阅读说明：本技术 着色分散液、记录介质、及疏水性纤维的印染方法 (Coloring dispersion liquid, recording medium, and method for printing hydrophobic fiber ) 是由 松本贵博 萩原悠太 宫泽由昌 田中勇气 于 2020-05-19 设计创作，主要内容包括：本发明提供着色分散液,其含有(A)C.I.分散橙25、(B)C.I.分散橙49、62、71、73、148等特定色素、和水,将(A)C.I.分散橙25与(B)特定色素的总含量作为100质量份时的(B)特定色素的含量低于20质量份。另外,提供附着有该着色分散液的记录介质、及使用该着色分散液的疏水性纤维的印染方法。(The invention provides a coloring dispersion liquid, which contains (A) C.I. dispersed orange 25, (B) specific pigment such as C.I. dispersed oranges 49, 62, 71, 73 and 148, and water, wherein the content of the (B) specific pigment is less than 20 parts by mass when the total content of the (A) C.I. dispersed orange 25 and the (B) specific pigment is taken as 100 parts by mass. Also provided are a recording medium having the coloring dispersion adhered thereto, and a method for printing hydrophobic fibers using the coloring dispersion.)

1. A coloring dispersion liquid containing (A) C.I. disperse orange 25, (B) at least 1 coloring matter selected from the coloring matters represented by the following formula (1) and the coloring matters represented by the following formula (2), and water,

the content of the (B) pigment is less than 20 parts by mass when the total content of the (a) c.i. dispersed orange 25 and the (B) pigment is 100 parts by mass.

[ chemical formula 1]

(in the formula (1), R¹And R²Each independently represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent, and n represents an integer of 1 to 7. )

[ chemical formula 2]

(in the formula (2), R³Represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent, R⁴And R⁵Each independently represents a hydrogen atom or a halogen atom, and X represents an oxygen atom, -OCONH-, -OCO-, or-OCOCH₂-, m represents an integer of 1 to 7. )

2. The coloring dispersion liquid according to claim 1, wherein the content of the (B) pigment is 0.1 to 15 parts by mass, based on 100 parts by mass of the total content of the (A) C.I. dispersed orange 25 and the (B) pigment.

3. The coloring dispersion liquid according to claim 1, wherein the content of the (B) pigment is 0.5 to 5 parts by mass, based on 100 parts by mass of the total content of the (A) C.I. dispersed orange 25 and the (B) pigment.

4. The coloring dispersion liquid according to any one of claims 1 to 3, wherein the pigment represented by formula (1) is C.I. disperse orange 73.

5. A coloring dispersion liquid according to any one of claims 1 to 4, which further contains a dispersant.

6. The colored dispersion liquid according to claim 5, wherein the dispersant contains at least 1 selected from the group consisting of a styrene- (meth) acrylic acid-based copolymer, a formaldehyde condensate of an aromatic sulfonic acid or a salt thereof, a polyoxyethylene aryl phenyl ether sulfate, and a polyoxyethylene naphthyl ether.

7. The coloring dispersion liquid according to claim 6, wherein the formaldehyde condensate of an aromatic sulfonic acid or a salt thereof comprises a sodium naphthalenesulfonate formaldehyde condensate or a salt thereof.

8. The coloring dispersion liquid according to claim 6 or 7, wherein the formaldehyde condensate of an aromatic sulfonic acid or a salt thereof comprises a formaldehyde condensate of a creosote sulfonic acid or a salt thereof.

9. The coloring dispersion liquid according to any one of claims 6 to 8, wherein the polyoxyethylene aryl phenyl ether is polyoxyethylene styrene phenyl ether, and the polyoxyethylene aryl phenyl ether sulfate is polyoxyethylene styrene phenyl ether sulfate.

10. A pigmented dispersion according to any one of claims 6 to 9 wherein said dispersant further comprises a phytosterol compound.

11. The coloring dispersion liquid according to any one of claims 1 to 10, further comprising a yellow dye, a blue dye, and an orange dye different from the (a) c.i. disperse orange 25 and the (B) pigment.

12. A recording medium having the coloring dispersion liquid according to any one of claims 1 to 11 attached thereto.

13. The recording medium of claim 12, wherein the recording medium is a hydrophobic fiber.

14. A method of printing hydrophobic fibers comprising:

a printing step of attaching droplets of the coloring dispersion liquid according to any one of claims 1 to 11 to an intermediate recording medium to obtain a recorded image; and

and a transfer step of bringing a hydrophobic fiber into contact with the surface of the intermediate recording medium to which the coloring dispersion liquid adheres, and performing a heat treatment to thereby transfer the recording image to the hydrophobic fiber.

Technical Field

The present invention relates to a coloring dispersion liquid, a recording medium to which the coloring dispersion liquid is attached, and a method for printing hydrophobic fibers using the coloring dispersion liquid.

Background

In recent years, recording methods have been proposed for printing by inkjet without plate making, and printing by inkjet printing (inkjet printing) has also been performed for printing fibers including fabrics and the like. Printing by ink jet printing has various advantages over conventional printing methods such as screen printing: no plate making; resources are saved; energy is saved; high-precision presentation is easy to carry out; and so on.

Here, hydrophobic fibers represented by polyester fibers are usually dyed with a water-insoluble coloring material. Therefore, it is generally necessary to use a dispersion ink which is obtained by dispersing a water-insoluble coloring material in water and has good properties such as dispersion stability as an aqueous ink for printing hydrophobic fibers by ink jet printing.

Inkjet printing methods for hydrophobic fibers can be broadly classified into direct printing methods and sublimation transfer methods. The direct printing method is a printing method in which ink is directly applied (printed) to a hydrophobic fiber and then a dye in the ink is dyed to the hydrophobic fiber by heat treatment such as high-temperature steaming. On the other hand, the sublimation transfer method is the following printing method: after ink is applied (printed) on an intermediate recording medium (such as a special transfer paper), the ink application surface of the intermediate recording medium is superimposed on the hydrophobic fiber, and then the dye is transferred from the intermediate recording medium to the hydrophobic fiber by heat.

The sublimation transfer method is mainly used for printing and dyeing processes of carp flags and the like, and an easily sublimable dye having excellent transfer suitability for hydrophobic fibers by heat treatment is used for the ink. The processing step includes the following two steps, namely, (1) a printing step: a step of applying a dye ink to an intermediate recording medium by an ink jet printer, (2) a transfer step: a step of transferring and dyeing the dye from the intermediate recording medium to the fiber by heat treatment; since commercially available transfer paper can be widely used, pretreatment of the fibers is not required, and the washing step is omitted.

As the ink used in the sublimation transfer method, an aqueous ink in which a water-insoluble dye is dispersed in water is generally used. For example, patent document 1 describes the following: an aqueous ink is prepared by adding a water-soluble organic solvent as a humectant (anti-drying agent), a surfactant as a surface tension adjuster, and other additives (pH adjuster, antiseptic/antifungal agent, defoaming agent, etc.) to a dye dispersion obtained by dispersing a water-insoluble dye selected from a disperse dye and an oil-soluble dye in water with a dispersant to optimize physical properties such as particle size, viscosity, surface tension, and pH.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2005/121263

Disclosure of Invention

Problems to be solved by the invention

However, as a result of studies by the inventors of the present application on a conventional aqueous ink obtained by dispersing a water-insoluble dye in water, it was found that, even when the dispersion stability of a dye dispersion liquid is relatively good, when a component such as a surfactant is added to the dye dispersion liquid to prepare an aqueous ink, particles in the aqueous ink aggregate, and the dispersion stability is lowered.

The invention provides a coloring dispersion liquid which has excellent dispersion stability and can inhibit aggregation of particles during storage, a recording medium on which the coloring dispersion liquid is adhered, and a printing method of hydrophobic fiber using the coloring dispersion liquid.

Means for solving the problems

Specific means for solving the above problems include the following embodiments.

1)

A coloring dispersion liquid containing (A) C.I. disperse orange 25, (B) at least 1 coloring matter selected from the coloring matters represented by the following formula (1) and the coloring matters represented by the following formula (2), and water,

the content of the (B) pigment is less than 20 parts by mass when the total content of the (a) c.i. dispersed orange 25 and the (B) pigment is 100 parts by mass.

