Colored resin particle dispersion, ink, ink set, inkjet printing method, method for producing oil-soluble dye, and printed product

Abstract

A colored resin particle dispersion, ink, ink set, inkjet printing method and printed product, wherein the colored resin particle dispersion contains water and colored resin particles, wherein the colored resin particles contain a polymer P containing a hydrophilic group and an oil-soluble dye, wherein the oil-soluble dye contains an oil-soluble dye (D), and the oil-soluble dye (D) is a water-soluble reactive dye modified with an alkyl group having 4 or more carbon atoms or a counter cation in an acid dye is exchanged with an organic cation containing an alkyl group having 4 or more carbon atoms.

Description

Technical Field

[0001] The present invention relates to a colored resin particle dispersion, ink, ink set, inkjet printing and dyeing method, a method for producing an oil-soluble dye, and a printed and dyed product. Background Art

[0002] Various studies are being conducted on the technology of forming images by inkjet method. In recent years, forming images on cloth by inkjet method is also being conducted. This type of image formation is called inkjet printing.

[0003] For example, Patent Document 1 discloses an inkjet recording water-based ink as an ink most suitable for an inkjet recording method having excellent water resistance, light resistance and storage stability, wherein the ink mainly comprises water, a pigment and a resin and contains at least one azo pigment having a specific structure.

[0004] Furthermore, in Patent Document 2, as an inkjet printing ink composition having excellent storage stability and continuous printing stability, in which the cured ink does not burden the nozzle due to wiping maintenance, is friendly to the printing environment and printing equipment, and can produce good printed products, there is disclosed an inkjet printing ink composition comprising: (A) an organic acid having a lactone structure having a hydroxyl group as a substituent, in which one or more hydroxyl groups are chlorinated with an alkali; (B) a colorant; (C) a styrene-(meth)acrylic acid copolymer; (D) glycerol; and (E) a polyurethane resin.

[0005] Patent Document 1: Japanese Patent Application Publication No. 2002-20661

[0006] Patent Document 2: Japanese Patent Application Publication No. 2018-150401 Summary of the invention

[0007] Technical issues to be solved by the invention

[0008] In image formation using ink containing a color material and water (ie, aqueous ink), there is a need to form an image with higher optical density.

[0009] In order to improve the optical density of an image, it is believed that it is effective to use an oil-soluble dye (i.e., an oil-soluble dye) as a colorant in ink. It is believed that when an image is formed on a recording medium using an ink containing an oil-soluble dye, the oil-soluble dye can be aggregated at a high density on the surface and / or surface layer of the recording medium, thereby forming an image with excellent optical density.

[0010] However, inks containing oil-soluble dyes and water may have poor storage stability.

[0011] From the above viewpoints, it is considered desirable to provide an aqueous ink that can form an image having excellent optical density and also has excellent storage stability.

[0012] An object of one embodiment of the present invention is to provide a colored resin particle dispersion and ink that can form an image having excellent optical density and also have excellent storage stability.

[0013] Another aspect of the present invention is to provide an ink set including the above-mentioned ink and an inkjet printing method using the above-mentioned ink.

[0014] Another aspect of the present invention aims to provide a method for producing an oil-soluble dye, which can produce an oil-soluble dye suitable as a dye in the above-mentioned colored resin particle dispersion.

[0015] Another aspect of the present invention aims to provide a printed product having an image excellent in optical density.

[0016] Means for solving technical problems

[0017] Specific methods for solving the problem include the following.

[0018] <1> A colored resin particle dispersion comprising:

[0019] water; and

[0020] Colored resin particles, comprising a polymer P containing a hydrophilic group and an oil-soluble dye,

[0021] The oil-soluble dye includes an oil-soluble dye (D) obtained by modifying a water-soluble reactive dye with an alkyl group having 4 or more carbon atoms or by replacing a counter cation in an acid dye with an organic cation containing an alkyl group having 4 or more carbon atoms.

[0022] <2> A colored resin particle dispersion comprising:

[0023] water; and

[0024] Colored resin particles, comprising an oil-soluble dye and a polymer P containing a hydrophilic group,

[0025] The oil-soluble dye includes an oil-soluble dye (D1) represented by the following formula (D1).

[0026] [Chemical formula 1]

[0027]

[0028] In formula (D1),

[0029] R 1 ~R10 each independently represents a hydrocarbon group having 1 to 60 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom, a hydrogen atom, a chlorine atom, a nitro group, an amino group, a sulfo group or a salt of a sulfo group,

[0030] Two Xs + represents an inorganic cation or an organic cation,

[0031] Among them, satisfying R 1 ~R 10 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the organic cations is at least one of an organic cation containing an alkyl group having 4 or more carbon atoms.

[0032] <3> The colored resin particle dispersion according to <2>, wherein

[0033] The oil-soluble dye (D1) is an oil-soluble dye (D2) represented by the following formula (D2).

[0034] [Chemical formula 2]

[0035]

[0036] In formula (D2),

[0037] R 11 and R 12 each independently represents a hydrocarbon group having 1 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom,

[0038] Two Xs + represents an inorganic cation or an organic cation,

[0039] Among them, satisfying R 11 and R 12 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the organic cations is at least one of an organic cation containing an alkyl group having 4 or more carbon atoms.

[0040] <4> The colored resin particle dispersion according to <2> or <3>, wherein

[0041] The oil-soluble dye (D1) is an oil-soluble dye (D3) represented by the following formula (D3).

[0042] [Chemical formula 3]

[0043]

[0044] In formula (D3),

[0045] R13 ~R 16 each independently represents a hydrocarbon group having 1 to 25 carbon atoms or a hydrogen atom which may contain an oxygen atom, a nitrogen atom or a sulfur atom,

[0046] Two Xs + represents an inorganic cation or an organic cation,

[0047] Among them, satisfying R 13 ~R 16 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the organic cations is at least one of an organic cation containing an alkyl group having 4 or more carbon atoms.

[0048] <5> The colored resin particle dispersion according to <4>, wherein

[0049] In formula (D3),

[0050] R 13 ~R 16 At least one of them is a group containing an alkyl group having 4 or more carbon atoms,

[0051] Two Xs + Each is K + Or Na + .

[0052] <6> The colored resin particle dispersion according to any one of <1> to <5>, wherein

[0053] The hydrophilic group-containing polymer P further contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

[0054] [Chemical formula 4]

[0055]

[0056] In formula (1),

[0057] L 1 represents a hydrocarbon group,

[0058] The two *1s represent the bonding positions respectively.

[0059] In formula (2),

[0060] L 2 represents a hydrocarbon group having 2 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, or a polymer chain having a number average molecular weight of 500 or more consisting of a polyether chain, a polyester chain, a polycaprolactone chain, a polycarbonate chain, a polybutadiene chain, a polyisoprene chain or a polyolefin chain,

[0061] Y1 and Y 2 Each independently represents -O-, -S- or -NRz-,

[0062] Rz represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0063] The two *2s represent the bonding positions respectively.

[0064] <7> The colored resin particle dispersion according to <6>, wherein

[0065] L in formula (2) 2 It is a polymer chain having a number average molecular weight of 500 or more and composed of a polycarbonate chain or a polyether chain.

[0066] <8> The colored resin particle dispersion according to any one of <1> to <7>, wherein

[0067] The glass transition temperature of the hydrophilic group-containing polymer P is 50° C. or lower.

[0068] <9> The colored resin particle dispersion according to any one of <1> to <8>, wherein

[0069] The hydrophilic group in the hydrophilic group-containing polymer P is at least one selected from the group consisting of a carboxyl group and a salt of a carboxyl group.

[0070] <10> The colored resin particle dispersion according to any one of <1> to <9>, wherein

[0071] The weight average molecular weight of the hydrophilic group-containing polymer P is 8,000 to 30,000.

[0072] <11> An ink comprising the colored resin particle dispersion according to any one of <1> to <10>.

[0073] <12> The ink according to <11>, which is used as an inkjet ink.

[0074] <13> The ink according to <11> or <12>, which is used as a textile printing ink.

[0075] <14> An ink set comprising two or more inks,

[0076] At least one of the two or more inks is the ink described in any one of <11> to <13>.

[0077] <15> An inkjet printing and dyeing method, comprising:

[0078] A step of applying the ink described in any one of <11> to <13> to a fabric by an inkjet method; and

[0079] The process of obtaining a printed product by heat-treating the cloth to which ink has been applied.

[0080] <16> A method for producing an oil-soluble dye, comprising the step of obtaining the oil-soluble dye by method (1) or method (2), wherein in method (1), a water-soluble reactive dye is reacted with a primary amine compound containing a group containing an alkyl group having more than 4 carbon atoms, a secondary amine compound containing a group containing an alkyl group having more than 4 carbon atoms, a hydroxy compound containing a group containing an alkyl group having more than 4 carbon atoms, or a thiol compound containing a group containing an alkyl group having more than 4 carbon atoms, and in method (2), an acid dye is reacted with a salt of an organic cation containing an alkyl group having more than 4 carbon atoms.

[0081] <17> A printed article comprising: a cloth and an image,

[0082] The image comprises an oil-soluble dye (D) and a polymer P containing a hydrophilic group. The oil-soluble dye (D) is a water-soluble reactive dye modified with an alkyl group having 4 or more carbon atoms or a counter cation in an acid dye is replaced with an organic cation containing an alkyl group having 4 or more carbon atoms.

[0083] Effects of the Invention

[0084] According to one aspect of the present invention, a colored resin particle dispersion and an ink are provided that can form an image having excellent optical density and have excellent storage stability.

[0085] According to another aspect of the present invention, there are provided an ink set including the above ink and an inkjet printing method using the above ink.

[0086] According to still another aspect of the present invention, there is provided a method for producing an oil-soluble dye, the method being capable of producing an oil-soluble dye suitable as a dye in the above-mentioned colored resin particle dispersion.

[0087] According to still another aspect of the present invention, there is provided a printed product having an image excellent in optical density. DETAILED DESCRIPTION

[0088] In the present invention, a numerical range expressed using "to" indicates a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0089] In the present invention, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition represents the total amount of the plurality of substances present in the composition unless otherwise specified.

[0090] In the numerical ranges described stepwise in the present invention, the upper limit or lower limit described in a certain numerical range may be replaced by the upper limit or lower limit of another numerical range described stepwise, or may be replaced by the value shown in the Examples.

[0091] In the present invention, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0092] In the present invention, the "image" refers to the entire film (including the coating film) formed using the printing ink.

[0093] The concept of "image" in the present invention also includes solid images.

[0094] [Colored resin particle dispersion (first embodiment)]

[0095] The colored resin particle dispersion according to the first aspect of the present invention contains:

[0096] water; and

[0097] Colored resin particles, comprising a polymer P containing a hydrophilic group and an oil-soluble dye,

[0098] The oil-soluble dye includes an oil-soluble dye (D) obtained by modifying a water-soluble reactive dye with an alkyl group having 4 or more carbon atoms or by replacing a counter cation in an acid dye with an organic cation containing an alkyl group having 4 or more carbon atoms.

[0099] In the present invention, "water-soluble" means that the amount of the compound dissolved in 100 g of distilled water at 25°C is more than 1 g, and "water-insoluble" means that the amount of the compound dissolved in 100 g of distilled water at 25°C is 1 g or less.

[0100] In the present invention, the "oil-soluble dye" refers to a dye having a solubility in methyl ethyl ketone at 20°C (hereinafter also referred to as "MEK solubility") of 5% by mass or more.

[0101] Hereinafter, a water-soluble reactive dye modified with an alkyl group having 4 or more carbon atoms to obtain an oil-soluble dye (D) is sometimes expressed as an "oil-solubilized water-soluble reactive dye", and an oil-soluble dye (D) obtained by exchanging the counter cation in an acid dye with an organic cation containing an alkyl group having 4 or more carbon atoms is sometimes expressed as an "oil-solubilized acid dye".

[0102] As the oil-soluble dye, a water-insoluble dye, that is, a dye which dissolves in 100 g of distilled water at 20° C. in an amount of 1 g or less is preferred.

[0103] The colored resin particle dispersion of the first embodiment can form an image having excellent optical density and is also excellent in storage stability.

[0104] It is believed that the reason why an image with excellent optical density can be formed is that the oil-soluble dye (D) obtained by dissolving a water-soluble reactive dye or an acid dye in oil has oil solubility, so that the oil-soluble dye (D) is aggregated at a high density on the surface and / or surface layer of the recording medium (e.g., cloth).

[0105] On the other hand, inks containing oil-soluble dyes and water may have poor storage stability.

[0106] However, the colored resin particle dispersion of the first embodiment is also excellent in storage stability.

[0107] As a first factor that enables the effect of storage stability to be obtained, it is considered that the dispersion stability of the colored resin particles in the colored resin particle dispersion of the first embodiment is ensured because the colored resin particles contain the polymer P having a hydrophilic group.

[0108] As a second factor that enables the effect of storage stability to be obtained, it is considered that the water-soluble reactive dye and acid dye that are the raw materials of the oil-soluble dye (D) originally contain a hydrophilic group, and the oil-soluble dye (D) also contains the hydrophilic group (that is, the oil-soluble dye (D) contained in the colored resin particles has self-dispersibility).

[0109] It is considered that these two factors work together to exert the above-mentioned effect of the storage stability of the colored resin particle dispersion.

[0110] In the examples described below, the ejection properties and storage stability of the ink containing the colored resin particle dispersion were evaluated as indicators of the storage stability of the colored resin particle dispersion.

[0111] Hereinafter, each component that may be contained in the colored resin particle dispersion of the first embodiment will be described.

[0112] <Water>

[0113] The colored resin particle dispersion of the first embodiment contains water.

[0114] The content of water in the colored resin particle dispersion of the first embodiment is, for example, 40% by mass or more, preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total amount of the colored resin particle dispersion of the first embodiment.

[0115] The upper limit of the water content depends on the amount of solid content in the colored resin particle dispersion of the first embodiment, but is, for example, 90% by mass based on the total amount of the colored resin particle dispersion of the first embodiment.

[0116] <Colored resin particles>

[0117] The colored resin particle dispersion of the first embodiment contains colored resin particles.

[0118] The colored resin particles contain a polymer P having a hydrophilic group and an oil-soluble dye.

[0119] (Oil-soluble dye (D))

[0120] The oil-soluble dye contains an oil-soluble dye (D).

[0121] The oil-soluble dye (D) is a water-soluble reactive dye modified with an alkyl group having 4 or more carbon atoms or a dye in which the counter cation in the acid dye is replaced with an organic cation containing an alkyl group having 4 or more carbon atoms.

[0122] In the oil-soluble dye (D), the alkyl group having 4 or more carbon atoms preferably has 4 to 25 carbon atoms, more preferably 4 to 20 carbon atoms, further preferably 4 to 12 carbon atoms, and further preferably 4 to 10 carbon atoms.

[0123] The alkyl group having 4 or more carbon atoms may be a linear alkyl group or a branched alkyl group.

[0124] In the present invention, of course, the water-soluble reactive dye has water solubility, and the acid dye also has water solubility.

[0125] Water-soluble reactive dyes and acid dyes are not oil-soluble.

[0126] -Water-soluble reactive dyes-

[0127] The water-soluble reactive dye as one embodiment of the raw material of the oil-soluble dye (D) is preferably a dye containing an anion having a dye skeleton, a counter cation, and a reactive group.

[0128] As the water-soluble reactive dye, the following water-soluble reactive dye (DA) is preferable.

