, 12 to 15, and 25 to 30 containing an emulsion polymer were superior in storage stability when contained in the resin composition, compared with the resins of Examples 10 and 11.

[0312] The resins of Examples 1 to 9, 12 to 15, and 25 to 30, in which the content of the unreacted monomer is 0.1 mass % or less in the total amount of the resin, can form a coating film having higher anti-blocking properties than the resins of Examples 16 to 19 by inclusion in the resin composition.

[0313] The resins of Examples 1 to 9, 12 to 15, and 25 to 30 containing the monomer A having a side chain partial SP value in the range of 8.0 to 11.0 can form a coating film having higher solvent resistance than the resin of Example 20 by being included in the resin composition.

[0314] The resins of Examples 1 to 9, 12 to 15, and 25 to 30 containing the monomer A having a water / 1-octanol partition coefficient (LogP) in the range of 1.9 to 4.8 can form coating films having higher solvent resistance than the resin of Example 21 by being included in the resin composition.

[0315] The resins of Examples 1 to 9, 12 to 15, and 25 to 30 containing a resin having a Tg in the range of 0° C. to 120° C. can form a coating film having high solvent resistance and adhesion compared to the resin of Example 22 by being included in the resin composition.

[0316] In addition, the resins of Examples 1 to 9, 12 to 15, and 25 to 30, which contain monomer A at a ratio of 50% or more in the total amount of the copolymer and monomer B at a ratio of 0.1% or more and 10% or less in the total amount of the copolymer, can form a coating film having high solvent resistance, adhesion and anti-blocking properties by being included in the resin composition, compared with the resins of Examples 23 and 24.

[0317] On the other hand, the resins of Comparative Examples 1 to 3 not containing the monomer A and the resin of Comparative Example 4 not containing the monomer B could not form coating films having high solvent resistance or blocking resistance even if they were included in the resin composition, and could not exhibit the effects of the present invention.

Claims

1. A resin comprising a copolymer, wherein the copolymer comprises the following monomer A and monomer B as structural units: Monomer A: a monomer having at least one ring structure selected from an alicyclic structure, a heterocyclic structure, and an aromatic ring structure; Monomer B: a monomer having an acidic group or a basic group.

2. A resin dispersion comprising the resin according to claim 1 as a polymer fine particle dispersion.

3. The resin dispersion according to claim 2, wherein The resin contained in the polymer fine particle dispersion is an emulsion polymer.

4. The resin dispersion according to claim 2 or 3, wherein The content of unreacted monomers derived from the copolymer is 0.1% by mass or less in the total amount of the resin dispersion.

5. The resin dispersion according to any one of claims 2 to 4, wherein The monomer A has an SP value calculated for the chemical structure defined by R2 in the following formula (1), that is, a side chain SP value of 8.0 or more and 11.0 or less. CH2=C(R1)-R2 ···Formula (1) R1 is hydrogen or methyl.

6. The resin dispersion according to any one of claims 2 to 5, wherein The partition coefficient LogP of the monomer A in water / 1-octanol is 1.9 or more and 4.8 or less.

7. The resin dispersion according to any one of claims 2 to 6, wherein The Tg of the resin is 0° C. or higher and 120° C. or lower.

8. The resin dispersion according to any one of claims 2 to 7, wherein The monomer A is contained in the total amount of the copolymer at a ratio of 50% or more, The monomer B is contained in a ratio of 0.1% to 10% in the total amount of the copolymer. 9 . A resin composition comprising the resin dispersion according to claim 2 .

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