[ chemical formula 1]

(in the formula (1), R¹And R²Each independently represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent, and n represents an integer of 1 to 7. )

[ chemical formula 2]

(in the formula (2), R³Represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent, R⁴And R⁵Each independently represents a hydrogen atom or a halogen atom, and X represents an oxygen atom, -OCONH-, -OCO-, or-OCOCH₂-, m represents an integer of 1 to 7. )

2)

The coloring dispersion liquid according to claim 1), wherein the content of the pigment (B) is 0.1 to 15 parts by mass, based on 100 parts by mass of the total content of the pigment (B) and the pigment (C.I. dispersed orange 25 (A).

3)

The coloring dispersion liquid according to 1), wherein the content of the pigment (B) is 0.5 to 5 parts by mass, based on 100 parts by mass of the total content of the pigment (B) and the pigment (C.I. dispersed orange 25 (A).

4)

The coloring dispersion liquid according to any one of 1) to 3), wherein the pigment represented by the formula (1) is C.I. disperse orange 73.

5)

The colored dispersion liquid according to any one of 1) to 4), which further contains a dispersant.

6)

The colored dispersion liquid according to claim 5), wherein the dispersant contains at least 1 selected from the group consisting of a styrene- (meth) acrylic acid copolymer, a formaldehyde condensate of an aromatic sulfonic acid or a salt thereof, a polyoxyethylene aryl phenyl ether sulfate, and a polyoxyethylene naphthyl ether.

7)

The colored dispersion liquid according to claim 6), wherein the formaldehyde condensate of an aromatic sulfonic acid or a salt thereof comprises a sodium naphthalenesulfonate formaldehyde condensate or a salt thereof.

8)

The colored dispersion liquid according to 6) or 7), wherein the formaldehyde condensate of an aromatic sulfonic acid or a salt thereof comprises a formaldehyde condensate of a creosote sulfonic acid or a salt thereof.

9)

The coloring dispersion liquid according to any one of claims 6) to 8), wherein the polyoxyethylene aryl phenyl ether is polyoxyethylene styryl phenyl ether, and the polyoxyethylene aryl phenyl ether sulfate is polyoxyethylene styryl phenyl ether sulfate.

10)

The coloring dispersion liquid according to any one of claims 6) to 9), wherein the dispersant further contains a phytosterol compound.

11)

The colored dispersion liquid according to any one of 1) to 11), which further contains a yellow dye, a blue dye, and an orange dye different from the c.i. disperse orange 25 (a) and the pigment (B).

12)

A recording medium having the colored dispersion liquid according to any one of 1) to 11) adhered thereto.

13)

The recording medium according to claim 12), wherein the recording medium is a hydrophobic fiber.

14)

A method of printing hydrophobic fibers comprising:

a printing step of attaching droplets of the coloring dispersion liquid according to any one of 1) to 11) to an intermediate recording medium to obtain a recorded image; and

and a transfer step of bringing a hydrophobic fiber into contact with the surface of the intermediate recording medium to which the coloring dispersion liquid adheres, and performing a heat treatment to thereby transfer the recording image to the hydrophobic fiber.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a coloring dispersion liquid which has excellent dispersion stability and in which aggregation of particles during storage is suppressed, a recording medium to which the coloring dispersion liquid is attached, and a method for printing hydrophobic fibers using the coloring dispersion liquid.

Detailed Description

< coloring Dispersion >

The coloring dispersion liquid according to the present embodiment contains (a) c.i. disperse orange 25, (B) at least 1 kind of coloring matter selected from the coloring matter represented by the above formula (1) and the coloring matter represented by the above formula (2), and water. "c.i." is a shorthand for the color index. Hereinafter, each component contained in the coloring dispersion liquid according to the present embodiment will be described.

[ coloring agent ]

The coloring dispersion liquid according to the present invention contains (a) c.i. dispersed orange 25 and (B) at least 1 kind of coloring matter selected from the coloring matter represented by the above formula (1) and the coloring matter represented by the above formula (2) as coloring matters, and the content of the (B) coloring matter is less than 20 parts by mass when the total content of the (a) c.i. dispersed orange 25 and the (B) coloring matter is 100 parts by mass. Such a colored dispersion liquid tends to stabilize the dispersion state of the particles in the colored dispersion liquid. The content of the pigment (B) is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total content of the pigment (B) and the c.i. dispersed orange 25 (a).

In the above formula (1), R¹And R²Each independently represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent.

Examples of the C1-C7 alkyl group include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-hexyl and n-pentyl; branched alkyl groups such as isopropyl, sec-butyl, and tert-butyl; cyclic alkyl groups such as cyclobutyl, cyclopentyl and cyclohexyl; and so on. Among C1-C7 alkyl groups, C1-C4 alkyl groups are preferred, and ethyl groups are more preferred.

Examples of the substituent which the C1-C7 alkyl group may have include a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, a silanol group, a halogen atom, a cyano group, a nitro group, an amino group, an alkoxy group, an aryloxy group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarboxyl group, an arylcarboxyl group, a heterocyclic group, an aromatic ring group and the like, and these substituents may further have an arbitrary substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Examples of the amino group include an amino group, a methylamino group, an ethylamino group, an n-butylamino group, a phenylamino group, a dimethylamino group, a diethylamino group, a di-n-butylamino group, a diphenylamino group, a dinaphthylamino group, an ethylmethylamino group, and a methylphenylamino group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-butoxy group, and a tert-butoxy group.

Examples of the aryloxy group include a phenoxy group and a naphthoxy group.

Examples of the alkylcarbonyl group include an acetyl group, an ethylcarbonyl group, and an n-butylcarbonyl group.

Examples of the arylcarbonyl group include a phenylcarbonyl group, a naphthylcarbonyl group, and a fluorenylcarbonyl group.

Examples of the alkylcarboxyl group include a methylcarboxyl group, an ethylcarboxyl group, and an n-butylcarboxyl group.

Examples of the arylcarboxyl group include a phenylcarboxyl group and the like.

Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, thiazolyl, and benzothiazolyl.

Examples of the aromatic ring group include a phenyl group, a naphthyl group, and a fluorenyl group.

Among these, as R¹Preferably cyanoethyl as R²Preferably a hydrogen atom.

In the formula (1), n represents an integer of 1 to 7, preferably an integer of 1 to 4.

The substitution position of the nitro group substituted on the benzene ring in the above formula (1) may be any of the ortho-position, meta-position, and para-position with respect to the azo bond site.

Among the pigments represented by the above formula (1), preferred pigment is c.i. disperse orange 73.

In the above formula (2), R³Represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent, R⁴And R⁵Each independently represents a hydrogen atom or a halogen atom, and X represents an oxygen atom, -OCONH-, -OCO-, or-OCOCH₂-. Examples of the C1-C7 alkyl group which may have a substituent and the halogen atom include those described in the above formula (1).

In the formula (2), m represents an integer of 1 to 7, preferably an integer of 1 to 4.

Preferred examples of the coloring matter represented by the above formula (2) include c.i. disperse oranges 49, 62, 71, and 148.

The dye (B) is preferably a dye represented by the formula (1), and more preferably c.i. disperse orange 73.

The total content of the (a) c.i. dispersed orange 25 and the (B) pigment is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the coloring dispersion liquid.

The coloring dispersion liquid according to the present embodiment may further contain a colorant other than (a) c.i. disperse orange 25 and (B) a pigment. However, it is preferable that the content of (a) c.i. dispersed orange 25 is the largest.

Examples of the other colorant include pigments, disperse dyes, oil-soluble dyes, acid dyes, reactive dyes, and direct dyes, and the disperse dyes and the oil-soluble dyes are preferable, and the disperse dyes are more preferable.