[0129] [Chemical formula 5]

[0130]

[0131] In water-soluble reactive dyes (DA), D A represents an (m+n)-valent organic group having a dye skeleton, R a Represents a reactive group, A - represents an anionic group, Xa + represents the hydrogen ion (H + ) or an alkali metal ion, m represents an integer greater than 1, and n is an integer greater than 1.

[0132] As D A It is preferably an (m+n)-valent organic group having an azo dye skeleton, and more preferably an (m+n)-valent organic group having a disazo dye skeleton.

[0133] As R a The following reactive groups (R1) are preferred. In the reactive group (R1), Xb + represents a hydrogen ion or an alkali metal ion, and * represents a bonding position.

[0134] [Chemical formula 6]

[0135]

[0136] In water-soluble reactive dyes (DA), as A - The anionic group represented by - group) or carboxylate group (-COO - base).

[0137] In water-soluble reactive dyes (DA), as Xa + The alkali metal ion represented by is preferably Na + or K + .

[0138] In the water-soluble reactive dye (DA), m is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, further preferably 1 or 2, and further preferably 2.

[0139] In the water-soluble reactive dye (DA), n is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, further preferably 1 or 2, and further preferably 2.

[0140] As the water-soluble reactive dye, it is possible to appropriately select and use it from water-soluble reactive dyes using the term "Reactive" in the color index (CI) number.

[0141] Specific examples of the water-soluble reactive dye include:

[0142] CIReactive Black 5, 14;

[0143] CIReactive Yellow 15, 17, 23, 24, 37, 42, 57, 76, 145, 160, 167;

[0144] CIReactive Orange 7, 15, 16, 56, 72, 74, 82, 107;

[0145] CIReactive Red 21, 22, 23, 35, 106, 111, 112, 113, 114, 174, 180, 194, 195, 222, 223;

[0146] CIReactive Violet 4, 5, 22;

[0147] CIReactive Blue 19, 21, 27, 28, 38, 147, 194, 221, 222, 231;

[0148] CIReactive Brown 21, 46;

[0149] wait.

[0150] These specific examples all correspond to water-soluble reactive dyes (DA).

[0151] For example, the structures of CIReactive Black 5, CIReactive Yellow 145, CIReactive Orange 72, and CIReactive Red 195 are as follows.

[0152] In the following, the notation of "CI" may be omitted.

[0153] [Chemical formula 7]

[0154]

[0155] -Oil dissolution of water-soluble reactive dyes-

[0156] As described above, the oil solubilization of a water-soluble reactive dye is performed by modifying the water-soluble reactive dye with an alkyl group having 4 or more carbon atoms.

[0157] Here, "modifying a water-soluble reactive dye with an alkyl group having 4 or more carbon atoms" is preferably performed by modifying a part of the reactive group in the water-soluble reactive dye (preferably -OSO3 in the reactive group (R1)) - Xb + ) is substituted with a group containing an alkyl group having 4 or more carbon atoms.

[0158] The total number of carbon atoms in the group containing an alkyl group having 4 or more carbon atoms is preferably 4 to 60, more preferably 4 to 50, further preferably 4 to 30, and further preferably 4 to 25.

[0159] Examples of the group containing an alkyl group having 4 or more carbon atoms include a secondary amino group, a tertiary amino group, an alkoxy group which may be substituted, and a sulfanyl group which may be substituted.

[0160] As the group containing an alkyl group having 4 or more carbon atoms, a secondary amino group or a tertiary amino group is preferred from the viewpoint of excellent reactivity in oil solubility and further suppression of the generation of water-soluble by-products.

[0161] -Acid dyes-

[0162] The acid dye as another embodiment of the raw material of the oil-soluble dye (D) is preferably a dye containing an anion and a counter cation having a dye skeleton.

[0163] As the acid dye, the following acid dye (DB) is preferable.

[0164] [Chemical formula 8]

[0165]

[0166] In acid dye (DB), D B represents an n-valent organic group having a dye skeleton, A - represents an anionic group, Xb + represents the hydrogen ion (H + ) or an alkali metal ion, and n represents an integer greater than 1.

[0167] D in acid dye (DB) B , A - , Xb + The preferred forms of n and n are respectively the same as D in the water-soluble reactive dye (DA) A , A - , Xa + The preferred manner for and n is the same.

[0168] The acid dye can be appropriately selected from acid dyes using the term "Acid" in the color index (CI) number.

[0169] Specific examples of the acid dye include:

[0170] CIAcid Black 1, 2, 3, 24, 24:1, 26, 31, 50, 52, 52:1, 58, 60, 63, 63S, 107, 109, 112, 119, 132, 140, 155, 172, 187, 188, 194, 207, 222;

[0171] C.I.Acid Yellow 1,3,6、11,17,18,19,23,25,36,38,40,40:1,42,44,49,59,59:1,61,65,67,72,73,79,99,104,159,169,176,184,193,200,204,207,215,219,219:1,220,230,232,235,241,242,246;

[0172] C.I.Acid Orange 3、7、8、10、19、22、24、51、51S、56、67、74、80、86、87、88、89、94、95、107、108、116、122、127、140、142、144、149、152、156、162、166、168;

[0173] C.I.Acid Red 1、6、8、9、13、18、27、35、37、52、54、57、73、82、88、97、97:1、106、111、114、118、119、127、131、138、143、145、151、183、195、198、211、215、217、225、226、249、251、254、256、257、260、261、265、266、274、276、277、289、296、299、315、318、336、337、357、359、361、362、364、366、399、407、415、447;

[0174] C.I.Acid Vioret 17,19,21,42,43,47,48,49,54,66,78,90,97,102,109,126;

[0175] C.I.Acid Blue 1、7、9、15、23、25、40、61:1、62、72、74、80、83、90、92、103、104、112、113、114、120、127、127:1、128、129、138、140、142、156、158、171、182、185、193、199、201、203、204、205、207、209、220、221、224、225、229、230、239、258、260、264、277:1、278、279、280、284、290、296、298、300、317、324、333、335、338、342、350;

[0176] CIAcid Green 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109;

[0177] CIAcid Brown 2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413;

[0178] wait.

[0179] The structure of CIAcid Black 1 (hereinafter, "CI" may be abbreviated) which is one specific example of the acid dye is as follows.

[0180] [Chemical formula 9]

[0181]

[0182] -Oil dissolution of acid dyes-

[0183] The oil solubilization of the acid dye is carried out by exchanging the counter cation in the acid dye with an organic cation containing an alkyl group having 4 or more carbon atoms.

[0184] In the present invention, “the counter cation in the acid dye is exchanged with an organic cation containing an alkyl group having 4 or more carbon atoms” means that the counter cation in the acid dye is exchanged with an organic cation containing an alkyl group having 4 or more carbon atoms by a counter cation exchange reaction.

[0185] The total carbon number of the organic cation containing an alkyl group having 4 or more carbon atoms is preferably 4 to 60, more preferably 4 to 50, further preferably 4 to 30, and further preferably 4 to 25.

[0186] As the organic cation containing an alkyl group having 4 or more carbon atoms, an organic ammonium ion containing an alkyl group having 4 or more carbon atoms is preferred.

[0187] From the viewpoint of further improving the optical density of an image, the oil-soluble dye (D) is preferably a dye in which a water-soluble reactive dye is modified with an alkyl group having 4 or more carbon atoms.

[0188] The molecular weight of the oil-soluble dye (D) is not particularly limited, but is preferably 2,000 or less, more preferably 1,500 or less.

[0189] The lower limit of the molecular weight of the oil-soluble dye (D) depends on the skeleton of the dye, and is, for example, 600 or more, and more preferably 700 or more.

[0190] (Method for producing oil-soluble dye (D))

[0191] As a method for producing the oil-soluble dye (D), the following method (hereinafter referred to as production method (D)) is preferred.

[0192] The preparation method (D) comprises the step of obtaining an oil-soluble dye by the method (1) or the method (2),

[0193] In the method (1), a water-soluble reactive dye is reacted with a primary amine compound containing a group having an alkyl group with more than 4 carbon atoms, a secondary amine compound containing a group having an alkyl group with more than 4 carbon atoms, a hydroxy compound containing a group having an alkyl group with more than 4 carbon atoms, or a thiol compound containing a group having an alkyl group with more than 4 carbon atoms, and in the method (2), an acid dye is reacted with a salt of an organic cation containing an alkyl group with more than 4 carbon atoms.

[0194] The preparation method (D) may include other steps as necessary.

[0195] The oil-soluble dye obtained in the step of obtaining the oil-soluble dye corresponds to the above-mentioned oil-soluble dye (D).

[0196] In each compound used in the step of obtaining the oil-soluble dye, the preferred number of carbon atoms of the "alkyl group having 4 or more carbon atoms" is as described above.

[0197] Hereinafter, the method (1) and the method (2) in the step of obtaining the oil-soluble dye will be described.

[0198] -Method (1)-

[0199] In the method (1), the water-soluble reactive dye is solubilized in oil (that is, the water-soluble reactive dye is modified with an alkyl group having 4 or more carbon atoms) as described below to obtain the above-mentioned oil-soluble dye (D).

[0200] In method (1),

[0201] Make water-soluble reactive dyes

[0202] Primary amine compound containing a group containing an alkyl group having 4 or more carbon atoms

[0203] When the reaction is carried out, as the aforementioned oil-soluble dye (D),

[0204] An oil-soluble dye having a structure in which a part of the reactive groups in a water-soluble reactive dye is substituted with a secondary amino group containing a group having an alkyl group having 4 or more carbon atoms (for example, d-4 to d-6 in the examples described below) can be obtained.

[0205] The total number of carbon atoms in the primary amine compound including a group having an alkyl group having 4 or more carbon atoms is preferably 4 to 60, more preferably 4 to 50, further preferably 4 to 30, and further preferably 4 to 25.

[0206] In method (1),

[0207] Make water-soluble reactive dyes

[0208] Secondary amine compound containing a group containing an alkyl group having 4 or more carbon atoms

[0209] When the reaction is carried out, as the aforementioned oil-soluble dye (D),

[0210] Oil-soluble dyes having a structure in which part of the reactive groups in the water-soluble reactive dye is substituted with a tertiary amino group containing a group having an alkyl group having 4 or more carbon atoms (for example, d-7 to d-10 in the examples described below) can be obtained.

[0211] The total number of carbon atoms in the secondary amine compound including a group having an alkyl group having 4 or more carbon atoms is preferably 4 to 60, more preferably 4 to 50, further preferably 4 to 30, and further preferably 4 to 25.

[0212] In method (1),

[0213] Make water-soluble reactive dyes

[0214] Hydroxyl compounds containing a group containing an alkyl group having 4 or more carbon atoms

[0215] When the reaction is carried out, as the aforementioned oil-soluble dye (D),

[0216] An oil-soluble dye having a structure (e.g., d-2 in the examples described later) can be obtained, in which a part of the reactive group in the water-soluble reactive dye (preferably -OSO3 in the reactive group (R1)) is - Xb + The same shall apply hereinafter. ) is substituted with a monovalent organic group consisting of a group containing an alkyl group having 4 or more carbon atoms and an ether bond (-O-).

[0217] The total number of carbon atoms in the hydroxy compound including a group having an alkyl group having 4 or more carbon atoms is preferably 4 to 60, more preferably 4 to 50, further preferably 4 to 30, and further preferably 4 to 25.

[0218] In method (1),

[0219] Make water-soluble reactive dyes

[0220] Thiol compound containing a group containing an alkyl group having 4 or more carbon atoms

[0221] When the reaction is carried out, as the aforementioned oil-soluble dye (D),

[0222] An oil-soluble dye having a structure in which a part of the reactive group in the water-soluble reactive dye is substituted with a monovalent organic group consisting of a group containing an alkyl group having 4 or more carbon atoms and a thioether bond (-S-) can be obtained (for example, d-3 in the examples described later).

[0223] The total number of carbon atoms in the thiol compound including the group containing an alkyl group having 4 or more carbon atoms is preferably 4 to 60, more preferably 4 to 50, further preferably 4 to 30, and further preferably 4 to 25.

[0224] The reaction temperature of the reaction in the method (1) is, for example, 40 to 100°C, preferably 40 to 90°C, more preferably 50 to 90°C, and further preferably 50 to 80°C.

[0225] The reaction time of the reaction in the method (1) is, for example, 0.3 to 8 hours, preferably 0.5 to 6 hours, and more preferably 1 to 4 hours.

[0226] The reaction in the method (1) is preferably carried out in an organic solvent as a reaction solvent.

[0227] Examples of the organic solvent include ethyl acetate and methyl ethyl ketone.

[0228] When the reaction in method (1) is carried out in a reaction solvent, it is preferred to add water to the obtained reaction solution to precipitate the product (ie, the oil-soluble dye).

[0229] -Method (2)-

[0230] In method (2), the counter cation in the acid dye is substituted with an organic cation containing an alkyl group having at least 4 carbon atoms by reacting the acid dye with a salt containing an organic cation containing an alkyl group having at least 4 carbon atoms. Thus, the acid dye is oil-solubilized to obtain the above-mentioned oil-soluble dye (D).

[0231] The total number of carbon atoms in the salt containing an organic cation having an alkyl group having 4 or more carbon atoms is preferably 4 to 60, more preferably 4 to 50, further preferably 4 to 30, and further preferably 4 to 25.

[0232] As the anion in the salt containing the organic cation having an alkyl group having 4 or more carbon atoms, a halide ion (e.g., Cl - Br - ).

[0233] Preferred aspects of the reaction conditions in method (2) (reaction temperature, reaction time, reaction solvent, etc.) are the same as those in method (1).

[0234] From the viewpoint of further improving the optical density of the image, the step of obtaining the oil-soluble dye is preferably a step of obtaining the oil-soluble dye by the method (1).

[0235] (Preferred embodiment of the oil-soluble dye (D))

[0236] As one of the preferred embodiments of the oil-soluble dye (D), an oil-soluble dye (D1) represented by the following formula (D1) can be mentioned.

[0237] The oil-soluble dye (D1) contains the dye skeleton of Reactive Black 5 which is a water-soluble reactive dye, and contains the dye skeleton of Acid Black 1 which is an acid dye.

[0238] Therefore, the oil-soluble dye (D1) in the colored resin particle dispersion of the first embodiment can be obtained by dissolving Reactive Black 5 or Acid Black 1 in oil.

[0239] However, in the colored resin particle dispersion of the second embodiment described below, the oil-soluble dye (D1) is not limited to the one obtained by dissolving Reactive Black 5 or Acid Black 1 in oil.

[0240] [Chemical formula 10]

[0241]

[0242] In formula (D1),

[0243] R 1 ~R 10 each independently represents a hydrocarbon group having 1 to 60 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom, a hydrogen atom, a chlorine atom, a nitro group, an amino group, a sulfo group or a salt of a sulfo group,

[0244] Two Xs + represents an inorganic cation or an organic cation,

[0245] Among them, satisfying R 1 ~R 10 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the organic cations is at least one of an organic cation containing an alkyl group having 4 or more carbon atoms.

[0246] In formula (D1), R 1 ~R 10The hydrocarbon group having 1 to 60 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom respectively represented means an organic group having a total of 1 to 60 carbon atoms which contains carbon atoms and hydrogen atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom.

[0247] R 1 ~R 10 The hydrocarbon group which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom represented by each may be a hydrocarbon group which does not contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom.

[0248] Examples of the hydrocarbon group not containing an oxygen atom, a nitrogen atom, a sulfur atom, and a chlorine atom include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and an alkaryl group.

[0249] The concept of the hydrocarbon group containing an oxygen atom includes, for example, a hydroxyalkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group and the like.

[0250] The concept of the hydrocarbon group containing a nitrogen atom includes, for example, an alkylamino group (ie, a monoalkylamino group or a dialkylamino group), an alkylaminoalkyl group, and the like.