Specific examples of the disperse dye include c.i. disperse yellow 3, 4, 5, 7,9, 13, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 201, 202, 204, 210, 211, 215, 216, 218, 224, 231, 232, 241, and the like; c.i. disperse oranges 1,3, 5, 7, 11, 13, 17, 20, 21, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142, etc.; c.i. disperse red 1,4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 279, 257, 277, 278, 281, 289, 310, 302, 303, 298, 288, 298, 324, 328, 311, 343, etc.; c.i. disperse violet 1,4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, etc.; c.i. disperse green 6: 1. 9, etc.; c.i. disperse brown 1,2, 4, 9, 13, 19, 27, etc.; c.i. disperse blue 3, 7,9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 343, 359, 360, etc.; c.i. disperse black 1,3, 10, 24, etc.; and so on. These disperse dyes may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Specific examples of the oil-soluble dye include c.i. solvent yellow 2, 6, 14, 16, 21, 25, 29, 30, 33, 51, 56, 77, 80, 82, 88, 89, 93, 116, 150, 163, 179 and the like; c.i. solvent orange 1,2, 14, 45, 60, etc.; c.i. solvent red 1,3, 7, 8, 9, 18, 19, 23, 24, 25, 27, 49, 100, 109, 121, 122, 125, 127, 130, 132, 135, 218, 225, 230, etc.; c.i. solvent violet 13, etc.; c.i. solvent green 3, etc.; c.i. solvent brown 3,5, etc.; c.i. solvent blue 2, 11, 14, 24, 25, 35, 36, 38, 48, 55, 59, 63, 67, 68, 70, 73, 83, 105, 111, 132, etc.; c.i. solvent black 3,5, 7, 23, 27, 28, 29, 34, etc.; and so on. These oil-soluble dyes may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In addition, it may be used in combination with a disperse dye or the like.

For example, when the colored dispersion liquid according to the present embodiment is made to have a black hue, the colored dispersion liquid according to the present embodiment may further contain a yellow dye, a blue dye, and an orange dye different from the c.i. disperse orange 25 (a) and the pigment (B).

The content of the other colorant is preferably 10% by mass or less, and more preferably 8% by mass or less, based on the total amount of the coloring dispersion liquid.

[ Water ]

The water is preferably water containing a small amount of impurities, such as ion-exchanged water, distilled water, and ultrapure water. In addition, water subjected to sterilization treatment may be used.

The content of water in the coloring dispersion liquid may be appropriately selected depending on the use. The content of water in the coloring dispersion liquid is usually 200 to 8500 parts by mass per 100 parts by mass of the total of (a) c.i. dispersed orange 25 and (B) a coloring matter.

[ dispersing agent ]

The colorant dispersion liquid according to the present embodiment preferably further contains a dispersant. The dispersant preferably contains at least 1 kind selected from the group consisting of a styrene- (meth) acrylic acid-based copolymer, a formaldehyde condensate of an aromatic sulfonic acid or a salt thereof, a polyoxyethylene aryl phenyl ether sulfate, and a polyoxyethylene naphthyl ether.

The styrene- (meth) acrylic copolymer is a copolymer of a styrene monomer and a (meth) acrylic monomer. Specific examples of the copolymer include an (α -methyl) styrene-acrylic acid copolymer, an (α -methyl) styrene-acrylic acid-acrylate copolymer, an (α -methyl) styrene-methacrylic acid-acrylate copolymer, an (α -methyl) styrene-acrylate- (anhydrous) maleic acid copolymer, an acrylate-styrene sulfonic acid copolymer, and an (α -methyl) styrene-methacryloyl sulfonic acid copolymer. In the present specification, "(meth) acrylic acid" is used in a meaning including "acrylic acid" and "methacrylic acid". In addition, "(α -methyl) styrene" is used in a meaning including "α -methylstyrene" and "styrene".

The mass average molecular weight of the styrene- (meth) acrylic acid copolymer is, for example, preferably 1000 to 20000, more preferably 2000 to 19000, and still more preferably 5000 to 17000. The mass average molecular weight of the styrene- (meth) acrylic acid-based copolymer can be measured by a GPC (gel permeation chromatography) method.

The acid value of the styrene- (meth) acrylic copolymer is, for example, preferably 50 to 250mgKOH/g, more preferably 100 to 250mgKOH/g, and still more preferably 150 to 250 mgKOH/g. When the acid value is 50mgKOH/g or more, the solubility in water is improved and the dispersion stabilizing ability tends to be improved. Further, when the acid value is 250mgKOH/g or less, the following tendency is exhibited: since the affinity with an aqueous medium is increased, the occurrence of bleeding in an image after printing can be suppressed. The acid value of the resin is expressed as mg of KOH required for neutralizing 1g of the resin, and can be measured in accordance with JIS-K3054.

The glass transition temperature of the styrene- (meth) acrylic copolymer is, for example, preferably 45 to 135 ℃, more preferably 55 to 120 ℃, and still more preferably 60 to 110 ℃.

Examples of commercially available products of styrene- (meth) acrylic copolymers include Joncryl 67, 678, 680, 682, 683, 690, 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6639, and PDX-6102B, PDX-6124 (manufactured by BASF Co., Ltd.). Of these, Joncryl 67 (mass average molecular weight: 12500, acid value: 213mgKOH/g), 678 (mass average molecular weight: 8500, acid value: 215mgKOH/g), 682 (mass average molecular weight: 1700, acid value: 230mgKOH/g), 683 (mass average molecular weight: 4900, acid value: 215mgKOH/g), 690 (mass average molecular weight: 16500, acid value: 240mgKOH/g) are preferred, and Joncryl 678 is more preferred.

Examples of the formaldehyde condensate of an aromatic sulfonic acid or a salt thereof include various formaldehyde condensates of creosote sulfonic acid, cresolsulfonic acid, phenolsulfonic acid, β -naphthalenesulfonic acid, β -naphtholsulfonic acid, β -naphthalenesulfonic acid, benzenesulfonic acid, cresolsulfonic acid, 2-naphthol-6-sulfonic acid, ligninsulfonic acid, and the like, and salts thereof (sodium salt, potassium salt, lithium salt, and the like). Among these, preferred are formaldehyde condensates of creosote sulfonic acid, β -naphthalenesulfonic acid, lignin sulfonic acid, methylnaphthalenesulfonic acid, or salts thereof.

The formaldehyde condensate of an aromatic sulfonic acid or a salt thereof can also be obtained in the form of a commercially available product. For example, the formaldehyde condensate of β -naphthalenesulfonic acid or a salt thereof includes delmol N (manufactured by kao corporation). Examples of the formaldehyde condensate of creosol sulfonic acid or a salt thereof include Demol C (manufactured by Kao corporation) and LAVELIN W series (manufactured by first Industrial pharmaceutical Co., Ltd.). As the formaldehyde condensate of a specific aromatic sulfonic acid or a salt thereof, Demol SN-B (manufactured by Kao corporation) and the like can be mentioned. Examples of the formaldehyde condensate of methylnaphthalenesulfonic acid or a salt thereof include LAVELIN AN series (first industrial pharmaceutical company). Among these, the Demol N, LAVELIN AN series and the LAVELIN W series are preferable, the Demol N and the LAVELIN W series are more preferable, and the LAVELIN W series is further preferable. Examples of the lignosulfonic acid include vanilex N, vanilex RN, vanilex G, and PEARLLEX DP (manufactured by japan paper company). Among these, VANILLEX RN, VANILLEX N, and VANILLEX G are preferable.

Examples of the polyoxyethylene arylphenyl ether include styrylphenol compounds such as polyoxyethylene styrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, and polyoxyethylene tetraphenylphenyl ether; benzyl phenol compounds such as polyoxyethylene benzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, and polyoxyethylene tribenzyl phenyl ether; cumylphenol compounds such as polyoxyethylene cumylphenyl ether; polyoxyethylene naphthyl phenyl ether, polyoxyethylene biphenyl ether, polyoxyethylene phenoxyphenyl ether; and so on.

The number of repetition of the polyoxyethylene group in the polyoxyethylene arylphenyl ether is preferably 1 to 30, more preferably 15 to 30. When the number of repetitions is 1 or more, the compatibility with an aqueous solvent or the like tends to be excellent. When the number of repetitions is 30 or less, the viscosity tends not to be too high.

Among polyoxyethylene arylphenyl ethers, polyoxyethylene styrylphenyl ether is preferred. Examples of commercially available products of polyoxyethylene styrylphenyl ether include PIONIN D-6112, PIONIN D-6115, PIONIN D-6120, PIONIN D-6131, PIONIN D-6512, TAKESURF D-6413, DTD-51, PIONIN D-6112, and PIONIN D-6320 (manufactured by Zhuben oil & fat Co., Ltd.); TS-1500, TS-2000, TS-2600, SM-174N (manufactured by Toho chemical Co., Ltd.); EMULGEN A-60, EMULGEN A-90, EMULGEN A-500 (manufactured by Kao corporation); and so on.

Examples of the polyoxyethylene arylphenyl ether sulfate include the above-mentioned polyoxyethylene arylphenyl ether sulfate.

Among polyoxyethylene arylphenyl ether sulfates, polyoxyethylene styrylphenyl ether sulfates are preferred. Commercially available products of polyoxyethylene styrylphenyl ether sulfate include, for example, SM-57 and SM-210 (manufactured by Toho chemical Co., Ltd.).

Commercially available products of polyoxyethylene naphthyl ether include Noigen EN series (first Industrial pharmaceutical Co., Ltd.), PIONIN D-7240 (manufactured by Takara Shuzo Co., Ltd.), and the like.

The coloring dispersion liquid according to the present embodiment may contain a conventionally known nonionic dispersant in addition to the above. Examples of the nonionic dispersant include an alkylene oxide adduct of phytosterol, an alkylene oxide adduct of cholesterol, a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene fatty acid ester, a sorbitan fatty acid ester, a polyoxyethylene alkylamine, a glycerin fatty acid ester, an oxyethylene oxypropylene block polymer, and substituted derivatives thereof. Among these, alkylene oxide adducts of phytosterols (also referred to as phytosterol compounds) and alkylene oxide adducts of cholestanols (also referred to as cholestanol compounds) are preferred, and phytosterol compounds are more preferred.

The alkylene oxide adduct of phytosterol is preferably C2-C4 alkylene oxide adduct of phytosterol, and more preferably ethylene oxide adduct. In the present specification, "phytosterols" are used in a meaning including both "phytosterols" and "hydrogenated phytosterols". Examples of the ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterols and ethylene oxide adducts of hydrogenated phytosterols.

The alkylene oxide adduct of a cholesterol alcohol is preferably a C2-C4 alkylene oxide adduct of a cholesterol alcohol, and more preferably an ethylene oxide adduct. In the present specification, "cholestanol" is used in a meaning including both "cholestanol" and "hydrogenated cholestanol". Examples of the ethylene oxide adduct of a cholestanol include an ethylene oxide adduct of cholestanol and an ethylene oxide adduct of hydrogenated cholestanol.

The addition amount of the alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) per 1 mole of phytosterol or cholestanol is preferably about 10-50 moles, and HLB is preferably about 13-20.

Examples of commercially available products of alkylene oxide adducts of phytosterols include NIKKOL BPS-20, NIKKOL BPS-30 (both manufactured by Nikko Chemicals, Ltd., ethylene oxide adducts of phytosterols), NIKKOL BPSH-25 (the same as above, ethylene oxide adducts of hydrogenated phytosterols), and the like. Examples of commercially available products of alkylene oxide adducts of cholestanols include NIKKOL DHC-30 (an ethylene oxide adduct of cholestanol, manufactured by Nikko Chemicals Co., Ltd.).

The above-mentioned dispersant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The content of the dispersant is preferably 1 to 300% by mass, more preferably 5 to 120% by mass, based on the total amount of the (a) c.i. dispersed orange 25 and the (B) pigment.

[ additives ]

The coloring dispersion liquid according to the present embodiment may contain additives other than those described above. Examples of the additives include water-soluble organic solvents, preservatives, surfactants, pH adjusters, chelating agents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity adjusters, pigment dissolving agents, antioxidants, and resin emulsions. Among these, the coloring dispersion liquid according to the present embodiment preferably contains at least 1 selected from the group consisting of a water-soluble organic solvent, a preservative, a surfactant, and a pH adjuster.

The content of the water-soluble organic solvent is preferably 0 to 90% by mass, and more preferably 0.01 to 85% by mass, based on the total amount of the coloring dispersion liquid. The total content of the other additives is preferably 0 to 50% by mass, and more preferably 0.01 to 10% by mass, based on the total amount of the coloring dispersion liquid.

Examples of the water-soluble organic solvent include glycol solvents, polyhydric alcohols, and pyrrolidones. Examples of the glycol-based solvent include glycerin, polyglycerin (#310, #750, #800), diglycerin, triglycerin, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, nonaglycerol, decaglycerol, undecalaglycerol, dodecaglycerol, tridecylglycerol, tetradecaglycerin, and the like. Examples of the polyhydric alcohol include C2-C6 polyhydric alcohols having 2 to 3 alcoholic hydroxyl groups; a di-or tri-C2-C3 alkylene glycol; a poly-C2-C3 alkylene glycol having 4 or more repeating units and a molecular weight of about 20000 or less, preferably a liquid polyalkylene glycol or the like. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1, 3-propanediol, 1, 2-butanediol, thiodiglycol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 3-methyl-1, 3-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 3-methyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, glycerin, trimethylolpropane, 1, 3-pentanediol, 1, 5-pentanediol and the like. Examples of the pyrrolidones include 2-pyrrolidone and N-methyl-2-pyrrolidone. For convenience, a compound that is dissolved in water and functions as a wetting agent is also included in the water-soluble organic solvent. Examples of such compounds include urea, ethylene urea, and saccharides.

In view of the storage stability of the colored dispersion liquid according to the present embodiment, the water-soluble organic solvent is preferably a solvent having low solubility of the colorant, and particularly preferably glycerin and a solvent other than glycerin (preferably a polyol other than glycerin) are used in combination.

Examples of the preservative include compounds of organic sulfur, organic nitrogen sulfur, organic halogen, halogenated allyl sulfone, iodopropargyl, N-halogenated alkyl sulfide, nitrile, pyridine, 8-hydroxyquinoline, benzothiadiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, indanone bromide, benzyl bromoacetate, inorganic salt, and the like. Specific examples of the organic halogen-based compound include sodium pentachlorophenate. Specific examples of the pyridine oxide compound include 2-pyridinethiol-1-oxide sodium salt and the like. Specific examples of the isothiazolin-based compound include 1, 2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, and 2-methyl-4-isothiazolin-3-one calcium chloride. Specific examples of the other antiseptic and antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, and PROXEL GXL (S) and PROXEL XL-2(S) which are trade names manufactured by LONZA.

Examples of the surfactant include known surfactants such as anionic, cationic, amphoteric, nonionic, silicone, and fluorine surfactants.

Examples of the anionic surfactant include alkylsulfonates, alkylcarboxylates, α -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and salts thereof, N-acylmethyltaurates, alkylsulfate polyoxyalkyl ether sulfates, alkylsulfate polyoxyethylene alkyl ether phosphates, rosin soaps, castor oil sulfates, lauryl alcohol sulfates, alkylphenol phosphates, alkyl phosphates, alkylaryl sulfonates, diethyl sulfosuccinates, diethyl hexyl sulfosuccinates, and dioctyl sulfosuccinates. Examples of commercially available products include HITENOL LA-10, LA-12, LA-16, NEOHITENOL ECL-30S, ECL-45, all of which are manufactured by first Industrial pharmaceutical Co.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

Examples of the amphoteric surfactant include lauryl dimethyl glycine betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amide propyl dimethyl glycine betaine, poly octyl poly aminoethyl glycine, imidazoline derivatives, and the like.

Examples of the nonionic surfactant include ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; esters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, and polyoxyethylene stearate; acetylene glycol (alcohol) systems such as 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, and 3, 5-dimethyl-1-hexyne-3-ol; SURFYNOL104, 105, 82, 465, OLFINE STG, and the like, manufactured by Air Products Japan, inc; polyglycol ether systems (e.g., Tergitol 15-S-7 manufactured by SIGMA-ALDRICH Co., Ltd.); and so on.

Examples of the silicone surfactant include polyether-modified silicone and polyether-modified polydimethylsiloxane. Examples of commercially available products include BYK-347 (polyether-modified siloxane) manufactured by BYK-Chemie; BYK-345, BYK-348 (polyether modified polydimethylsiloxane), and the like.

Examples of the fluorine-based surfactant include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain, and the like. Examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30 and FS-31 (manufactured by DuPont Co., Ltd.); PF-151N, PF-154N (manufactured by Omnova, Inc.); and so on.