[0251] The concept of the hydrocarbon group containing a sulfur atom includes, for example, a thiol alkyl group, an alkylthio group, and the like.

[0252] The concept of the hydrocarbon group containing an oxygen atom and a sulfur atom includes, for example, an alkylsulfonyl group, an arylsulfonyl group, an alkoxyalkylthio group, an alkylthioalkylsulfonyl group, an alkoxyalkylsulfonyl group, and the like.

[0253] The concept of the hydrocarbon group containing an oxygen atom, a nitrogen atom and a sulfur atom includes, for example, an alkoxyalkylaminoalkylsulfonyl group, an alkylaminoalkylsulfonyl group and the like.

[0254] The concept of the hydrocarbon group containing a chlorine atom includes groups in which the hydrogen atoms in the above specific examples are substituted with chlorine atoms.

[0255] R 1 ~R 10 The number of carbon atoms of each of the hydrocarbon groups having 1 to 60 which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom is preferably 1 to 50.

[0256] As R 1 ~R 10 The hydrocarbon group having 1 to 60 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom represented by each is preferably a hydrocarbon group having 1 to 60 carbon atoms (more preferably 1 to 50 carbon atoms) which may contain an oxygen atom, a nitrogen atom or a sulfur atom.

[0257] R 1 ~R 10The hydrocarbon group having 1 to 60 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom represented by each of the above groups preferably contains a sulfonyl group.

[0258] As R 1 ~R 10 The hydrocarbon group having 1 to 60 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a chlorine atom represented by each is particularly preferably an alkylthioalkylsulfonyl group, an alkoxyalkylsulfonyl group, an alkoxyalkylaminoalkylsulfonyl group [i.e., a mono(alkoxyalkyl)aminoalkylsulfonyl group or a di(alkoxyalkyl)aminoalkylsulfonyl group] or an alkylaminoalkylsulfonyl group [i.e., a monoalkylaminoalkylsulfonyl group or a dialkylaminoalkylsulfonyl group].

[0259] R 1 ~R 10 The groups may be independently a hydrogen atom, a chlorine atom, a nitro group, an amino group, a sulfo group or a salt of a sulfo group.

[0260] As the salt of the sulfonic group, an alkali metal salt is preferred.

[0261] Two Xs + represents an inorganic cation or an organic cation,

[0262] As the inorganic cation, hydrogen ion (H + ) or an alkali metal ion, more preferably an alkali metal ion, further preferably K + Or Na + .

[0263] As the organic cation, an organic ammonium ion is preferred.

[0264] Formula (D1) satisfies R 1 ~R 10 At least one (more preferably at least two) of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one (more preferably two) of the cations is at least one of organic cations containing an alkyl group having 4 or more carbon atoms.

[0265] Preferred embodiments of the "group containing an alkyl group having 4 or more carbon atoms" and the "organic cation containing an alkyl group having 4 or more carbon atoms" in formula (D1) are the same as those described in the description of the oil-soluble dye (D).

[0266] From the viewpoint of further improving the optical density of the image, a preferred embodiment of formula (D1) is that R 1 ~R 10 At least one of the X is a group containing an alkyl group having 4 or more carbon atoms and the two X + K + Or Na + way.

[0267] From the viewpoint of further improving the optical density of an image, the oil-soluble dye (D1) is preferably an oil-soluble dye (D2) represented by the following formula (D2).

[0268] [Chemical formula 11]

[0269]

[0270] In formula (D2),

[0271] R 11 and R 12 each independently represents a hydrocarbon group having 1 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom,

[0272] Two Xs + represents an inorganic cation or an organic cation,

[0273] Among them, satisfying R 11 and R 12 At least one (more preferably two) of the groups is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one (more preferably two) of the cations is at least one of organic cations containing an alkyl group having 4 or more carbon atoms.

[0274] As preferred embodiments of each group and cation in formula (D2), reference can be made to preferred embodiments of each group and cation in formula (D1) as appropriate.

[0275] From the viewpoint of further improving the optical density of the image, a preferred embodiment of formula (D2) is that R 11 and R 12 At least one (more preferably two) of the X is a group containing an alkyl group having 4 or more carbon atoms and the two X + K + Or Na + way.

[0276] From the viewpoint of further improving the optical density of an image, the oil-soluble dye (D1) is more preferably an oil-soluble dye (D3) represented by the following formula (D3).

[0277] [Chemical formula 12]

[0278]

[0279] In formula (D3),

[0280] R 13 ~R 16each independently represents a hydrocarbon group having 1 to 25 carbon atoms or a hydrogen atom which may contain an oxygen atom, a nitrogen atom or a sulfur atom,

[0281] Two Xs + represents an inorganic cation or an organic cation,

[0282] Among them, satisfying R 13 ~R 16 At least one (more preferably at least two) of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one (more preferably two) of the cations is at least one of organic cations containing an alkyl group having 4 or more carbon atoms.

[0283] As preferred embodiments of each group and cation in formula (D3), reference can be made to preferred embodiments of each group and cation in formula (D1) as appropriate.

[0284] From the viewpoint of further improving the optical density of the image, a preferred embodiment of formula (D3) is: 13 ~R 16 At least one (more preferably at least two) of the X is a group containing an alkyl group having 4 or more carbon atoms and the two X + K + Or Na + way.

[0285] (Specific example of oil-soluble dye (D))

[0286] Hereinafter, specific examples of the oil-soluble dye (D) will be described, but the oil-soluble dye (D) is not limited to these specific examples.

[0287] Specific examples of the oil-soluble dye (D) include d-1 to d-10 described in the Examples below. d-1 to d-10 are also specific examples of the oil-soluble dye (D1).

[0288] (Other oil-soluble dyes)

[0289] The colored resin particles contain the above-mentioned oil-soluble dye (D), but may contain other oil-soluble dyes in addition to the oil-soluble dye (D) as necessary.

[0290] As other oil-soluble dyes, oil-soluble dyes using the word "Solvent" in the color index (CI) number can be used.

[0291] Specific examples of the oil-soluble dye include:

[0292] CI Solvent Yellow (Solvent Yellow) 2, 14, 16, 21, 33, 43, 44, 56, 82, 85, 93, 98, 114, 131, 135, 157, 160, 163, 167, 176, 179, 185, 189;

[0293] CI Solvent Red (Solvent Red) 8, 23, 24, 25, 49, 52, 109, 111, 119, 122, 124, 135, 146, 149, 150, 168, 169, 172, 179, 195, 196, 197, 207, 222, 227, 312, 313;

[0294] CI Solvent Blue (Solvent Blue) 3, 4, 5, 35, 36, 38, 44, 45, 59, 63, 67, 68, 70, 78, 83, 97, 101, 102, 104, 105, 111, 122;

[0295] CI Solvent Orange (Solvent Orange) 3, 14, 54, 60, 62, 63, 67, 86, 107;

[0296] CI Solvent Violet (Solvent Violet) 8, 9, 11, 13, 14, 26, 28, 31, 36, 59;

[0297] CI Solvent Green (Solvent Green) 3, 5, 7, 28;

[0298] CI Solvent Brown (Solvent Brown) 53;

[0299] CI Solvent Black (Solvent Black) 3, 5, 7, 27, 28, 29, 34;

[0300] wait.

[0301] The ratio of the oil-soluble dye (D) to the oil-soluble dye in the colored resin particles is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass.

[0302] (Polymer P)

[0303] The colored resin particles contain at least one polymer P containing a hydrophilic group.

[0304] The polymer P is not particularly limited except that it contains hydrophilic groups.

[0305] -Hydrophilic Group-

[0306] The polymer P comprises at least one hydrophilic group.

[0307] As described above, the hydrophilic group in the polymer P contributes to the dispersion stability of the colored resin particles in the colored resin particle dispersion.

[0308] As the hydrophilic group, an anionic group or a nonionic group is preferred, and an anionic group is more preferred from the viewpoint of excellent effect of improving dispersion stability.

[0309] For example, when comparing anionic groups and nonionic groups of the same molecular weight, the anionic group has a more excellent effect of improving dispersion stability. That is, when the molecular weight of the anionic group (particularly preferably at least one selected from the group including a carboxyl group and a salt of a carboxyl group) is relatively small, the effect of improving dispersion stability can also be fully exerted.

[0310] Examples of the nonionic group include groups having a polyether structure, and a monovalent group containing a polyalkylene oxide group is preferred.

[0311] The anionic group may be neutralized or may not be neutralized.

[0312] Examples of the unneutralized anionic group include a carboxyl group, a sulfo group, a sulfate group, a phosphonic acid group, and a phosphoric acid group.

[0313] Examples of the anionic group to be neutralized include salts of carboxyl groups, salts of sulfonic groups, salts of sulfate groups, salts of phosphonic acid groups, and salts of phosphoric acid groups.

[0314] In the present invention, the neutralized anionic group refers to an anionic group in the form of a "salt" (for example, a salt of a carboxyl group (for example, -COONa)).

[0315] Neutralization can be performed using, for example, an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide, etc.) or an organic amine (eg, triethylamine, etc.).

[0316] As the hydrophilic group in the polymer P, from the viewpoint of dispersion stability,

[0317] Preferably, anionic groups

[0318] More preferably, at least one selected from the group consisting of a carboxyl group, a carboxyl salt, a sulfonyl group, a sulfonyl salt, a sulfate group, a sulfate salt, a phosphonic acid group, a phosphonic acid salt, a phosphoric acid group, and a phosphoric acid salt,

[0319] More preferably, at least one selected from the group consisting of a carboxyl group and a salt of a carboxyl group is used.

[0320] As the "salt" among the salts of carboxyl group, sulfonate group, sulfate group, phosphonate group and phosphate group, an alkali metal salt or an organic amine salt is preferred, and an alkali metal salt is more preferred.

[0321] As the alkali metal in the alkali metal salt, K or Na is preferred.

[0322] Furthermore, when the polymer P contains an anionic group (for example, at least one selected from the group including a carboxyl group and a salt of a carboxyl group) as a hydrophilic group, when the total millimole number of anionic groups (for example, a carboxyl group and a salt of a carboxyl group) contained in 1 g of the polymer P is taken as the acid value of the polymer P, from the viewpoint of dispersion stability, the acid value of the polymer P is preferably 0.10 mmol / g to 2.00 mmol / g, and more preferably 0.30 mmol / g to 1.50 mmol / g.

[0323] Furthermore, when the polymer P has an anionic group as a hydrophilic group, the neutralization degree of the anionic group in the polymer P is preferably 50% to 100%, and more preferably 70% to 90%.

[0324] Here, the degree of neutralization refers to the ratio of the "number of neutralized anionic groups" in the polymer P to the "total number of unneutralized anionic groups (e.g., carboxyl groups) and the number of neutralized anionic groups (e.g., salts of carboxyl groups)" (i.e., the ratio [number of neutralized anionic groups / (number of unneutralized anionic groups + number of neutralized anionic groups)]).

[0325] The degree of neutralization (%) of the polymer P can be determined by neutralization titration.

[0326] -Glass transition temperature (Tg)-

[0327] From the viewpoint of further improving the optical density and abrasion resistance of an image, the glass transition temperature (Tg) of the polymer P is preferably 60° C. or lower, more preferably 50° C. or lower, further preferably 45° C. or lower, and further preferably 40° C. or lower.

[0328] The lower limit of Tg of the polymer P is not particularly limited, and examples of the lower limit of Tg include -50°C and -40°C.

[0329] In the present invention, the glass transition temperature (Tg) of the polymer P refers to a value measured using differential scanning calorimetry (DSC).

[0330] The specific measurement of the glass transition temperature is carried out in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011).

[0331] The glass transition temperature in the present invention is an extrapolated glass transition start temperature (hereinafter, sometimes referred to as Tig).

[0332] The method for measuring the glass transition temperature will be described in more detail below.

[0333] When the glass transition temperature is determined, the device is maintained at a temperature about 50°C lower than the expected glass transition temperature until it stabilizes, and then heated at a heating rate of 20°C / min to a temperature about 30°C higher than the temperature at which the glass transition ends, and a differential thermal analysis (DTA) curve or a DSC curve is prepared.

[0334] The extrapolated glass transition start temperature (Tig), i.e., the glass transition temperature in this specification, is obtained as the following temperature: the temperature of the intersection of a straight line obtained by extending the baseline on the low temperature side of a DTA curve or a DSC curve toward the high temperature side and a tangent line drawn at the point where the gradient of the curve of the step-like change part of the glass transition is the largest.

[0335] -Weight average molecular weight (Mw)-

[0336] From the viewpoint of further improving the dispersion stability of the colored resin particles, the weight average molecular weight (Mw) of the polymer P is preferably 5,000 to 50,000, more preferably 6,000 to 40,000, further preferably 8,000 to 30,000, and further preferably 10,000 to 30,000.

[0337] In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) refer to values ​​calculated in terms of polystyrene by gel permeation chromatography (GPC).

[0338] As the column used, for example, TSKgel (registered trademark) SuperHZM-H, TSKgel (registered trademark) SuperHZ4000, and TSKgel (registered trademark) SuperHZ200 (all manufactured by TOSOH CORPORATION) are used.

[0339] - Type of polymer P -

[0340] The type of polymer P is not particularly limited.

[0341] Examples of the polymer P include polyurethane resins, acrylic resins, polyester resins, polyether resins, polycaprolactone resins, polycarbonate resins, polybutadiene resins, polyisoprene resins, and polyolefin resins.

[0342] Here, the polyurethane resin refers to a resin containing at least one selected from the group consisting of a urethane bond, a urea bond, and a thiourethane bond.

[0343] Therefore, the polyurethane resin may contain, in addition to the above bonds, a polyether chain, a polyester chain, a polycaprolactone chain, a polycarbonate chain, a polybutadiene chain, a polyisoprene chain, a polyolefin chain, and the like.

[0344] From the viewpoint of further improving the optical density and abrasion resistance of an image, the polymer P is preferably a polyurethane resin.

[0345] From the above viewpoints, a more preferred embodiment is an embodiment in which the polymer P contains a structural unit represented by the following formula (1) (hereinafter also referred to as "unit (1)") and a structural unit represented by the following formula (2) (hereinafter also referred to as "unit (2)").

[0346] -Structural unit represented by formula (1) (unit (1))-

[0347] When the polymer P contains a structural unit represented by the following formula (1) (hereinafter also referred to as "unit (1)"), the polymer P may contain only one type of unit (1) or two or more types of units (1).

[0348] [Chemical formula 13]

[0349]

[0350] In formula (1), L 1 represents a hydrocarbon group, and the two *1s represent the bonding positions respectively.

[0351] The unit (1) is preferably bonded to at least a structural unit represented by the formula (2) (hereinafter, also referred to as "unit (2)").

[0352] As L 1 The hydrocarbon group represented by is not particularly limited.

[0353] By L 1 The hydrocarbon group represented by may be a straight-chain hydrocarbon group, a branched hydrocarbon group, a hydrocarbon group containing an aromatic ring, or a hydrocarbon group containing an alicyclic structure.

[0354] As L 1 The hydrocarbon group represented by

[0355] A divalent hydrocarbon group selected from the group P1 consisting of an alkylene group which may have a branched structure and / or an alicyclic structure, an alkylene group which may have a branched structure and / or an alicyclic structure, an alkenylene group which may have a branched structure and / or an alicyclic structure, and an arylene group;

[0356] A divalent hydrocarbon group formed by bonding two or more selected from the above group P1;

[0357] wait.

[0358] By L 1 The hydrocarbon group represented by is preferably 1 to 20 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms.