As the pH adjuster, any substance may be used as long as the pH of the coloring dispersion can be controlled within a range of about 5 to 11 without adversely affecting the prepared coloring dispersion. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide (ammonia); carbonates of alkali metals such as lithium carbonate, sodium hydrogen carbonate, and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate; and the like, preferably triethanolamine.

Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.

Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite (diisopropyjjjjjjjjm ammonium nitrate), pentaerythritol tetranitrate, dicyclohexylammonium nitrite (dicyclohexylammonium nitrate), and the like.

Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine, and polyimine.

The viscosity modifier may include a water-soluble polymer compound other than the water-soluble organic solvent, and examples thereof include polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

Examples of the dye dissolver include urea, epsilon-caprolactam, and ethylene carbonate.

As the antioxidant, various organic and metal complex-based fading inhibitors can be used. Examples of the organic discoloration inhibitor include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the discoloration inhibitor of the metal complex include nickel complexes and zinc complexes.

Examples of the resin emulsion include emulsions formed of acrylic resins, epoxy resins, urethane resins, polyether resins, polyamide resins, unsaturated polyester resins, phenol resins, silicone resins, fluorine resins, polyethylene resins (vinyl chloride, vinyl acetate, polyvinyl alcohol, and the like), alkyd resins, polyester resins, amino materials (melanin resins, urea resins, melanin-formaldehyde resins, and the like), and the like. The resin emulsion may contain 2 or more resins. In addition, 2 or more resins may form a core/shell structure. Among the resin emulsions, a urethane resin emulsion is preferable.

The urethane resin emulsion is available as a commercial product, and is usually an emulsion having a solid content concentration of 30 to 60 mass%. Commercially available urethane resin emulsions include PERMARIN UA-150, PERMARIN 200, PERKOTO UX-320 (manufactured by Sanyo chemical Co., Ltd.); HYDRAN WLS-201 and 210 and HW-312B (available from DIC Co., Ltd.); SUPER FLEX 150, 170, 470 (manufactured by first Industrial pharmaceutical Co., Ltd.); and so on. Among these, examples of the polycarbonate-based urethane resin include PERMARIN UA-310, 3945; YUKOTO UX-320; and so on. Further, examples of the polyether urethane resin include PERMARIN UA-150, 200; YUKOTO UX-340; and so on.

The SP value of the urethane resin in the urethane resin emulsion is preferably 8 to 24 (cal/cm)³)^1/2More preferably 8 to 17 (cal/cm)³)^1/2More preferably 8 to 11 (cal/cm)³)^1/2. The SP value of the urethane resin can be calculated by the Fedors method. When the urethane resin has an acidic group and the acidic group is neutralized to prepare an emulsion, the SP value of the urethane resin before neutralization is used.

When the urethane resin in the urethane resin emulsion has an acidic group such as a carboxyl group, a sulfo group, or a hydroxyl group, the acidic group may be alkali-alkylated. For example, the acidic group can be alkali-salted by adding a basic compound to an aqueous solution prepared by adding a urethane resin having an acidic group to water and stirring the mixture, and adjusting the pH to 6.0 to 12.0. Examples of the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide; and so on. The basic compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

[ preparation method of coloring Dispersion liquid, etc. ]

Examples of the method for producing the coloring dispersion liquid according to the present embodiment include the following methods: an aqueous dispersion containing (a) c.i. dispersed orange 25, (B) a coloring matter, and a dispersing agent is prepared, and if necessary, an additive such as a water-soluble organic solvent is further added.

Examples of the method for preparing the aqueous dispersion include known methods such as stirring and mixing the components constituting the aqueous dispersion using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a high-pressure emulsifier, and the like. For example, when a sand mill is used, first, the respective components and beads as a dispersion medium are charged into the sand mill. As the beads, glass beads having a particle diameter of 0.01 to 1mm, zirconia beads, or the like can be used. The amount of the beads used is preferably 2 to 6 parts by mass per 1 part by mass of the object to be dispersed. Subsequently, the sand mill was operated to perform dispersion treatment. The dispersion treatment is preferably carried out at 1000 to 2000rpm for 1 to 20 hours. Then, after the dispersion treatment, the beads are removed by filtration or the like, whereby an aqueous dispersion can be obtained.

The prepared colored dispersion can be subjected to microfiltration using a membrane filter or the like. In particular, when the colored dispersion is used as an ink for ink jet textile printing, fine filtration is preferably performed for the purpose of preventing clogging of nozzles and the like. The pore size of the filter used for the microfiltration is usually 0.1 to 1 μm, preferably 0.1 to 0.8. mu.m.

The viscosity of the colored dispersion liquid according to the present embodiment at 25 ℃ is preferably about 3 to 20mPa · s when measured by an E-viscometer, from the viewpoint of ejection response at high speed. The surface tension of the colored dispersion liquid according to the present embodiment at 25 ℃ is preferably about 20 to 45mN/m as measured by a plate method. In practice, the ejection amount, response speed, ink droplet flight characteristics, and the like of the inkjet printer to be used can be adjusted to appropriate physical property values in consideration of the ejection amount, response speed, ink droplet flight characteristics, and the like.

The coloring dispersion liquid according to the present embodiment can be used in various fields, and is suitable for water-based inks for writing, water-based printing inks, information recording inks, textile printing, and the like. The coloring dispersion liquid according to the present embodiment is particularly preferably used as an ink for ink jet textile printing.

According to the colored dispersion liquid of the present embodiment, it is possible to effectively prevent the particles in the colored dispersion liquid from aggregating during storage and increasing the average particle diameter, and to effectively prevent the particles from settling during storage. That is, according to the coloring dispersion liquid of the present embodiment, the dispersion state of the particles in the coloring dispersion liquid can be stably maintained.

The colored dispersion liquid according to the present embodiment has good initial filling properties into a head of an ink jet printer, and also has good continuous printing stability. Further, bleeding of the image on the printed paper does not occur, and a clear image can be obtained.

< recording Medium >

The recording medium according to the present embodiment is a recording medium to which the coloring dispersion liquid according to the present embodiment described above is attached. The recording medium is not particularly limited as long as recording can be performed using the coloring dispersion liquid according to the present embodiment, and examples thereof include fibers, paper (plain paper, inkjet paper, and the like), and the like. In particular, the recording medium according to the present embodiment is preferably a hydrophobic fiber to which the coloring dispersion liquid according to the present embodiment is attached.

Examples of the hydrophobic fibers include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended fibers using 2 or more of these fibers. In the present specification, the hydrophobic fibers include blend fibers of these hydrophobic fibers with regenerated fibers such as rayon and natural fibers such as cotton, silk and wool. Fibers having an ink-receiving layer (barrier layer) among these fibers are also known, and such fibers are also included in hydrophobic fibers. The method of forming the ink-receiving layer is known, and the fiber having the ink-receiving layer can also be obtained in the form of a commercially available product. The material, structure, and the like of the ink receiving layer are not particularly limited, and may be appropriately used according to the purpose and the like.

< printing and dyeing method of hydrophobic fiber >

The method of printing hydrophobic fibers according to the present embodiment is a method of printing hydrophobic fibers using the colored dispersion liquid according to the present embodiment. Methods for printing hydrophobic fibers can be broadly classified into direct printing methods and sublimation transfer methods.

The direct printing method includes: a printing step of attaching droplets of the coloring dispersion to hydrophobic fibers by an ink jet printer to obtain recorded images such as characters and patterns; a fixing step of fixing the dye in the coloring dispersion liquid attached to the hydrophobic fiber in the printing step to the hydrophobic fiber by heat; and a washing step of washing the unfixed dye remaining in the hydrophobic fiber.

The fixing process is generally carried out using known steaming or baking. As the steaming, for example, the following methods can be cited: the dye is dyed (also referred to as wet heat fixing) to the hydrophobic fiber by treating the hydrophobic fiber with a high-temperature steam generator at a temperature of about 170 to 180 ℃ for about 10 minutes, or with a high-pressure steam generator at a temperature of about 120 to 130 ℃ for about 20 minutes, respectively. Examples of baking (hot melt) include the following methods: the hydrophobic fiber is treated at 190 to 210 ℃ for about 6 to 120 seconds, whereby the dye is dyed (also referred to as dry heat fixing) to the hydrophobic fiber.