[0359] Examples of the compound for forming unit (1) (hereinafter also referred to as "compound for forming unit (1)") include diisocyanate compounds having a structure in which each of the two "-NH-(C=O)-*1" in unit (1) is substituted with an isocyanate group (-NCO group).

[0360] Specific examples of the compound for forming the unit (1) are shown below.

[0361] However, the compound for forming the unit (1) is not limited to the following specific examples.

[0362] [Chemical formula 14]

[0363]

[0364] Furthermore, as the bifunctional isocyanate compound, the bifunctional isocyanate compound derived from the above-mentioned specific examples can also be used, for example, Duranate (registered trademark) D101, D201, A101 (manufactured by Asahi Kasei Corporation) and the like can be mentioned.

[0365] -Structural unit represented by formula (2)-

[0366] When the polymer P contains a structural unit represented by the following formula (2) (hereinafter also referred to as "unit (2)"), the polymer P may contain only one type of unit (2) or two or more types of units (2).

[0367] [Chemical formula 15]

[0368]

[0369] In formula (2),

[0370] L 2 represents a hydrocarbon group having 2 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, or a polymer chain having a number average molecular weight of 500 or more consisting of a polyether chain, a polyester chain, a polycaprolactone chain, a polycarbonate chain, a polybutadiene chain, a polyisoprene chain or a polyolefin chain,

[0371] Y 1 and Y 2 Each independently represents -O-, -S- or -NRz-,

[0372] Rz represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0373] The two *2s represent the bonding positions respectively.

[0374] Here, the hydrocarbon group having 2 to 50 carbon atoms and containing oxygen atoms, nitrogen atoms or sulfur atoms included in the concept of "hydrocarbon group having 2 to 50 carbon atoms which may contain oxygen atoms, nitrogen atoms or sulfur atoms" refers to an organic group having a structure in which at least one carbon atom in the hydrocarbon group consisting only of carbon atoms and hydrogen atoms is substituted by an oxygen atom, a nitrogen atom or a sulfur atom, and refers to a group having 2 to 50 carbon atoms.

[0375] As L 2 A hydrocarbon group having 2 to 50 carbon atoms (hereinafter also referred to as "a hydrocarbon group represented by L) which may contain an oxygen atom, a nitrogen atom or a sulfur atom 2 The term "alkyl" refers to a hydrocarbon group "represented by"), preferably an unsubstituted or substituted alkylene group.

[0376] Examples of the substituent in the alkylene group having a substituent include an alkoxy group, an alkylcarbonyloxy group, an alkylthio group, an amino group, a monoalkylamino group, and a dialkylamino group.

[0377] The unit (2) is preferably bonded to at least the unit (1).

[0378] In formula (2), from the viewpoint of further improving the optical density and abrasion resistance of the image, L 2 The hydrocarbon group represented by is preferably 4-50 carbon atoms, more preferably 6-40 carbon atoms.

[0379] From the perspective of further improving the optical density and abrasion resistance of the image, L 2 Hydrocarbon

[0380] It is preferably a chain hydrocarbon group having 4 to 25 carbon atoms and having a branched structure which may contain an oxygen atom, a nitrogen atom or a sulfur atom.

[0381] More preferably, it is an unsubstituted branched alkylene group having 6 to 25 carbon atoms, an alkoxylated branched alkylene group having 6 to 25 carbon atoms (i.e., a branched alkylene group substituted with an alkoxy group), or an alkylcarbonyloxylated branched alkylene group having 6 to 25 carbon atoms (i.e., a branched alkylene group substituted with an alkylcarbonyloxy group).

[0382] The number of carbon atoms of the alkoxy group in the alkoxylated branched alkylene group having 6 to 25 carbon atoms is preferably 1 to 23, more preferably 4 to 22.

[0383] The alkylcarbonyloxy group in the alkylcarbonyloxy branched alkylene group having 6 to 25 carbon atoms preferably has 2 to 23 carbon atoms, and more preferably has 6 to 22 carbon atoms.

[0384] From the perspective of further improving the optical density and abrasion resistance of the image, L 2The hydrocarbon group represented by is also preferably an alkylene group having 2 or more carbon atoms substituted by a substituent A.

[0385] The substituent A is preferably at least one selected from the group consisting of a straight-chain alkyl group having 2 or more carbon atoms, a branched-chain alkyl group having 3 or more carbon atoms, a straight-chain alkoxy group having 2 or more carbon atoms, a branched-chain alkoxy group having 3 or more carbon atoms, a straight-chain alkoxyalkyl group having 2 or more carbon atoms, and a branched-chain alkoxyalkyl group having 3 or more carbon atoms.

[0386] By L 2 The number average molecular weight (Mn) of the polymer chain represented is 500 or more.

[0387] By L 2 The Mn of the polymer chain represented by is preferably 500 to 50,000, more preferably 1,000 to 40,000, further preferably 1,000 to 30,000, further preferably 1,000 to 10,000, further preferably 1,000 to 5,000.

[0388] By L 2 The polymer chain represented is composed of a polyether chain, a polyester chain, a polycaprolactone chain, a polycarbonate chain, a polybutadiene chain, a polyisoprene chain or a polyolefin chain.

[0389] Examples of the polyether chain include a polyethylene glycol chain, a polypropylene glycol chain, and a polytetramethylene glycol chain.

[0390] Examples of the polyester chain include a residue obtained by removing hydroxyl groups at both terminals from the compound (2-17) PEs described later.

[0391] Examples of the polycaprolactone chain include a residue obtained by removing hydroxyl groups at both terminals from the compound (2-19) PCL described later.

[0392] Examples of the polycarbonate chain include a residue obtained by removing hydroxyl groups at both terminals from the compound (2-18) PC described later.

[0393] From the viewpoint of further improving the abrasion resistance of the image and the storage stability of the colored resin particle dispersion, L 2 A polymer chain having a number average molecular weight of 500 or more composed of a polycarbonate chain or a polyether chain is preferred.

[0394] L 2 The embodiment of a polymer chain having a number average molecular weight of 500 or more composed of a polycarbonate chain is particularly advantageous from the viewpoint of the abrasion resistance of an image.

[0395] L 2 The embodiment of a polymer chain having a number average molecular weight of 500 or more and composed of a polyether chain is particularly advantageous from the viewpoint of storage stability of the colored resin particle dispersion.

[0396] From the viewpoint of further improving the abrasion resistance of the image and the storage stability of the colored resin particle dispersion, the polymer P preferably contains:

[0397] L in formula (2) 2 The units (2) are polymer chains having a number average molecular weight of 500 or more and are composed of polycarbonate chains;

[0398] L in formula (2) 2 The unit (2) is a polymer chain having a number average molecular weight of 500 or more and composed of a polyether chain.

[0399] The polycarbonate chain preferably contains an alkylene group having 2 to 12 carbon atoms (preferably 3 to 8, more preferably 3 to 6), and more preferably is a residue obtained by removing hydroxyl groups at both terminals from the compound (2-18) PC described later.

[0400] The polyether chain is preferably a polyethylene glycol chain (a residue obtained by removing hydroxyl groups at both terminals from the compound (2-22) PEG described below) or a polypropylene glycol chain (a residue obtained by removing hydroxyl groups at both terminals from the compound (2-16) PPG described below).

[0401] In formula (2), Y 1 and Y 2 Each independently represents -O-, -S- or -NRz-, and Rz represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0402] Rz is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, further preferably a hydrogen atom, a methyl group or an ethyl group, further preferably a hydrogen atom.

[0403] As Y 1 and Y 2 Each of -O- or -S- is preferred, and -O- is more preferred.

[0404] As a compound for forming unit (2) (hereinafter also referred to as "compound for forming unit (2)"),

[0405] It is preferred that the "*2-Y" in unit (2) 1 -" and "-Y 2 -*2" is a compound having a structure in which a hydroxyl group, a thiol group or an amino group is substituted (for example, a diol compound, a dithiol compound, a diamine compound, etc.),

[0406] It is further preferred that the "*2-Y" in unit (2) 1 -" and "-Y 2 -*2" are each substituted with a hydroxyl group.

[0407] As for forming L 2 The compound for forming the unit (2) is the unit (2) of the polymer chain, and in the case where the compound for forming the unit (2) is a diol compound, the compound for forming the unit (2) is a polymer diol.

[0408] More specifically, the polymer diol may be polyether diol, polyester diol, polycaprolactone diol, polycarbonate diol, polybutadiene diol, polyisoprene diol or polyolefin diol.

[0409] Specific examples of the compound for forming the unit (2) are shown below.

[0410] However, the compound for forming the unit (2) is not limited to the following specific examples.

[0411] [Chemical formula 16]

[0412]

[0413] In compounds (2-12) to (2-15), nC7H 15 、nC9H 19 、nC 11 H 23 and nC 17 H 35 They represent n-heptyl, n-nonyl, n-undecyl and n-heptadecyl, respectively.

[0414] Compound (2-16) PPG is polypropylene glycol which is an example of polyether diol, and n is the number of repetitions.

[0415] Compound (2-17) PEs is polyester diol, n is the number of repetitions, Ra, Rb 1 and Rb 2 Each independently represents a divalent hydrocarbon group having 2 to 25 carbon atoms. The n Ra in compound (2-17) PEs may be the same or different. The n Rb in compound (2-17) PEs 1 It can be the same or different.

[0416] Compound (2-18) PC is polycarbonate diol, n is the number of repetitions, Rc 1 and Rc 2 Each of the n Rc in compound (2-18) PC is independently an alkylene group having 2 to 12 carbon atoms (preferably 3 to 8, more preferably 3 to 6). 1 It can be the same or different.

[0417] Compound (2-19) PCL is polycaprolactone diol, n and m are the repeating numbers, and Rd is an alkylene group having 2 to 25 carbon atoms.

[0418] Compound (2-22) PEG is polyethylene glycol which is an example of polyether diol, and n is the number of repetitions.

[0419] As the compound for forming the unit (2), in addition to the above-mentioned compounds, the following compounds can be mentioned.

[0420] [Chemical formula 17]

[0421]

[0422] [Chemical formula 18]

[0423]

[0424] Examples of the compound for forming the unit (2) include polybutadiene diol (hereinafter also referred to as "PBD"), polyisoprene diol (hereinafter also referred to as "PIP"), polyolefin diol, and the like, in addition to the above-mentioned compounds.

[0425] As the polymer diol of the compound for forming the unit (2), a commercially available product can be used.

[0426] For commercially available products of polymer diols, reference can be made to Examples described below.

[0427] In addition, for commercially available products of polymer diols, reference can also be made to paragraph 0111 of International Publication No. 2016 / 152254.

[0428] From the viewpoint of further improving the optical density and abrasion resistance of the image, the total content of the units (1) and (2) in the polymer P is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, relative to the total amount of the polymer P.

[0429] In the polymer P, the molar ratio of the unit (2) to the unit (1) (hereinafter also referred to as "molar ratio [unit (2) / unit (1)]") is preferably 0.20 or more and less than 1.00, more preferably 0.30 or more and 0.90 or less, and further preferably 0.50 or more and 0.90 or less.

[0430] -Structural unit having a hydrophilic group-

[0431] The polymer P preferably contains at least one structural unit having a hydrophilic group.

[0432] Specific examples and preferred embodiments of the hydrophilic group are as described above.

[0433] The structural unit having a hydrophilic group is preferably formed using a compound for introducing a hydrophilic group described later as a raw material.

[0434] As the structural unit having a hydrophilic group, a structural unit represented by the following formula (3) which is a structural unit having an anionic group (hereinafter also referred to as “unit (3)”) is particularly preferred.

[0435] [Chemical formula 19]

[0436]

[0437] In formula (3), R X1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, A represents an anionic group, and two *3s represent bonding positions, respectively.

[0438] The unit (3) is preferably bonded to at least the unit (1).

[0439] Examples of the anionic group represented by A are the same as the above-mentioned examples of the anionic group.

[0440] As the anionic group represented by A, a carboxyl group or a salt of a carboxyl group is preferred.

[0441] The polymer P may contain the unit (3) in which A is a carboxyl group and the unit (3) in which A is a salt of a carboxyl group.

[0442] The content of the structural unit having a hydrophilic group (for example, unit (3)) based on the total amount of the polymer P is preferably 3% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

[0443] The content of the structural unit having an anionic group relative to the total amount of the polymer P can be adjusted in consideration of the acid value of the polymer P (mmol / g).

[0444] - Compounds for introducing hydrophilic groups -

[0445] Introduction of a hydrophilic group into the polymer P can be performed using a compound for introducing a hydrophilic group.

[0446] Among the compounds for introducing a hydrophilic group, as a compound for introducing an anionic group,

[0447] Examples include compounds in which hydrogen atoms are bonded to each of the two *3 in unit (3);

[0448] α-amino acids (specifically, lysine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine) and the like;

[0449] wait.

[0450] Examples of the compound in which a hydrogen atom is bonded to each of the two *3 in the unit (3) include 2,2-dimethylolpropionic acid (DMPA) and 2,2-dimethylolbutanoic acid (DMBA).

[0451] As the compound for introducing anionic groups, an inorganic base such as sodium hydroxide and potassium hydroxide, or an organic base such as triethylamine may be used, and at least a part of the anionic groups may be neutralized before use.

[0452] Furthermore, the neutralization of the anionic groups may be performed during the formation process of the polymer P (for example, during the formation process of the colored resin particles) (see Examples described below).

[0453] As the nonionic group-introducing compound among the hydrophilic group-introducing compounds, a compound having a polyether structure is preferred, and a compound having a polyoxyalkylene group is more preferred.

[0454] The polymer P may contain other structural units in addition to the structural units mentioned above.

[0455] Among them, when the polymer P contains a structural unit having a hydrophilic group, the total content of the unit (1), the unit (2) and the structural unit having a hydrophilic group is preferably 80% by mass or more relative to the total amount of the polymer P from the viewpoint of the optical density and abrasion resistance of the image and the dispersion stability of the colored resin particles.

[0456] -Preferred Embodiments of Polymer P-

[0457] The polymer P preferably contains:

[0458] a compound for forming unit (1) (preferably a diisocyanate compound having a structure in which each of the two "-NH-(C=O)-*1" in unit (1) is substituted with an isocyanate group (-NCO group);

[0459] The compound for forming unit (2) (preferably having a 1 -" and "-Y 2 -*2" are substituted with a hydroxyl group, a thiol group or an amino group); and

[0460] The structure of a reaction product of a compound for introducing a hydrophilic group (preferably a compound having a hydrogen atom bonded to each of the two *3 in the unit (3)).

[0461] Furthermore, the polymer P preferably contains a urethane bond.

[0462] Examples of urethane bonds include: 1 and Y 2A urethane bond formed by bonding the unit (2) in which each of them is in the form of -O-, a urethane bond formed by bonding the unit (1) and the unit (3), and the like.

[0463] The structure of the terminal of the main chain of the polymer P is not particularly limited. The terminal group of the main chain of the polymer P is preferably an alkyl group having 1 to 20 (more preferably 1 to 10, and even more preferably 1 to 6) carbon atoms.

[0464] Regarding the alkyl group having 1 to 20 carbon atoms (more preferably 1 to 10, and further preferably 1 to 6) as the terminal, for example, an alcohol having 1 to 20 carbon atoms (more preferably 1 to 10, and further preferably 1 to 6), a thiol having 1 to 20 carbon atoms (more preferably 1 to 10, and further preferably 1 to 6), a monoalkylamine having 1 to 20 carbon atoms (more preferably 1 to 10, and further preferably 1 to 6), or the like can be used as a capping agent.

[0465] Furthermore, from the viewpoint of further improving the optical density and abrasion resistance of an image, the polymer P is preferably a chain polymer.

[0466] Here, the chain polymer refers to a polymer having no cross-linking structure.

[0467] The chain polymer may contain a cyclic structure. Of course, the chain polymer may contain a branched structure.

[0468] From the viewpoint of further improving the optical density and abrasion resistance of the image, the content of the polymer P in the colored resin particles is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more relative to the solid content of the colored resin particles.

[0469] From the viewpoint of further improving the optical density of the image, the content of the polymer P in the colored resin particles is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less, relative to the solid content of the colored resin particles.

[0470] In the present invention, when the colored resin particles contain a solvent (for example, an oily organic solvent described below. The same applies hereinafter), the solid content of the colored resin particles refers to the total amount after removing the solvent, and when the colored resin particles do not contain a solvent, it refers to the total amount of the colored resin particles.

[0471] In the present invention, when the colored resin particles contain a solvent, the solid content of the colored resin particles refers to all components except the solvent, and when the colored resin particles do not contain a solvent, it refers to all components of the colored resin particles.

[0472] A preferred embodiment of the method for synthesizing the polymer P is an embodiment in which a compound for forming the unit (1), a compound for forming the unit (2) and a compound for introducing a hydrophilic group are reacted in the presence of an oily organic solvent described later.

[0473] Furthermore, the polymer P may be formed by synthesizing a polymer in which anionic groups as hydrophilic groups are not neutralized using the synthesis method of this type, using the polymer as one of the raw materials to prepare a colored resin particle dispersion, and neutralizing the anionic groups of the polymer during the preparation stage.

[0474] From the viewpoint of further improving the optical density of the image, the content of the oil-soluble dye in the colored resin particles is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more, relative to the solid content of the colored resin particles.

[0475] From the viewpoint of further improving the optical density and abrasion resistance of the image, the content of the oil-soluble dye in the colored resin particles is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the solid content of the colored resin particles.

[0476] From the viewpoint of further improving the optical density of the image, the ratio of the mass content of the polymer P to the mass content of the oil-soluble dye (hereinafter also referred to as "mass content ratio [P / dye]") is preferably 0.10 to 4.00, more preferably 0.10 to 2.50, further preferably 0.20 to 2.50, further preferably 0.20 to 1.50, further preferably 0.25 to 1.00.

[0477] (Other ingredients)

[0478] The colored resin particles may contain other components in addition to the polymer P and the oil-soluble dye as necessary, or may not contain other components in addition to the polymer P and the oil-soluble dye.

[0479] From the viewpoint of further improving the optical density and abrasion resistance of an image, the total content of the polymer P and the oil-soluble dye in the colored resin particles is preferably 80% by mass or more based on the solid content of the colored resin particles.

[0480] Furthermore, from the viewpoint of further improving the optical density and abrasion resistance of the image, the solid content of the colored resin particles is preferably 80% by mass or more based on the total amount of the colored resin particles.

[0481] As other components that may be contained in the colored resin particles, an oily organic solvent may be mentioned.

[0482] When the colored resin particles contain an oily organic solvent, the oily organic solvent contained may be only one kind or two or more kinds.

[0483] The oily organic solvent refers to an organic solvent having a solubility in water at 20° C. of 10% by mass or less.

[0484] The solubility of the oily organic solvent in water at 20° C. is preferably 5% by mass or less, and more preferably 1% by mass or less. When the solubility of the oily organic solvent in water at 20° C. is 5% by mass or less, the oil (organic component) and water are less likely to mix during emulsification, thereby further improving the synthetic suitability and stability of the colored resin particles.

[0485] The oily organic solvent may include any of a volatile oily organic solvent and a non-volatile oily organic solvent. Among these, a non-volatile oily organic solvent is more likely to exist in the colored resin particles.

[0486] Here, the volatile oily organic solvent refers to an oily organic solvent having a boiling point of less than 100° C. Examples of the volatile oily organic solvent include ester solvents such as ethyl acetate and ketone solvents such as methyl ethyl ketone.

[0487] The nonvolatile organic solvent refers to an oily organic solvent having a boiling point exceeding 100°C.

[0488] The nonvolatile oily organic solvent is preferably one having a boiling point of 180° C. or higher from the viewpoint of exhibiting nonvolatility during reaction and dispersion stability during storage of a colored resin particle dispersion or ink.

[0489] In addition, the boiling point in the present invention is a value of the boiling point under standard conditions (1 atmospheric pressure, 25° C.). 1 atmospheric pressure=101.325 kPa.

[0490] Specific examples of non-volatile oily organic solvents include non-halogen phosphates (e.g., TCP manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.), alkyl-substituted aromatic compounds (e.g., Alkene KS-41 manufactured by ENEOS Corporation, KMC500 manufactured by KUREHA CORPORATION), long-chain alkyl-substituted ester compounds (e.g., methyl laurate KS-33 manufactured by NOF CORPORATION, tri(2-ethylhexanoic acid)glycerol manufactured by FUJIFILM Wako Pure Chemical Corporation), dibasic acid esters (e.g., DBE manufactured by INVISTA, dimethyl succinate, dimethyl glutarate, diisopropyl succinate manufactured by Tokyo Chemical Industry Co., Ltd.), alkylene glycol derivatives (e.g., ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dibutyl ether, diethylene glycol dibenzoate manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

[0491] From the viewpoint of solubility of the dye represented by formula (MA), DBE, dimethyl succinate, dimethyl glutarate, diisopropyl succinate, tri(2-ethylhexanoin)glycerol, diethylene glycol monobutyl ether acetate, or diethylene glycol dibutyl ether is particularly preferred.

[0492] When the colored resin particles contain an oily organic solvent, the content of the oily organic solvent is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass, based on the solid content of the colored resin particles.

[0493] (Volume average particle size)

[0494] The volume average particle size of the colored resin particles is preferably 200 nm or less, more preferably 20 nm to 200 nm, and further preferably 40 nm to 150 nm. When the volume average particle size of the colored resin particles is 200 nm or less, the ejection properties of the inkjet ink are more excellent.

[0495] The volume average particle size of the colored resin particles referred to herein refers to a value measured using a particle size distribution measuring apparatus (for example, NANOTRAC UPA EX150, manufactured by Nikkiso Co., Ltd., trade name).

[0496] The colored resin particle dispersion of the first embodiment contains water and the above-mentioned colored resin particles.

[0497] The colored resin particle dispersion of the first embodiment may contain components other than water and the colored resin particles, or may not contain components other than water and the colored resin particles.

[0498] From the viewpoint of further improving the optical density and abrasion resistance of an image, the total content of water and colored resin particles in the colored resin particle dispersion is preferably 80% by mass or more based on the total amount of the colored resin particle dispersion.

[0499] <An example of a method for producing a colored resin particle dispersion>

[0500] The production method for producing the colored resin particle dispersion of the first embodiment is not particularly limited.

[0501] An example of the method for producing the colored resin particle dispersion according to the first embodiment (hereinafter also referred to as “production method A”) is described below.

[0502] Preparation method A includes the following steps:

[0503] A step of preparing an oil phase component, wherein the oil phase component includes an oily organic solvent (i.e., a volatile oily organic solvent and / or a non-volatile oily organic solvent), a polymer P or a polymer P before neutralization of an anionic group as a hydrophilic group, and an oil-soluble dye;

[0504] A step of preparing a water phase component, wherein the water phase component comprises water (and a neutralizing agent as required); and

[0505] In the emulsification step, the oil phase component and the water phase component are mixed and the resulting mixture is emulsified to obtain an emulsion.

[0506] In the production method A, the colored resin particles are formed and the formed colored resin particles are dispersed in water through the emulsification step, thereby obtaining a colored resin particle dispersion in which the colored resin particles are dispersed in water.

[0507] When an oil phase component containing a polymer P before anionic groups as hydrophilic groups are neutralized is used as the oil phase component, and an aqueous phase component containing water and a neutralizing agent is used as the aqueous phase component, in the emulsification step, at least a portion of the anionic groups in the polymer P before the anionic groups are neutralized is neutralized, thereby forming colored resin particles containing the polymer P containing neutralized anionic groups (e.g., -COONa).

[0508] As the neutralizing agent, a basic compound such as sodium hydroxide, potassium hydroxide, or triethylamine can be used.

[0509] The emulsification method in the emulsification step is not particularly limited, and examples thereof include emulsification using an emulsification device such as a homogenizer (for example, a disperser).

[0510] The rotation speed of the disperser during emulsification is, for example, 5000 rpm to 20000 rpm, preferably 10000 rpm to 15000 rpm. Here, rpm is an abbreviation of revolutions per minute.

[0511] The rotation time during emulsification is, for example, 1 to 120 minutes, preferably 3 to 60 minutes, more preferably 3 to 30 minutes, and further preferably 5 to 15 minutes.

[0512] The emulsification in the emulsification step may be performed under heating.

[0513] By performing emulsification under heating, the colored resin particles can be formed more efficiently.

[0514] Furthermore, by emulsifying under heating, at least a part of the oily organic solvent in the oil phase component can be easily removed from the mixture.

[0515] The heating temperature during emulsification under heating is preferably 35°C to 70°C, more preferably 40°C to 60°C.

[0516] Furthermore, the preparation method A may include a heating step of heating the emulsion or a mixture of the emulsion and water to remove at least a part of the oily organic solvent.

[0517] The heating temperature in the heating step is preferably 35°C to 70°C, more preferably 40°C to 60°C.

[0518] [Colored resin particle dispersion (second embodiment)]

[0519] The colored resin particle dispersion according to the second aspect of the present invention contains:

[0520] water; and

[0521] Colored resin particles, comprising a polymer P containing a hydrophilic group and an oil-soluble dye,

[0522] The oil-soluble dye includes the aforementioned oil-soluble dye (D1).

[0523] In the colored resin particle dispersion of the second embodiment, the oil-soluble dye (D1) is not limited to the "oil-soluble dye (D) in which a water-soluble reactive dye is modified with an alkyl group having 4 or more carbon atoms or a counter cation in an acid dye is replaced with an organic cation containing an alkyl group having 4 or more carbon atoms" in the first embodiment. That is, the raw material and production method of the oil-soluble dye (D1) are not particularly limited.

[0524] Except for the above, the colored resin particle dispersion of the second embodiment is the same as the colored resin particle dispersion of the first embodiment, and the preferred embodiments are also the same.

[0525] The colored resin particle dispersion of the first embodiment and the colored resin particle dispersion of the second embodiment may have conceptually overlapping parts.

[0526] That is, the oil-soluble dye (D1) in the colored resin particle dispersion of the second embodiment may correspond to the oil-soluble dye (D) in the first embodiment.

[0527] Preferred embodiments of the oil-soluble dye (D1) are as described in the description of the first embodiment.

[0528] 〔Ink〕

[0529] The ink of the present invention contains the above-mentioned colored resin particle dispersion of the present invention (that is, the colored resin particle dispersion of the first embodiment of the present invention or the colored resin particle dispersion of the second embodiment of the present invention. The same shall apply hereinafter).

[0530] In other words, the ink of the present invention contains the components (at least water and colored resin particles) in the above-mentioned colored resin particle dispersion of the present invention.

[0531] The content of water in the ink of the present invention is, for example, 40% by mass or more, preferably 50% by mass or more, and more preferably 60% by mass or more, relative to the total amount of the ink.

[0532] The upper limit of the water content also depends on the amount of solid content in the ink, but is, for example, 90% by mass relative to the total amount of the ink.

[0533] The solid content of the colored resin particles in the ink of the present invention is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass, based on the total amount of the ink.

[0534] <Aqueous organic solvent>

[0535] The ink of the present invention preferably contains at least one aqueous organic solvent.

[0536] This makes the ink excellent in stability (that is, less likely to cause precipitation, etc.), and also excellent in ejection properties when used as an inkjet ink.

[0537] Here, the "aqueous" in the aqueous organic solvent means that the amount of the solvent that dissolves in 100 g of distilled water at 25°C is more than 1 g.

[0538] The amount dissolved in the aqueous organic solvent is preferably 5 g or more, more preferably 10 g or more, and even more preferably 20 g or more.

[0539] Examples of the aqueous organic solvent include alcohol solvents, amide solvents, nitrile solvents, polyalkylene glycol solvents, polyalkylene glycol alkyl ether solvents, and the like. An alcohol solvent or an amide solvent is preferred.

[0540] Examples of the aqueous organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, butanediol, 1,2,6-hexanetriol, thioglycol, hexanediol, glycerol, diglycerol, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether ...butyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Nitrile, polyethylene glycol (for example, molecular weight 400-800), hydroxyethyl pyrrolidone, hydroxypropyl pyrrolidone, valerolactam, caprolactam, heptanolactam, polyethylene glycol monomethyl ether (molecular weight 400), polyethylene glycol monomethyl ether (molecular weight 550), polyethylene glycol dimethyl ether (molecular weight 500), tripropylene glycol, tetrapropylene glycol, polypropylene glycol (molecular weight 400), polypropylene glycol (molecular weight 600), polypropylene glycol (molecular weight 700), etc.

[0541] Regarding aqueous organic solvents,

[0542] It preferably contains at least one selected from the group consisting of trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, glycerol, 2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol and ethylene glycol monobutyl ether,

[0543] More preferably, it comprises at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, glycerol, 2-pyrrolidone and ethylene glycol monobutyl ether,

[0544] More preferably, the polyol contains at least one selected from the group consisting of ethylene glycol, glycerol, 2-pyrrolidone and tetraethylene glycol.

[0545] The content of the aqueous organic solvent in the ink is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 30% by mass, based on the total amount of the ink.

[0546] When the content of the aqueous organic solvent is within the above range, the ink has excellent stability (precipitation is less likely to occur) and also has excellent ejection properties as an inkjet ink.

[0547] <Cross-linking agent>

[0548] The ink of the present invention may also further comprise at least one cross-linking agent.

[0549] The crosslinking agent is preferably a compound having at least two crosslinking groups.

[0550] As the crosslinkable group possessed by the crosslinking agent, a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, etc. are preferable.

[0551] Examples of the cross-linking agent include blocked isocyanate compounds, oxazoline compounds, and carbodiimide compounds.

[0552] in,

[0553] Preferred are blocked isocyanate compounds in which a TMP (trimethylolpropane) adduct or isocyanurate of a diisocyanate (e.g., HDI (hexamethylene diisocyanate), H6XDI (hydrogenated xylene diisocyanate), IPDI (isophorone diisocyanate), H12MDI (dicyclohexylmethane diisocyanate)) is blocked by a blocking agent; or; a carbodiimide compound.

[0554] As the blocking agent in the blocked isocyanate compound, DEM (diethyl malonate), DIPA (diisopropylamine), TRIA (1,2,4-triazole), DMP (3,5-dimethylpyrazole) or MEKO (methyl ethyl ketone oxime) is preferred from the viewpoint of dissociation temperature.

[0555] The blocked isocyanate compound can also be used as an oligomer obtained by reacting a part of its isocyanate group with a polyol, a polycarbonate, a polyester, a polyether, or the like.

[0556] As the carbodiimide compound, CARBODILITE water-based resin crosslinking agent E-02, E-03A, and E-05 (these are product names) manufactured by Nisshinbo Chemical Inc. are preferred, and E-05 is particularly preferred from the viewpoint of storage stability and reactivity.

[0557] The dissociation temperature of the crosslinking agent is preferably lower from the viewpoint of crosslinking efficiency, but is preferably higher from the viewpoint of storage stability.

[0558] From the viewpoint of these balances, the dissociation temperature is preferably 90°C to 180°C, more preferably 90°C to 120°C, and particularly preferably 110°C to 120°C.