The washing step is a step of washing the obtained fibers with warm water and, if necessary, water. The warm water, water used for cleaning may contain a surfactant. The washed hydrophobic fibers are preferably dried at 50 to 120 ℃ for 5 to 30 minutes.

In another aspect, a sublimation transfer method includes: a printing step of obtaining a recorded image such as characters and patterns by adhering droplets of the coloring dispersion to an intermediate recording medium by an ink jet printer; and a transfer step of bringing the hydrophobic fibers into contact with the surface of the intermediate recording medium to which the coloring dispersion adheres, and performing a heat treatment to thereby transfer the recording image to the hydrophobic fibers.

The intermediate recording medium is preferably one in which the dye in the attached colored dispersion liquid does not aggregate on the surface thereof and which does not inhibit sublimation of the dye when transferring a recorded image to the hydrophobic fiber. As an example of such an intermediate recording medium, there is a paper having an ink receiving layer formed on the surface thereof by using inorganic fine particles such as silica, and a special paper for ink jet can be used.

The heat treatment in the transfer step may be a dry heat treatment usually performed at about 190 to 200 ℃.

The method for printing hydrophobic fibers according to the present embodiment may further include a pretreatment step of the hydrophobic fibers for the purpose of preventing bleeding and the like. Examples of the pretreatment step include the following steps: an aqueous solution (pretreatment liquid) containing a paste, an alkaline substance, an anti-reducing agent, and a cosolvent is applied to the hydrophobic fibers before the colored dispersion is attached.

Examples of the paste include natural gums such as guar gum and locust bean gum; starches; seaweeds such as sodium alginate and gloiopeltis; plant skins such as pectic acid; cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose; modified starches such as carboxymethyl starch; synthetic pastes such as polyvinyl alcohol and polyacrylate; etc., preferably sodium alginate.

Examples of the basic substance include alkali metal salts of inorganic acids or organic acids; salts of alkaline earth metals; a compound which liberates a base upon heating; and the like, preferably alkali metal hydroxides and alkali metal salts. Specific examples thereof include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide; alkali metal salts of inorganic compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium phosphate; alkali metal salts of organic compounds such as sodium formate and sodium trichloroacetate; and the like, preferably sodium bicarbonate.

The anti-reducing agent is preferably sodium m-nitrobenzenesulfonate.

The cosolvent includes ureas such as urea and dimethylurea, and urea is preferable.

The paste, the alkaline substance, the anti-reducing agent and the cosolvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The mixing ratio of the components in the pretreatment liquid is, for example, 0.5 to 5% by mass of the paste, 0.5 to 5% by mass of the sodium bicarbonate, 0 to 5% by mass of the sodium m-nitrobenzenesulfonate, 1 to 20% by mass of the urea, and the balance of water.

Examples of the method for adhering the pretreatment liquid to the hydrophobic fibers include a padding method. The preferable pad-out rate of pad dyeing is about 40-90%, and more preferably about 60-80%.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the examples, "part" means part by mass and "%" means% by mass, respectively, unless otherwise specified. The aqueous dispersions and inks using the same in the examples are included in the coloring dispersion.

< preparation example 1: preparation of emulsion 1

Joncryl 678 (manufactured by BASF) (20 parts) was put into a mixture of 25% sodium hydroxide (6 parts), ion-exchanged water (54 parts), and propylene glycol (20 parts), and the mixture was stirred for 5 hours while the temperature was raised to 90 to 120 ℃ to obtain emulsion 1 of Joncryl 678.

< preparation example 2: preparation of Y54 Dispersion

Glass beads having a diameter of 0.2mm were added to a mixture of Kayaset Yellow AG (manufactured by Japan chemical corporation, c.i. disperse Yellow 54) (30 parts), LAVELIN W-40 (an aqueous solution of a creosote sodium sulfonate formaldehyde condensate, manufactured by first industrial pharmaceutical co., ltd.) (22.5 parts), PROXEL GXL (manufactured by LONZA) (0.2 part), SURFYNOL104 PG50 (a product obtained by diluting SURFYNOL104 (an acetylene glycol surfactant, manufactured by Air Products Japan, inc.) with propylene glycol to a concentration of 50% (0.4 part), and ion-exchanged water (46.9 parts), which are sublimation dyes, and dispersion treatment was performed by a sand mill under cooling conditions for about 15 hours. To the obtained liquid, ion-exchanged water (77.5 parts) and LAVELIN W-40(22.5 parts) were added to adjust the dye content to 15%, and then the mixture was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC, Inc., filter pore size: 0.5 μm) to obtain a Y54 dispersion.

< preparation example 3: preparation of B360 Dispersion

Glass beads having a diameter of 0.2mm were added to a mixture of c.i. disperse blue 360(30 parts), LAVELIN W-40(22.5 parts), PROXEL GXL (0.2 parts), SURFYNOL104 PG50(0.4 parts) and ion-exchanged water (46.9 parts) as sublimation dyes, and the mixture was dispersed with a sand mill for about 15 hours under cooling conditions. To the obtained liquid, ion-exchanged water (47.5 parts) and LAVELIN W-40(52.5 parts) were added to adjust the dye content to 15%, and then the mixture was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC, Inc., filter pore size: 0.5 μm) to obtain a B360 dispersion.

< preparation example 4: preparation of Or60 Dispersion

Glass beads having a diameter of 0.2mm were added to a mixture of c.i. solvent orange 60(30 parts), LAVELIN W-40(22.5 parts), PROXEL GXL (0.2 parts), SURFYNOL104 PG50(0.4 parts) and ion-exchanged water (46.9 parts) as sublimation dyes, and dispersion treatment was performed for about 15 hours under cooling conditions using a sand mill. Ion-exchanged water (47.5 parts) and LAVELIN W-40(52.5 parts) were added to the obtained solution to adjust the dye content to 15%, and then the mixture was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm) to obtain an Or60 dispersion.

< examples 1 to 8: preparation of aqueous Dispersion 1 to 8

Glass beads having a diameter of 0.2mm were added to the mixture of the components described in tables 1 to 2, and the mixture was dispersed with a sand mill under water cooling for about 15 hours. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm) to prepare aqueous dispersions 1 to 8, respectively. In tables 1 to 2, the numerical values of the respective components indicate the number of added parts.

< comparative examples 1 to 2: preparation of aqueous Dispersion 9 to 10

Glass beads having a diameter of 0.2mm were added to the mixture of the components shown in Table 2 below, and the mixture was dispersed with a sand mill under water cooling for about 15 hours. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm) to prepare aqueous dispersions 9 to 10, respectively.

[ Table 1]

[ Table 2]

Abbreviations and the like in tables 1 to 2 represent the following.

LAVELIN W-40: aqueous solution of sodium creosote sulfonate Formaldehyde polycondensate (first Industrial pharmaceutical Co., Ltd.)

BPS-30: NIKKOL BPS-30 (ethylene oxide adduct of phytosterol, manufactured by Nikko Chemicals Co., Ltd.)

PROXEL GXL: antiseptic and mildew-proof agent (manufactured by LONZA corporation)

SURFYNOL104 PG 50: SURFYNOL104 (acetylenic diol surfactant, manufactured by Air Products Japan, Inc.) was diluted to 50% concentration with propylene glycol.

< examples 9 to 16: preparation of aqueous orange ink 1-8

Aqueous orange inks 1 to 8 were prepared by mixing the aqueous dispersions 1 to 8 obtained in examples 1 to 8 with the components described in tables 3 to 4, stirring for 30 minutes, and then filtering the mixture with a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter having a pore size of 0.5 μm). In tables 3 to 4, the numerical values of the respective components represent the number of added parts.

< comparative examples 3 to 4: preparation of aqueous orange ink 9-10

Aqueous orange inks 9 to 10 were prepared by mixing the aqueous dispersions 9 to 10 obtained in comparative examples 1 to 2 with the components shown in Table 4, stirring for 30 minutes, and then filtering the mixture with a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter having a pore size of 0.5 μm).

[ Table 3]

[ Table 4]

Abbreviations and the like in tables 3 to 4 represent the following.