[0559] Furthermore, it is preferred that the crosslinking agent be blended into the ink as a water-soluble or self-emulsifiable crosslinking agent by imparting a hydrophilic group. In this state, the viscosity of the blended ink can be set to a low viscosity and excellent redispersibility can be achieved.

[0560] The cross-linking agent may be in the form of cross-linking agent particles.

[0561] From the viewpoint of improving the ejection properties in inkjet, the average particle size of the crosslinking agent particles is preferably 200 nm or less.

[0562] The average particle size referred to here may be a value of a volume average particle size (MV) measured using a particle size distribution analyzer (NANOTRAC UPA EX150, manufactured by Nikkiso Co., Ltd., trade name).

[0563] The crosslinking agent particles are not particularly limited, and examples thereof include ELASTRON BN-77 (blocked isocyanate, particle size of 19 nm, dissociation temperature of 120° C. or more, manufactured by DKS Co. Ltd.), ELASTRON BN-27 (blocked isocyanate, particle size of 108 nm, dissociation temperature of 180° C. or more, manufactured by DKS Co. Ltd.), DURANATE WM44-70G (blocked isocyanate, particle size of 42 nm, dissociation temperature of about 90° C., manufactured by Asahi Kasei Corporation), and TRIXENE AQUABI200 (blocked isocyanate, particle size of 94 nm, dissociation temperature of 110-120° C., manufactured by BAXENDEN).

[0564] When the ink contains a crosslinking agent, the content of the crosslinking agent in the ink is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1 to 5% by mass, based on the total amount of the ink.

[0565] <Pigment>

[0566] From the viewpoint of adjusting the hue or increasing the color density, the ink of the present invention may further contain at least one pigment.

[0567] As the pigment, for example, there can be mentioned:

[0568] Carbon black, aniline black;

[0569] CI Pigment Yellow 3, 12, 53, 55, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185;

[0570] CI Pigment Red 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219;

[0571] CI Pigment Violet 19, 23;

[0572] CI Pigment Orange 36, 43, 64;

[0573] CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17:1, 56, 60, 63;

[0574] CI Pigment Green 36;

[0575] wait.

[0576] When the ink of the present invention contains a pigment, the content of the pigment in the ink is preferably 0.5 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 0.5 to 5% by mass, based on the total amount of the ink.

[0577] In the present invention, when preparing the ink, a water dispersion of a pigment in which the pigment is dispersed in water using a dispersant (also referred to as a "pigment water dispersion") can also be used. As the pigment water dispersion, for example, the pigment dispersion described in Japanese Patent Application Laid-Open No. 2012-7148 can be used. In addition, as the pigment water dispersion, commercial products such as Pro-jet Black APD1000 (manufactured by FUJIFILM Imaging Colorants, Inc.) can also be used.

[0578] As the pigment, a self-dispersible pigment can also be used.

[0579] Self-dispersible pigments are pigments that can be dispersed in water without using a dispersant. For example, self-dispersible pigments include pigments in which at least one of hydrophilic groups such as carbonyl, hydroxyl, carboxyl, sulfonic, and phosphoric acid groups and salts thereof is introduced directly or via other groups through chemical bonds to the surface of the pigment.

[0580] The self-dispersible pigment is preferably self-dispersible carbon black.

[0581] Examples of self-dispersible pigments that can be used include self-dispersible carbon blacks CAB-O-JET 200, CAB-O-JET 300, CAB-O-JET 400 (all manufactured by Cabot Corporation), BONJET CW-1 (500 μmol / g as a carboxyl group), BONJET CW-2 (470 μmol / g as a carboxyl group) (all manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), and Aqua-Black 162 (about 800 μmol / g as a carboxyl group) manufactured by Tokai Carbon Co., Ltd.

[0582] As the pigment, either an aqueous dispersion of a pigment obtained by dispersing the pigment in water using a dispersant or a self-dispersible pigment can be preferably used.

[0583] <Paraffin>

[0584] The ink of the present invention may also contain at least one paraffin wax.

[0585] This can further improve the abrasion resistance of the image.

[0586] It is preferred that the paraffin wax exists in the ink of the present invention in the form of particles.

[0587] Hereinafter, paraffin wax in the form of particles is referred to as "paraffin wax particles".

[0588] As the paraffin wax particles, it is preferable to use a dispersion in which paraffin wax is dispersed in water.

[0589] As the paraffin wax, polyethylene wax, paraffin wax or carnauba wax is preferred.

[0590] The melting point of paraffin wax is preferably in the range of 60° C. to 120° C., more preferably in the range of 60° C. to 100° C., from the viewpoint of improving stability and friction. By increasing the melting point, the stability of the printing ink can be improved, while on the other hand, not making the melting point higher than the required melting point is effective for improving friction.

[0591] The melting point of paraffin wax can be measured by a general melting point measuring instrument.

[0592] The volume average particle size (MV) of the wax particles is preferably 0.3 μm or less, more preferably 0.2 μm or less, and particularly preferably 0.1 μm or less, from the viewpoint of ejectability in inkjet.

[0593] The volume average particle size can be measured by the same method as that of the above-mentioned colored resin particles.

[0594] When the ink of the present invention contains paraffin wax, the content of the paraffin wax is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and further preferably 1 to 5% by mass, based on the total amount of the ink.

[0595] As the paraffin particles, commercially available products may be used.

[0596] Examples of commercially available products include Polylon L-787 (manufactured by Chukyo Yushi Co., Ltd., polyethylene, nonionic, melting point of 102° C., volume average particle size of 0.1 μm), Hydrin-703 (manufactured by Chukyo Yushi Co., Ltd., paraffin, anionic, melting point of 75° C., volume average particle size of 0.1 μm), R108 (manufactured by Chukyo Yushi Co., Ltd., paraffin, nonionic, melting point of 66° C., volume average particle size of 0.2 μm), and Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd., carnauba, nonionic, melting point of 83° C., volume average particle size of 0.07 μm).

[0597] <Surfactant>

[0598] The ink of the present invention can contain at least one surfactant.

[0599] The surfactant is not particularly limited, and known surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants can be used.

[0600] As the surfactant, from the viewpoint of ejection properties when used as an inkjet ink, a nonionic surfactant is preferred, and among them, an acetylene surfactant is particularly preferred.

[0601] Examples of commercially available acetylene-based surfactants include Surfynol (registered trademark) series manufactured by Nissin Chemical Co., Ltd. and OLFINE (registered trademark) series manufactured by Nissin Chemical Co., Ltd.

[0602] When the ink of the present invention contains a surfactant, the content of the surfactant is preferably 0.1 to 2.0% by mass, more preferably 0.5 to 2.0% by mass, based on the total amount of the ink, from the viewpoint of ejection properties when used as an inkjet ink.

[0603] <Other ingredients>

[0604] The ink of the present invention may contain other components besides the above components.

[0605] Examples of other components include dyes other than the above-mentioned oil-soluble dyes, pigments, crosslinking agents, paraffin waxes, pH adjusters, fluorescent whitening agents, surface tension adjusters, defoaming agents, drying inhibitors, lubricants, thickeners, ultraviolet absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity adjusters, rust inhibitors, reduction inhibitors, preservatives, mildew inhibitors, and chelating agents.

[0606] Regarding other components, reference can also be made to the description of International Publication No. 2017 / 131107.

[0607] <Application>

[0608] The use of the ink of the present invention is not particularly limited.

[0609] The ink of the present invention is used as, for example, an inkjet ink. When the ink of the present invention is used as an inkjet ink, the ejection properties from an inkjet head can be ensured.

[0610] Furthermore, as described above, the ink of the present invention can form an image having excellent optical density and abrasion resistance on a cloth, and therefore the ink of the present invention is suitable as an ink for textile printing, and particularly suitable as an ink for inkjet textile printing.

[0611] When the ink of the present invention is used as an inkjet ink, the surface tension of the ink is preferably 20 mN / m to 70 mN / m, more preferably 25 mN / m to 60 mN / m.

[0612] The surface tension mentioned here refers to the value measured at 25°C.

[0613] The surface tension can be measured, for example, using Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0614] Furthermore, when the ink of the present invention is used as an inkjet ink, the viscosity of the ink is preferably 40 mPa·s or less, and more preferably 30 mPa·s or less.

[0615] The viscosity mentioned here is a value measured at 25°C.

[0616] As the viscometer, for example, a VISCOMETER TV-22 type viscometer (manufactured by TOKI SANGYO CO., LTD.) can be used.

[0617] 〔Ink Set〕

[0618] The ink of the present invention may be used alone or in the form of an ink set.

[0619] The ink set mentioned here includes two or more inks, and at least one of the two or more inks is an ink set as the ink of the present invention.

[0620] That is, the ink set may be an ink set consisting of two or more inks of the present invention, or may be an ink set consisting of one or more inks of the present invention and one or more other inks.

[0621] Furthermore, the ink set may further include an aqueous pre-treatment liquid described below.

[0622] As an example of the ink set, there can be mentioned an embodiment in which the ink set includes a black ink, a yellow ink, a magenta ink, and a blue ink, and at least one ink in the ink set is the ink of the present invention.

[0623] Among this aspect, an aspect in which the black ink is the ink of the present invention is particularly preferred.

[0624] [Inkjet printing method]

[0625] The ink of the present invention can be used for image formation on all substrates, and is particularly suitable for image formation on cloth.

[0626] As an example of forming an image on cloth, the following inkjet printing method A can be cited.

[0627] Inkjet printing method A comprises the following steps:

[0628] A step of applying the ink of the present invention to a cloth by an inkjet method (hereinafter also referred to as "ink applying step"); and

[0629] A step of heat-treating the cloth to which the ink is applied (hereinafter also referred to as a "heat-treating step").

[0630] According to the inkjet printing method A, an image having excellent optical density and abrasion resistance can be formed on a cloth.

[0631] Specific examples of cloth will be described later.

[0632] In the inkjet printing method A, a transfer step, a printing paste application step, and the like, which are sometimes provided in a general printing method, are unnecessary.

[0633] Furthermore, the inkjet printing method A does not require a steam treatment step (i.e., a step of fixing an image by steam treatment) which is sometimes provided in a general inkjet printing method. In a general inkjet printing method, in particular, a steam treatment step is sometimes performed to ensure the optical density and abrasion resistance of an image.

[0634] In the inkjet printing method A, even when the steam treatment step is omitted, an image having excellent optical density and abrasion resistance can be formed on the fabric.

[0635] In the inkjet printing method A, the fabric on which the image is formed may be a fabric pretreated with an aqueous pretreatment liquid containing a coagulant.

[0636] When the fabric to be image-formed is a pre-treated fabric, in the image-forming step, an image with high color density is formed on the fabric surface by the action of the coagulant. Then, in the heat-treating step, the image penetrates into the fabric by the action of the polymer P. Through these processes, an image with better optical density and abrasion resistance can be fixed to the fabric.

[0637] The fabric subjected to the pretreatment may be a fabric prepared in advance before the inkjet printing method A is performed.

[0638] Furthermore, the inkjet printing method A may include a pretreatment step before the image forming step, in which an aqueous pretreatment liquid containing a coagulant is applied to the fabric to obtain a pretreated fabric.

[0639] Hereinafter, each step that may be included in the inkjet printing method A will be described.

[0640] (Pretreatment process)

[0641] The pretreatment step is a step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated fabric.

[0642] The method for applying the aqueous pretreatment liquid to the fabric is not particularly limited, and examples thereof include a coating method, a padding method, an inkjet method, a spray method, and a screen printing method.

[0643] The coagulant contained in the aqueous pretreatment liquid is not particularly limited as long as it has the function of aggregating the colored resin particles, but is preferably at least one selected from organic acids, polyvalent metal salts and cationic compounds, and more preferably at least one selected from polyvalent metal salts and cationic compounds.

[0644] -Polyvalent Metal Salts-

[0645] The polyvalent metal salt is a compound composed of a metal ion having a valence of two or more and an anion.

[0646] Specific examples thereof include calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate, magnesium chloride, magnesium acetate, magnesium sulfate, magnesium carbonate, barium sulfate, barium chloride, zinc sulfide, zinc carbonate, and copper nitrate.

[0647] -Cationic compounds-

[0648] The cationic compound is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound.

[0649] Examples of low molecular cationic compounds include (2-hydroxyethyl)trimethylammonium chloride, benzoylcholine chloride, benzyltriethylammonium chloride, acetohydrazide trimethylammonium chloride, 1-butyl-1-methylpyrrolidine chloride, 3-hydroxy-4-(trimethylammonium)butyrate hydrochloride, glycidyltrimethylammonium chloride, L-carnitine hydrochloride, and alkylcarbonyloxyethyltrimethylammonium chloride having 6 to 30 carbon atoms.

[0650] As the cationic compound of the polymer, for example, cationic polymers soluble in water and positively charged in water, such as polyacrylamine or its derivatives, amine-epihalohydrin copolymers or other quaternary ammonium salt type cationic polymers, can be cited. In addition, water-dispersible cationic polymers can also be used according to circumstances.

[0651] From the viewpoint of further improving the washing fastness of images in printed materials, low molecular weight cationic compounds are preferred.

[0652] The molecular weight of the low molecular cationic compound is preferably 1,000 or less, more preferably 500 or less.

[0653] The coagulant may be used alone or in combination of two or more.

[0654] The aqueous pretreatment liquid contains, for example, the aforementioned coagulant and water.

[0655] The aqueous pretreatment liquid may further contain other components such as an aqueous organic solvent and a surfactant.

[0656] As the components that may be contained in the aqueous pre-treatment liquid, the components that may be contained in the ink may be appropriately referred to.

[0657] (Ink applying process)

[0658] The ink application step is a step of applying the ink of the present invention to the fabric by an inkjet method.

[0659] In the present invention, the cloth to which the ink is applied in the ink applying step may be referred to as a colored cloth.

[0660] The application of ink in the ink application step can be performed using a known inkjet recording device.

[0661] The inkjet recording apparatus is not particularly limited, and any known inkjet recording apparatus that can achieve a target resolution can be arbitrarily selected and used.

[0662] As an example of the inkjet recording apparatus, there is exemplified an apparatus including an ink supply system, a temperature sensor, and a heating mechanism.

[0663] The ink supply system includes, for example, an original tank containing the ink of the present invention, a supply pipe, an ink supply tank directly in front of the inkjet head, a filter, and a piezoelectric inkjet head. The piezoelectric inkjet head can be driven in the following manner: it can eject multi-size dots of preferably 1 pL (picoliter) to 100 pL, more preferably 8 pL to 30 pL, at a resolution of preferably 320 dpi × 320 dpi to 4000 dpi × 4000 dpi, more preferably 400 dpi × 400 dpi to 1600 dpi × 1600 dpi, and further preferably 720 dpi × 720 dpi. In addition, dpi (dot per inch: dots per inch) means the number of dots per 2.54 cm (1 inch).

[0664] (Heat treatment process)

[0665] The heat treatment step is a step of heat-treating the cloth to which the ink is applied.

[0666] The heat treatment in this step can provide an image having excellent optical density and abrasion resistance.

[0667] The temperature of the heat treatment in the heat treatment step (the temperature of the ink applied to the fabric) is preferably 100°C to 220°C, more preferably 130°C to 200°C.

[0668] The time of the heat treatment in the heat treatment step is preferably 20 seconds to 300 seconds, more preferably 30 seconds to 240 seconds, and further preferably 40 seconds to 180 seconds.

[0669] The heat treatment in the heat treatment step may be a steam treatment known in inkjet printing, but a heat treatment other than a steam treatment is preferred from the viewpoint of simplifying the process.

[0670] As a heat treatment other than steam treatment, a heat treatment in which the cloth (ie, colored cloth) to which the ink is applied is subjected to heat pressing is preferred. In this heat treatment, the ink in the colored cloth can be heat treated by heat pressing the colored cloth.

[0671] Hot pressing can be performed using a known hot press machine.

[0672] As described above, in the inkjet printing method A, even when the steam treatment is omitted, an image having excellent optical density and abrasion resistance can be formed on the fabric by heat treatment other than the steam treatment.

[0673] The inkjet printing method A may include other steps besides the above steps.

[0674] As other steps, for example, there may be mentioned well-known steps in the inkjet textile printing method, such as a post-treatment step of post-treating the colored cloth after the heat treatment step with a post-treatment agent.

[0675] <Cloth>

[0676] Inkjet printing method A can be applied to various fabrics.

[0677] The types of fibers in the cloth include synthetic fibers such as nylon, polyester, and acrylonitrile; semi-synthetic fibers such as acetate and rayon; natural fibers such as cotton, silk, and wool; mixed fibers consisting of two or more selected from the group consisting of synthetic fibers, semi-synthetic fibers, and natural fibers; and the like.

[0678] As the type of fiber in the cloth, at least one selected from cotton and polyester is preferred.

[0679] Examples of the form of the fabric include woven fabric, knitted fabric, and nonwoven fabric.

[0680] The cloth may also be cloth for cloth products.

[0681] Examples of the fabric product include clothing (for example, T-shirts, long-sleeved sweatshirts, jerseys, shorts, wetsuits, dresses, shirts, etc.), bedding, handkerchiefs, and the like.

[0682] [Other image forming methods]

[0683] Of course, the ink of the present invention can also be used in image forming methods other than inkjet printing method A.

[0684] As an image forming method other than the inkjet printing method A, there can be mentioned a method in which the fabric in the inkjet printing method A is replaced with a substrate other than fabric.

[0685] As a base material other than cloth, a plastic base material is mentioned, for example.

[0686] Examples of the plastic in the plastic substrate include polyvinyl chloride (PVC) resin, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate (PET), polyethylene (PE), polystyrene (PS), polypropylene (PP), polycarbonate (PC), polyvinyl acetal, acrylic resin, and the like.

[0687] Plastic substrates can be corona treated.

[0688] The ink of the present invention can form an image with excellent adhesion not only on a general plastic substrate such as a PET substrate but also on a substrate with which it is difficult to ensure adhesion in image formation using a water-based ink.

[0689] Examples of substrates that are difficult to ensure adhesion to an image in image formation using a water-based ink include hydrophobic substrates having no polar group.

[0690] Examples of the hydrophobic substrate having no polar group include a PS substrate, a corona-treated PP substrate (sometimes referred to as "corona PP"), a PE substrate, and a PE-laminated paper substrate.

[0691] 〔Printed and dyed materials〕

[0692] The printed and dyed article of the present invention comprises cloth and an image.

[0693] The above-mentioned image contains the aforementioned oil-soluble dye (D) or oil-soluble dye (D1) and a polymer P containing a hydrophilic group.

[0694] The printed textile of the present invention may include other elements as necessary.

[0695] The printed product of the present invention has an image having excellent optical density.

[0696] The reason why this effect is exerted is as described above.

[0697] Preferred embodiments of the fabric, the oil-soluble dye (D), the oil-soluble dye (D1), and the hydrophilic group-containing polymer P are also as described above.

[0698] The image may contain components other than those described above as necessary. Regarding the components that may be contained in the image, reference may be made to the components in the ink of the present invention described above.

[0699] The method for producing the printed textile of the present invention is not particularly limited.

[0700] The printed product of the present invention can be produced, for example, using the ink of the present invention, and can preferably be produced by the inkjet printing method A described above.

[0701] Example

[0702] Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.

[0703] [Preparation of oil-soluble dye (D) and comparative compound]

[0704] Specific examples of the oil-soluble dye (D) d-1 to d-10 and comparative dyes R-1 and R-2 were prepared, respectively, and the MEK solubility of these specific examples was measured (the results are shown in Table 1 described later).

[0705] d-1 to d-10 correspond to specific examples of the oil-soluble dye (D1).

[0706] These specific examples were obtained by dissolving the following Reactive Black 5 or Acid Black 1 in oil.

[0707] Among them, R-1 and R-2 as comparative dyes had no oil solubility (MEK solubility was 5% by mass or more).

[0708] [Chemical formula 20]

[0709]

[0710] [Chemical formula 21]

[0711]

[0712] [Chemical formula 22]

[0713]

[0714] [Chemical formula 23]

[0715]

[0716] [Chemical formula 24]

[0717]

[0718] The specific operation of synthesizing each dye is shown below.

[0719] (Synthesis of d-6)

[0720] In a 300 mL three-necked eggplant flask, a solution of Reactive Black 5 (20 g; manufactured by Aldrich) in 11.84 g of water was stirred at 30°C for 1 hour, and then 5.1 g of tert-octylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation), 31.17 g of ethyl acetate, 10.39 g of methyl ethyl ketone and 5.71 g of sodium carbonate were added thereto, and stirred at 60°C for 2 hours. Then, 53.4 g of water was added thereto, and the mixture was cooled to 30°C and stirred for 2 hours. The precipitate obtained was collected by filtration and dried to obtain d-6. 1 The structure was identified by H-NMR (DMSO). The NMR data of d-6 are shown below.

[0721] -NMR data of d-6-

[0722] 1H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7 .49(s,1H),7.41(s,1H),3.48-3.44(q,4H),2.81-2.72(q,4H),1.29(s,4H),1.12(s,12H),0.93(s,18H)

[0723] (Synthesis of d-2 to d-5 and d-7 to d-9)

[0724] Change tert-octylamine to

[0725] The same number of moles of 2-ethylhexanol,

[0726] The same number of moles of 1-dodecyl mercaptan,

[0727] The same number of moles of 3-(2-ethylhexyloxy)propylamine,

[0728] The same number of moles of isobutylamine,

[0729] The same number of moles of dibutylamine,

[0730] The same number of moles of dihexylamine, or

[0731] Except for using the same molar amount of dioctylamine, the same method as in the synthesis of d-6 was followed to obtain d-2 to d-5 and d-7 to d-9.

[0732] These structures are also 1 The product was identified by H-NMR (DMSO).

[0733] -NMR data of d-2-

[0734] 1 H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7.49(s,1H ),7.41(s,1H),3.48-3.44(q,4H),2.81-2.72(q,4H),1.57-1.50(m,6H),1.31-1.12(m,16H),0.89-0.75(m,12H)

[0735] -NMR data of d-3-

[0736] 1H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7.49(s,1H),7.4 1(s,1H),3.15-3.44(m,8H),2.81-2.72(q,4H),2.41(t,4H),1.58-1.41(m,8H),1.29-1.25(m,32H),0.90-0.76(m,6H)

[0737] -NMR data of d-4-

[0738] 1 H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7.49(s,1H),7.41(s ,1H),3.48-3.44(q,6H),2.81-2.72(q,4H),2.50-2.41(m,4H),1.57-1.50(m,10H),1.31-1.12(m,16H),0.89-0.75(m,12H)

[0739] -NMR data of d-5-

[0740] 1 H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7.49(s ,1H),7.41(s,1H),3.48-3.44(q,4H),2.81-2.72(q,4H),2.50-2.41(m,4H),1.67(s,2H),0.89-0.75(m,12H)

[0741] -NMR data of d-7-

[0742] 1 H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7.49(s ,1H),7.41(s,1H),3.48-3.44(q,4H),2.81-2.72(q,4H),2.25(q,8H),1,29-1.12(m,16H),0.89-0.81(m,12H)

[0743] -NMR data of d-8-

[0744] 1 H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7.49(s ,1H),7.41(s,1H),3.48-3.44(q,4H),2.81-2.72(q,4H),2.25(q,8H),1,29-1.12(m,32H),0.89-0.81(m,12H)

[0745] -NMR data of d-9-

[0746] 1 H-NMR(400MHz,DMSO-d6):15.61-15.15(s,1H),10.65-10.48(d,2H),8.29(d,2H),8.18-7.90(m,6H),7.49(s ,1H),7.41(s,1H),3.48-3.44(q,4H),2.81-2.72(q,4H),2.25(q,8H),1,29-1.12(m,48H),0.89-0.81(m,12H)

[0747] (Synthesis of d-10)

[0748] D-10 was obtained in the same manner as in the synthesis of D-9, except that Reactive Black 5 in the form of K salt was used as a raw material instead of Reactive Black 5 in the form of Na salt, and that sodium carbonate was replaced with potassium carbonate in the same molar amount. 1 The structure was identified by H-NMR (DMSO). The NMR data were identical to those of d-9 and were therefore omitted.

[0749] (Synthesis of d-1)

[0750] After adding 141.9 g of a 10% by mass aqueous solution of benzyldimethyloctylammonium chloride to a 500 mL eggplant-shaped flask, 154.1 g of a 10% by mass aqueous solution of Acid Black 1 was added dropwise over 30 minutes, and stirred for 2 hours. The obtained precipitate was collected with a filter cloth and dried to obtain d-1. 1 The structure was identified by H-NMR (DMSO). The NMR data of d-1 are shown below.

[0751] -NMR data of d-1-

[0752] 1 H-NMR(400MHz,DMSO-d6):10.80(s,1H),10.58(s,1H),8.39(d,2H),8.23(d,2H),7.81(q,2H),7.61-7.42(m,13H ),7.40(s,1H),7.28(t,1H),4.51(s,4H),3.19-3.29(m,4H),2.91(s,12H),1.31-1.20(m,24H),0.89-0.80(t,6H)

[0753] (Synthesis of R-1)

[0754] R-1 was obtained in the same manner as in the synthesis of d-1 except that benzyldimethyloctylammonium chloride was replaced with benzyltrimethylammonium chloride in the same molar amount.

[0755] pass 1 The structure was confirmed by H-NMR (DMSO). NMR data are omitted.

[0756] (Synthesis of R-2)

[0757] R-2 was obtained in the same manner as in the synthesis of d-6 except that tert-octylamine was replaced with dipropylamine in the same molar amount.

[0758] pass 1 The structure was confirmed by H-NMR (DMSO). NMR data are omitted.

[0759] [Example 1]

[0760] <Synthesis of polymer P>

[0761] In a three-necked flask, add

[0762] 176.2 g of hexamethylene diisocyanate (HDI) as a compound for forming unit (1),

[0763] 68.1 g of 2,2-dimethylolpropionic acid (DMPA) as a compound for introducing a hydrophilic group,

[0764] 491.9 g of the compound "(2-18) PC T5651" (polycarbonate diol) as a compound for forming the unit (2), and

[0765] Ethyl acetate 1202.62 g,

[0766] Heating was performed at 70°C.

[0767] Here, the compound "(2-18) PC T5651" is DURANOL (registered trademark) T5651 manufactured by ASAHI KASEI CHEMICALS CORPORATION (simply referred to as "T5651" in the table). Mn is 1000. Rc 1 and Rc 2 are alkylene groups having 5 or 6 carbon atoms. ).

[0768] Next, 2.454 g of NEOSTANN U-600 (manufactured by NITTOH CHEMICAL CO., LTD., an inorganic bismuth catalyst; hereinafter also referred to as “U-600”) was added to the three-necked flask, and the mixture was stirred at 70° C. for 5 hours.

[0769] Next, 515.41 g of isopropyl alcohol and 711.75 g of ethyl acetate were added thereto, and the mixture was stirred at 70° C. for 3 hours.

[0770] The reaction solution after stirring for 3 hours was naturally cooled to room temperature (23° C.), and then the concentration was adjusted with ethyl acetate to obtain a 30 mass % solution of polymer P (the solvent was a mixed solution of ethyl acetate / isopropyl alcohol).

[0771] In addition, a part of the above-mentioned amount of isopropyl alcohol also functions as a terminal blocking agent for the polymer P.

[0772] Table 1 shows the type of compound (raw material) for forming each unit in the polymer P, Mw, Tg (° C.), and acid value (mmol / g).

[0773] <Preparation of pretreatment solution>

[0774] The components of the following composition were mixed to obtain a pretreatment liquid PC-1.

[0775] - Composition of pretreatment solution PC-1 -

[0776] PAS-H-1L (coagulant (diallyldimethylammonium chloride polymer), manufactured by NITTOBO MEDICAL CO., LTD., solid content 28% by mass) (100 parts by mass)

[0777] BYK348 (manufactured by BYK Japan KK) (5 parts by mass)

[0778] 2-Pyrrolidone (50 parts by mass)

[0779] Glycerin (50 parts by mass)

[0780] Water (845 parts by mass)

[0781] <Preparation of Colored Resin Particle Dispersion>

[0782] (Preparation of Oil Phase Components)

[0783] Ethyl acetate, a 30% by mass solution of the polymer P, and d-1 as the oil-soluble dye (D) were mixed and stirred for 15 minutes to obtain 149.8 g of an oil phase component having a solid content of 30% by mass.

[0784] In the preparation of the oil phase component, the usage amounts of the 30 mass % solution of polymer P and d-1 were adjusted as follows:

[0785] The content of the polymer P was 40% by mass based on the solid content of the produced colored resin particles.

[0786] The content of d-1 was 60% by mass based on the solid content of the produced colored resin particles.

[0787] The content mass ratio [P / dye] (that is, the ratio of the content mass of the polymer P to the content mass of the oil-soluble dye) in the produced colored resin particles was 0.67.

[0788] (Preparation of aqueous phase components)

[0789] An aqueous phase component was prepared by mixing 135.3 g of distilled water and sodium hydroxide as a neutralizing agent and stirring for 15 minutes.

[0790] In the produced colored resin particles, the amount of sodium hydroxide used as a neutralizing agent was adjusted so that the degree of neutralization (ie, the ratio of the number of sodium salts of carboxyl groups to the total number of carboxyl groups and sodium salts of carboxyl groups) became 90%.

[0791] (Preparation of Colored Resin Particle Dispersion)

[0792] The oil phase component and the water phase component were mixed, and the obtained mixture was emulsified at room temperature at 18000 rpm for 10 minutes using a homogenizer to obtain an emulsion. The obtained emulsion was added to 48.0 g of distilled water, and the obtained liquid was heated at 50° C. and stirred at 50° C. for 5 hours to distill off ethyl acetate and isopropyl alcohol from the liquid.

[0793] The mixture was diluted with distilled water so that the solid content of the liquid from which ethyl acetate and isopropyl alcohol were distilled off became 20% by mass, thereby obtaining a black colored resin particle dispersion containing colored resin particles and water.

[0794] The volume average particle size of the colored resin particles in the colored resin particle dispersion was 150 nm (the same also applies to Examples 2 to 17 and Comparative Examples 1 and 2 described later).

[0795] <Ink Preparation>

[0796] The colored resin particle dispersion, the following surfactant, glycerin and distilled water were mixed, and the resulting mixture was filtered through a membrane filter (pore size: 1 μm) made of polytetrafluoroethylene (PTFE) to obtain an ink having the following composition. The ink of Example 1 is a black ink.

[0797] -Ink composition-

[0798] Solid content of colored resin particles (ie, solid content in the above-mentioned colored resin particle dispersion) ... 10 parts by mass

[0799] Surfactant ("OLFINE E1010" manufactured by Nissin Chemical Co., Ltd.) ... 1 part by mass

[0800] Glycerin…20 parts by mass

[0801] · Distilled water…69 parts by mass

[0802] <Inkjet printing>

[0803] Inkjet printing was performed using the above pretreatment liquid and the above ink.