BYK-348: polyether modified polydimethylsiloxane (BYK-Chemie Co., Ltd.)

TEA-80: triethanolamine (Oxalis Chemicals Ltd.; product.)

PROXEL GXL: antiseptic and mildew-proof agent (manufactured by LONZA corporation)

< evaluation >

The following evaluation tests were carried out using the aqueous orange inks 1 to 10 prepared as described above. The results are shown in tables 5 to 6 below.

[ particle diameter Change test ]

The median particle diameter (D50, number average particle diameter) of the colorant in each aqueous orange ink stored at 60 ℃ for 5 days was measured using MICRO TRAC UPA EX150 (manufactured by Microtrac BEL), and evaluated according to the following criteria. A. B or C was evaluated well, and D was evaluated badly.

Evaluation criteria-

A: d50 below 140nm

B: d50 is 140nm or more and less than 160nm

C: d50 is 160nm or more and less than 170nm

D: d50 is 170nm or more

[ Settlement test ]

Absorbance Abs at the maximum absorption wavelength (. lamda.max) around 420nm measured at the time of preparing the ink was used₀And an absorbance Abs at a maximum absorption wavelength (. lamda.max) of about 420nm measured by dividing the supernatant of the ink stored at 60 ℃ for 5 days₁The sedimentation rate was calculated according to the following equation. The absorbance was measured for a diluted solution obtained by adding water to the ink and diluting the solution to 2000 times.

Sedimentation rate (%) { (Abs)₀-Abs₁)/Abs₀}×100

Then, the calculated sedimentation rate was evaluated according to the following criteria. A or B was evaluated well, and C was evaluated badly.

Evaluation criteria-

A: the sedimentation rate is lower than 20 percent

B: the sedimentation rate is more than 20 percent and less than 40 percent

C: the sedimentation rate is more than 40 percent

[ Table 5]

[ Table 6]

From the results in tables 5 to 6, it was confirmed that the aqueous orange inks of examples 9 to 16 prepared using the aqueous dispersions of examples 1 to 8 had a small number of coarse particles, good settling properties, and excellent storage stability because the particle size did not increase significantly during storage at high temperatures. On the other hand, the aqueous orange inks of comparative examples 3 to 4 prepared using the aqueous dispersions of comparative examples 1 to 2 had inferior storage stability to the aqueous orange inks of examples 9 to 16.

< examples 17 to 20: preparation of aqueous Dispersion 11 to 14

Glass beads having a diameter of 0.2mm were added to the mixture of the components shown in Table 7 below, and the mixture was dispersed with a sand mill under water cooling for about 15 hours. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size: 0.5 μm), to prepare aqueous dispersions 11 to 14, respectively. In table 7, the numerical values of the respective components indicate the number of added parts.

[ Table 7]

Abbreviations and the like in Table 7 represent the following, respectively.

PIONIN D-6320: polyoxyethylene styryl phenyl ether dispersant (manufactured by bamboo fat Co., Ltd.)

SM-57: polyoxyethylene styryl phenyl ether sulfate-based dispersant (manufactured by Toho chemical industry Co., Ltd.)

SM-210: polyoxyethylene styryl phenyl ether sulfate-based dispersant (manufactured by Toho chemical industry Co., Ltd.)

< examples 21 to 24: preparation of aqueous orange ink 11-14

Aqueous orange inks 11 to 14 were prepared by mixing the aqueous dispersions 11 to 14 obtained in examples 17 to 20 with the components shown in Table 8, stirring for 30 minutes, and then filtering the mixture with a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter having a pore size of 0.5 μm). In table 8, the numerical values of the respective components indicate the number of added parts.

[ Table 8]

< evaluation >

The particle diameter change test, the settling property test, and the following redispersibility evaluation test were performed using the aqueous orange inks 11 to 14 prepared as described above. The results are shown in table 9 below.

[ redispersibility evaluation test ]

25 μ L of each aqueous orange ink was dropped onto a glass plate and dried for 1 hour using a constant temperature and humidity machine at 60 ℃. To the obtained dried product, 10mL of ion-exchanged water was added dropwise at room temperature, and whether or not the product was redispersed was visually observed, and the evaluation was made according to the following criteria. The more the ink is redispersed, the more easily the clogging after drying is eliminated, and therefore the ink is excellent. A. B or C was evaluated well, and D was evaluated badly.

Evaluation criteria-

A: no residue was present and all were redispersed.

B: the residue remained slightly, but was mostly redispersed.

C: the residue remained largely but was slightly redispersed.

D: no redispersion was carried out at all.

[ Table 9]

From the results in Table 9, it was confirmed that the aqueous orange inks of examples 21 to 24 prepared using the aqueous dispersions of examples 17 to 20 had no significant increase in particle size during high-temperature storage, and thus had few coarse particles, good settling properties, and excellent storage stability. The redispersibility of the aqueous orange inks of examples 21 to 24 (particularly, the aqueous orange inks of examples 22 to 24 containing a polyoxyethylene styrylphenyl ether sulfate-based dispersant) was also good.

< examples 25 to 28: preparation of aqueous Dispersion 15 to 18

Glass beads having a diameter of 0.2mm were added to the mixture of the components shown in Table 10 below, and the mixture was dispersed with a sand mill under water cooling for about 15 hours. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm) to prepare aqueous dispersions 15 to 18, respectively. In table 10, the numerical values of the respective components indicate the number of added parts.

[ Table 10]

< examples 29 to 32: preparation of aqueous orange ink 15-18

Aqueous orange inks 15 to 18 were prepared by mixing the aqueous dispersions 15 to 18 obtained in examples 25 to 28 with the respective components shown in Table 11, stirring for 30 minutes, and then filtering the mixture with a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter having a pore size of 0.5 μm). In table 11, the numerical values of the respective components indicate the number of added parts.

[ Table 11]

< evaluation >

The particle diameter change test, the settling property test, and the redispersibility evaluation test were performed using the aqueous orange inks 15 to 18 prepared as described above. The results are shown in table 12 below.

[ Table 12]

From the results in Table 12, it was confirmed that the aqueous orange inks of examples 29 to 32 prepared using the aqueous dispersions of examples 25 to 28 had no significant increase in particle size during high-temperature storage, and thus had few coarse particles, good settling properties, and excellent storage stability. In addition, the water orange inks of examples 29 to 32 also have excellent redispersibility.

< examples 33 to 42: preparation of aqueous Dispersion 19 to 28

Glass beads having a diameter of 0.2mm were added to the mixture of each component described in tables 13 to 14 below, and dispersion treatment was performed for about 15 hours by a sand mill under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm) to prepare aqueous dispersions 19 to 28, respectively. In tables 13 to 14, the numerical values of the respective components represent the number of added parts.

< comparative example 5: preparation of aqueous Dispersion 29

Glass beads having a diameter of 0.2mm were added to the mixture of the components shown in Table 14 below, and the mixture was dispersed with a sand mill under water cooling for about 15 hours. The resulting liquid was filtered through a glass fiber filter GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm) to prepare an aqueous dispersion 29.

[ Table 13]

[ Table 14]

< examples 43 to 52: preparation of aqueous orange ink 19-28

Aqueous orange inks 19 to 28 were prepared by mixing the aqueous dispersions 19 to 28 obtained in examples 33 to 42 with the components described in tables 15 to 16, stirring for 30 minutes, and then filtering the mixture with a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter having a pore size of 0.5 μm). In tables 15 to 16, the numerical values of the respective components represent the number of added parts.

< comparative example 6: preparation of Water-based orange ink 29

The aqueous dispersion 29 obtained in comparative example 5 was mixed with each component shown in Table 16 below, stirred for 30 minutes, and then filtered through a glass fiber filter GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm), to prepare an aqueous orange ink 29.

[ Table 15]

[ Table 16]

< evaluation >

The particle diameter change test and the settling property test were performed using the aqueous orange inks 19 to 24 prepared as described above. The particle diameter change test, the settling property test, and the redispersibility evaluation test were performed using 25 to 29 aqueous orange inks. The results are shown in tables 17 to 18 below.