[0804] In short, cotton fabric is pretreated with the pretreatment liquid, the ink is applied to the pretreated cotton fabric to obtain a colored fabric, and the obtained colored fabric is heat-treated to obtain a printed fabric.

[0805] The details are shown below.

[0806] (Pretreatment of cotton fabrics)

[0807] The aqueous pretreatment liquid PC-1 was impregnated into cotton cloth (cotton width 40, manufactured by Shikisensha Co., Ltd.) at a liquid pass rate of 60% by a filling method, and dried for 24 hours.

[0808] Here, the squeeze rate (%) indicates the remaining amount (mass ratio) of the aqueous pre-treatment liquid relative to the fabric after the fabric containing the aqueous pre-treatment liquid is squeezed.

[0809] (Ink application)

[0810] The ink was applied to the pre-treated cotton cloth using an inkjet printer (PX-045A, manufactured by SEIKO EPSON CORPORATION) to form a solid image, thereby obtaining a colored cloth. The amount of ink applied was 15 g / m 2 .

[0811] (Heat treatment (hot pressing))

[0812] The colored cloth was dried at 20° C. for 12 hours.

[0813] The dried colored cloth was heat-treated at 140° C. for 120 seconds using a heat press (desktop automatic flatbed press AF-54TEN, manufactured by Asahi Kasei Corporation). The solid image in the dried colored cloth was heat-treated to obtain a printed product.

[0814] <Evaluation>

[0815] The following evaluations were carried out using the above ink and the above printed product.

[0816] Table 1 shows the results.

[0817] (Optical density of image)

[0818] The optical density (OD (Optical Density) value) of the image in the printed material was measured and evaluated according to the following evaluation criteria.

[0819] The OD value was measured using a colorimeter (Gretag Macbeth Spectrolino, manufactured by X-Rite Inc.).

[0820] In the following evaluation criteria, the level with the most excellent optical density of an image is SSS.

[0821] -Evaluation criteria for optical density of images-

[0822] SSS: OD value is above 1.7

[0823] SS: OD value is 1.6 or more and less than 1.7

[0824] S: OD value is 1.4 or more and less than 1.6

[0825] A: OD value is greater than 1.2 and less than 1.4

[0826] B: OD value is 1.0 or more and less than 1.2

[0827] C: OD value is 0.8 or more and less than 1.0

[0828] D: OD value is less than 0.8

[0829] (Washing fastness of image)

[0830] The wash fastness of the images in the printed matter was evaluated according to ISO 105-C06.

[0831] In the evaluation results of the washing fastness of the image, the level 5 was the most excellent in the washing fastness of the image.

[0832] (Abrasion resistance of image)

[0833] The rubbing resistance of the image in the printed product was evaluated according to ISO105-X12.

[0834] The abrasion resistance of the image was evaluated under dry conditions and wet conditions.

[0835] Here, the dry condition (simply indicated as "dry" in Table 1) refers to the condition of wiping with a dry white cloth containing no water, and the wet condition (simply indicated as "wet" in Table 1) refers to the condition of wiping with a white cloth containing water.

[0836] In the evaluation results of the abrasion resistance of the image, the level 5 was the most excellent abrasion resistance of the image.

[0837] In the evaluation results of washing resistance and rubbing resistance in Table 1,

[0838] The mark "1-2" means that it is higher than level 1 and lower than level 2.

[0839] The mark "2-3" means that it is higher than level 2 and lower than level 3.

[0840] The mark "3-4" means that it is higher than grade 3 and lower than grade 4.

[0841] The mark of "4-5" means higher than grade 4 and lower than grade 5.

[0842] (Ink ejection properties)

[0843] The ejection properties of the ink were evaluated as an index of the dispersion stability of the colored resin particles in the colored resin particle dispersion. The details are shown below.

[0844] The ink prepared and stored at room temperature for less than 1 day was ejected from the nozzle of an inkjet printer (manufactured by FUJIFILM Dimatix, Inc., DMP) for 30 minutes, and then the ejection was stopped. Five minutes after the ejection was stopped, the ink was ejected from the nozzle again on a polystyrene substrate ("Falcon Hi Impact Polystyrene" manufactured by Robert Horne) to form a 5 cm×5 cm solid image.

[0845] The obtained solid image was observed with the naked eye to confirm the presence or absence of dot omission due to the occurrence of non-ejecting nozzles, and the ink ejection properties were evaluated according to the following evaluation criteria.

[0846] In the following evaluation criteria, the most excellent ink ejection property was ranked A.

[0847] -Evaluation criteria for ejection properties-

[0848] A: The occurrence of dot omission due to the occurrence of non-ejecting nozzles was not confirmed, and a good image was obtained.

[0849] B: Occurrence of dot missing due to the occurrence of non-ejecting nozzles was slightly observed, but it was not a problem in practical use.

[0850] C: Dot missing occurred due to the generation of non-ejecting nozzles, and the image cannot be actually used.

[0851] D: Cannot be sprayed from the nozzle.

[0852] (Storage stability of ink)

[0853] The storage stability of the ink was evaluated as an index of the dispersion stability of the colored resin particles in the colored resin particle dispersion. The details are shown below.

[0854] The ink was stored at room temperature within 1 day after preparation, sealed in a container, and then stored at 50° C. for 4 weeks.

[0855] Using the ink after the lapse of 4 weeks, the same evaluation as the evaluation of the ejection properties of the above-mentioned ink was performed.

[0856] [Example 2 to Example 10]

[0857] The same operation as in Example 1 was carried out except that d-1 as the oil-soluble dye was changed to an oil-soluble dye shown in Table 1 having the same mass.

[0858] Table 1 shows the results.

[0859] [Examples 11 to 13 and 15 to 17]

[0860] The same operation as in Example 1 was performed except for the following points.

[0861] Table 1 shows the results.

[0862] - Changes from Example 1 -

[0863] In the synthesis of the polymer P contained in the ink, the total mass used of the compound for forming the unit (1) and the compound for forming the unit (2) and the molar ratio used [compound for forming the unit (2) / compound for forming the unit (1)] were not changed, but the combination of the type of the compound for forming the unit (1) and the type of the compound for forming the unit (2) was changed to the combination shown in Table 1. The type of the compound for forming the unit (1) and the type of the compound for forming the unit (2) in Table 1 correspond to the symbols of the above-mentioned specific examples, respectively.

[0864] In Example 13, the same molar number of "(2-22) PEG (Mn = 30,000)" and "(2-18) PCT5651" were used as the unit (2)-forming compound, and the total molar number was adjusted to be the same as the molar number of "(2-18) PCT5651" in Example 1.

[0865] The reaction conditions (reaction temperature and reaction time) were adjusted so that the weight average molecular weight of the polymer P would be 15,000.

[0866] [Example 14]

[0867] The same operation as in Example 13 was carried out except that the pretreatment liquid PC-1 was changed to the pretreatment liquid PC-2 having the following composition.

[0868] Table 1 shows the results.

[0869] - Composition of pretreatment solution PC-2 -

[0870] The following compound (X1)

[0871] ……10% by mass

[0872] 2-Pyrrolidone

[0873] ……16% by mass

[0874] ·2-Methyl-1,3-propanediol

[0875] ……9% by mass

[0876] ·water

[0877] ...the remainder to 100% by mass

[0878] [Chemical formula 25]

[0879]

[0880] [Comparative Example 1 and Comparative Example 2]

[0881] The same operation as in Example 1 was carried out except that d-1 as the oil-soluble dye was changed to a comparative dye shown in Table 1 having the same mass.

[0882] Table 1 shows the results.

[0883] The MEK solubility of the comparative dyes R-1 and R-2 is less than 5% by mass, and they are not oil-soluble dyes.

[0884] [Table 1]

[0885]

[0886] As shown in Table 1, in each example using an oil-soluble dye (D) in which a water-soluble reactive dye is modified with an alkyl group having 4 or more carbon atoms or a counter cation in an acid dye is replaced with an organic cation containing an alkyl group having 4 or more carbon atoms, the optical density of the image and the storage stability of the ink are excellent.

[0887] In contrast, in Comparative Example 1 using Comparative Dye R-1 in which the counter cation in the acid dye was replaced with an organic cation not containing an alkyl group having more than 4 carbon atoms, and Comparative Example 2 using Comparative Dye R-2 in which a water-soluble reactive dye was modified with an alkyl group having less than 3 carbon atoms, the optical density of the image and the storage stability of the ink were reduced. These Comparative Dyes R-1 and R-2 have a MEK solubility of less than 5% by mass and are not oil-soluble dyes.

[0888] Comparison between Example 1 and Examples 2 to 17 shows that when an oil-soluble dye (D) in which a water-soluble reactive dye is modified with an alkyl group having 4 or more carbon atoms is used (Examples 2 to 17), the optical density of the image is further improved.

[0889] Comparison between Examples 2 and 3 and Examples 4 to 17 shows that when an oil-soluble dye equivalent to the oil-soluble dye (D3) is used (Examples 4 to 17), the optical density of the image is further improved.

[0890] By comparing Examples 6 and 11 to 15 with Examples 16 and 17, it can be seen that when L in the unit (2) in the polymer P 2 In the case of a polymer chain having a number average molecular weight of 500 or more and composed of a polycarbonate chain or a polyether chain (Examples 6 and 11 to 15), the abrasion resistance of the image and the storage stability of the ink were further improved.

[0891] In the above, an embodiment group in which a black colored resin particle dispersion is used as the colored resin particle dispersion of the present invention is shown. However, of course, even when at least one colored resin particle dispersion of another color is used instead of the black colored resin particle dispersion or on the basis of the black colored resin particle dispersion, the same effect as the above-mentioned embodiment group can be obtained.

[0892] The entire contents of the invention of Japanese Patent Application No. 2019-180626 filed on September 30, 2019 are incorporated into this specification by reference.

[0893] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described as being incorporated by reference.

Claims

1. A colored resin particle dispersion comprising: water; and Colored resin particles, comprising an oil-soluble dye and a polymer P containing a hydrophilic group, The polymer P containing a hydrophilic group is selected from polyurethane resin, acrylic resin, polyester resin, polyether resin, polycaprolactone resin, polycarbonate resin, polybutadiene resin, polyisoprene resin, and polyolefin resin, and the hydrophilic group is selected from carboxyl, sulfonic, sulfate, phosphonic acid, phosphoric acid, carboxyl salt, sulfonic salt, sulfate salt, phosphonic acid salt, and phosphoric acid salt. The oil-soluble dye comprises an oil-soluble dye (D2) represented by the following formula (D2), In formula (D2), R 11 and R 12 each independently represents a hydrocarbon group having 1 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, Two Xs + represents an inorganic cation or an organic cation, in, Satisfy at least one of the following conditions: 11 and R 12 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the cations is an organic cation containing an alkyl group having 4 or more carbon atoms.

2. The colored resin particle dispersion according to claim 1, wherein The oil-soluble dye (D2) is an oil-soluble dye (D3) represented by the following formula (D3), In formula (D3), R 13 ~R 16 each independently represents a hydrocarbon group having 1 to 25 carbon atoms or a hydrogen atom which may contain an oxygen atom, a nitrogen atom or a sulfur atom, Two Xs + represents an inorganic cation or an organic cation, Among them, at least one of the following conditions is met: 13 ~R 16 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the cations is an organic cation containing an alkyl group having 4 or more carbon atoms.

3. The colored resin particle dispersion according to claim 2, wherein In the formula (D3), R 13 ~R 16 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, Two Xs + K + Or Na + .

4. The colored resin particle dispersion according to claim 1 or 2, wherein The hydrophilic group-containing polymer P further contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), In formula (1), L 1 represents a hydrocarbon group, The two *1s represent the bonding positions, In formula (2), L 2 represents a hydrocarbon group having 2 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, or a polymer chain having a number average molecular weight of 500 or more consisting of a polyether chain, a polyester chain, a polycaprolactone chain, a polycarbonate chain, a polybutadiene chain, a polyisoprene chain or a polyolefin chain, Y 1 and Y 2 Each independently represents -O-, -S- or -NRz-, Rz represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, The two *2s represent the bonding positions respectively.

5. The colored resin particle dispersion according to claim 4, wherein The L in the formula (2) 2 It is a polymer chain having a number average molecular weight of 500 or more and composed of a polycarbonate chain or a polyether chain.

6. The colored resin particle dispersion according to claim 1 or 2, wherein The glass transition temperature of the hydrophilic group-containing polymer P is 50° C. or lower.

7. The colored resin particle dispersion according to claim 1 or 2, wherein The hydrophilic group in the hydrophilic group-containing polymer P is at least one selected from the group consisting of a carboxyl group and a salt of a carboxyl group.

8. The colored resin particle dispersion according to claim 1 or 2, wherein The weight average molecular weight of the polymer P containing a hydrophilic group is 8,000 to 30,000. 9 . An ink comprising the colored resin particle dispersion according to claim 1 .

10. The ink according to claim 9 for use as an inkjet ink.

11. The ink according to claim 9, which is used as an ink for textile printing.

12. An ink set comprising two or more inks, At least one of the two or more inks is the ink according to any one of claims 9 to 11.

13. An inkjet printing and dyeing method comprising the following steps: A step of applying the ink according to any one of claims 9 to 11 to a cloth by an inkjet method; and A step of obtaining a printed product by heat-treating the cloth to which the ink has been applied.

14. A method for producing an oil-soluble dye, comprising the step of obtaining the oil-soluble dye by the method (1) or the method (2), wherein in the method (1), a water-soluble reactive dye is reacted with a primary amine compound containing a group containing an alkyl group having 4 or more carbon atoms, a secondary amine compound containing a group containing an alkyl group having 4 or more carbon atoms, a hydroxy compound containing a group containing an alkyl group having 4 or more carbon atoms, or a thiol compound containing a group containing an alkyl group having 4 or more carbon atoms, and in the method (2), an acid dye is reacted with a salt of an organic cation containing an alkyl group having 4 or more carbon atoms. The oil-soluble dye comprises an oil-soluble dye (D2) represented by the following formula (D2), In formula (D2), R 11 and R 12 each independently represents a hydrocarbon group having 1 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, Two Xs + represents an inorganic cation or an organic cation, in, Satisfy at least one of the following conditions: 11 and R 12 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the cations is an organic cation containing an alkyl group having 4 or more carbon atoms.

15. A printed and dyed article comprising: a cloth and an image, The image comprises an oil-soluble dye (D) and a polymer P containing a hydrophilic group, wherein the oil-soluble dye (D) is a water-soluble reactive dye modified by an alkyl group having 4 or more carbon atoms or a counter cation in an acid dye is replaced by an organic cation containing an alkyl group having 4 or more carbon atoms, The polymer P containing a hydrophilic group is selected from polyurethane resin, acrylic resin, polyester resin, polyether resin, polycaprolactone resin, polycarbonate resin, polybutadiene resin, polyisoprene resin, and polyolefin resin, and the hydrophilic group is selected from carboxyl, sulfonic, sulfate, phosphonic acid, phosphoric acid, carboxyl salt, sulfonic salt, sulfate salt, phosphonic acid salt, and phosphoric acid salt. The oil-soluble dye (D) comprises an oil-soluble dye (D2) represented by the following formula (D2), In formula (D2), R 11 and R 12 each independently represents a hydrocarbon group having 1 to 50 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, Two Xs + represents an inorganic cation or an organic cation, in, Satisfy at least one of the following conditions: 11 and R 12 At least one of them is a group containing an alkyl group having 4 or more carbon atoms, and two X + At least one of the cations is an organic cation containing an alkyl group having 4 or more carbon atoms.

Images