[ Table 17]

[ Table 18]

From the results in tables 17 to 18, it was confirmed that the aqueous orange inks of examples 43 to 52 prepared using the aqueous dispersions of examples 33 to 42 had no significant increase in particle size during high-temperature storage, and thus had few coarse particles, good settling properties, and excellent storage stability. In addition, the water orange inks of examples 49-52 also have excellent redispersibility. On the other hand, the aqueous orange ink of comparative example 6 prepared using the aqueous dispersion of comparative example 5 had inferior storage stability to the aqueous orange inks of examples 43 to 52.

< examples 53 to 58: preparation of aqueous orange ink 30-35 >

Aqueous black inks 1 to 6 were prepared by mixing the aqueous dispersions 3, 19, 25 to 28 obtained in examples 3, 33, 39 to 42 with the components shown in Table 19 below, stirring for 30 minutes, and then filtering the mixture through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm). In table 19, the numerical values of the respective components indicate the number of added parts.

[ Table 19]

< evaluation >

The aqueous orange inks 30 to 35 prepared as described above were filled in an ink jet printer (PX-504A manufactured by EPSON corporation) and TRANSJET EcoRI II 8385 (gram weight: 95 g/m) was used²) As intermediate recording media, intermediate recording media on which monochrome stereoscopic images of 100% Duty are printed are obtained, respectively. The ink-deposited surface of each of the obtained intermediate recording media was laminated with polyester cloth (tiprich), and then heat-treated at 200 ℃ for 30 seconds using a desk top automatic flatbed press (Asahi Garment Machinery co., ltd., AF-65TEN), whereby dyed materials dyed by the sublimation transfer method were obtained. The dyed material can obtain the expected color.

The particle diameter change test and the settling property test were performed using the aqueous orange inks 30 to 35 prepared as described above. The results are shown in table 20 below.

[ Table 20]

From the results in Table 20, it was confirmed that the aqueous orange inks of examples 53 to 58 had no significant increase in particle size during storage at high temperature, and thus had few coarse particles, good settling property, and excellent storage stability.

< examples 59 to 64: preparation of aqueous black ink 1-6

Aqueous black inks 1 to 6 were prepared by mixing the aqueous dispersions 3, 19, 25 to 28 obtained in examples 3, 33, 39 to 42 with the respective components shown in Table 21, stirring for 30 minutes, and then filtering the mixture through a glass fiber filter paper GC-50 (manufactured by ADVANTEC corporation, pore size of filter: 0.5 μm). In table 21, the numerical values of the respective components indicate the number of added parts.

[ Table 21]

< evaluation >

The aqueous black inks 1 to 6 prepared as described above were filled in an ink jet printer (PX-504A manufactured by EPSON corporation) and TRANSJET EcoRI II 8385 (gram weight: 95 g/m) was used²) As intermediate recording media, intermediate recording media on which monochrome stereoscopic images of 100% Duty are printed are obtained, respectively. The ink-deposited surface of each of the obtained intermediate recording media was laminated with polyester cloth (tiprich), and then heat-treated at 200 ℃ for 30 seconds using a desk top automatic flatbed press (Asahi Garment Machinery co., ltd., AF-65TEN), whereby dyed materials dyed by the sublimation transfer method were obtained.

The dye concentration of each of the obtained dyed materials was measured by using a spectrophotometer eXact (X-rite Co., Ltd.). Color measurement is carried out under the conditions of D65 light source, 2-degree angle of view and I stateThe process is carried out. Reflectance R at wavelength of 400-700 nm for each dyed material_λColor measurement is carried out by utilizing a Kubelka-Munk formula: K/S ═ 1-R_λ)²/2R_λThe K/S value was calculated. Then, a sum Σ K/S value as a K/S value at each wavelength is calculated. As a result, the sigma K/S values were all 400 or more in the case of using any of the aqueous black inks, and good color developability was exhibited.

The particle diameter change test and the settling property test were performed using the aqueous black inks 1 to 6 prepared as described above. The results are shown in Table 22 below.

[ Table 22]

From the results in Table 22, it was confirmed that the aqueous black inks of examples 59 to 64 had no significant increase in particle size during storage at high temperature, and thus had few coarse particles, good settling property, and excellent storage stability.

The claims (modification according to treaty clause 19)

(after modification)

A coloring dispersion liquid containing (A) C.I. disperse orange 25, (B) at least 1 coloring matter selected from the coloring matters represented by the following formula (1) and the coloring matters represented by the following formula (2), and water,

the content of the (B) pigment is less than 10 parts by mass when the total content of the (a) c.i. dispersed orange 25 and the (B) pigment is 100 parts by mass.

[ chemical formula 1]

(in the formula (1), R¹And R²Each independently represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent, and n represents an integer of 1 to 7. )

[ chemical formula 2]

(in the formula (2), R³Represents a hydrogen atom or a C1-C7 alkyl group which may have a substituent, R⁴And R⁵Each independently represents a hydrogen atom or a halogen atom, and X represents an oxygen atom, -OCONH-, -OCO-, or-OCOCH₂-, m represents an integer of 1 to 7. )

(after modification)

The coloring dispersion liquid according to claim 1, wherein the content of the (B) pigment is 0.1 parts by mass or more and less than 10 parts by mass, based on 100 parts by mass of the total content of the (a) c.i. dispersed orange 25 and the (B) pigment.

3. The coloring dispersion liquid according to claim 1, wherein the content of the (B) pigment is 0.5 to 5 parts by mass, based on 100 parts by mass of the total content of the (A) C.I. dispersed orange 25 and the (B) pigment.

4. The coloring dispersion liquid according to any one of claims 1 to 3, wherein the pigment represented by formula (1) is C.I. disperse orange 73.

5. A coloring dispersion liquid according to any one of claims 1 to 4, which further contains a dispersant.

6. The colored dispersion liquid according to claim 5, wherein the dispersant contains at least 1 selected from the group consisting of a styrene- (meth) acrylic acid-based copolymer, a formaldehyde condensate of an aromatic sulfonic acid or a salt thereof, a polyoxyethylene aryl phenyl ether sulfate, and a polyoxyethylene naphthyl ether.

7. The coloring dispersion liquid according to claim 6, wherein the formaldehyde condensate of an aromatic sulfonic acid or a salt thereof comprises a sodium naphthalenesulfonate formaldehyde condensate or a salt thereof.

8. The coloring dispersion liquid according to claim 6 or 7, wherein the formaldehyde condensate of an aromatic sulfonic acid or a salt thereof comprises a formaldehyde condensate of a creosote sulfonic acid or a salt thereof.

9. The coloring dispersion liquid according to any one of claims 6 to 8, wherein the polyoxyethylene aryl phenyl ether is polyoxyethylene styrene phenyl ether, and the polyoxyethylene aryl phenyl ether sulfate is polyoxyethylene styrene phenyl ether sulfate.

10. A pigmented dispersion according to any one of claims 6 to 9 wherein said dispersant further comprises a phytosterol compound.

11. The coloring dispersion liquid according to any one of claims 1 to 10, further comprising a yellow dye, a blue dye, and an orange dye different from the (a) c.i. disperse orange 25 and the (B) pigment.

12. A recording medium having the coloring dispersion liquid according to any one of claims 1 to 11 attached thereto.

13. The recording medium of claim 12, wherein the recording medium is a hydrophobic fiber.

14. A method of printing hydrophobic fibers comprising:

a printing step of attaching droplets of the coloring dispersion liquid according to any one of claims 1 to 11 to an intermediate recording medium to obtain a recorded image; and

and a transfer step of bringing a hydrophobic fiber into contact with the surface of the intermediate recording medium to which the coloring dispersion liquid adheres, and performing a heat treatment to thereby transfer the recording image to the hydrophobic fiber.

Statement or declaration (modification according to treaty clause 19)

The content of the (B) pigment in the claim 1 was modified from "less than 20 parts by mass" to "less than 10 parts by mass" with the total content of the (a) c.i. dispersed orange 25 and the (B) pigment being 100 parts by mass. This modification is made based on paragraph 0026 of the specification at the time of filing.

The pigment (B) content of claim 2 is modified from "0.1 to 15 parts by mass" to "0.1 part by mass or more and less than 10 parts by mass" when the total content of (A) C.I. dispersed orange 25 and (B) pigment is 100 parts by mass. This modification is made based on paragraph 0026 of the specification at the time of filing.