WO2013128725A1

WO2013128725A1 - Ink-jet-printing method, ink-jet-printing ink composition, and cloth

Info

Publication number: WO2013128725A1
Application number: PCT/JP2012/079560
Authority: WO
Inventors: 義顕近藤; 厚浩勝亦; 矢吹　嘉治
Original assignee: 富士フイルム株式会社
Priority date: 2012-02-29
Filing date: 2012-11-14
Publication date: 2013-09-06
Also published as: JP2013209786A

Abstract

An ink-jet-printing method has a printing step for applying, to a cloth including polyamide fibres, an ink-jet-printing ink composition including a compound which has a weight average molecular weight in the range of 800-2000, and which is represented by general formula (1) (in general formula (1): R¹ represents hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group; and R²-R⁴ each independently represent hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a sulfonyl group, an acyl group, a carboxyl group, a sulfo group, or a carbamoyl group, with the caveat that R² and R³ are not hydrogen at the same time).

Description

Inkjet printing method, ink composition for inkjet printing, and fabric

The present invention relates to an ink jet textile printing method, an ink composition for ink jet textile printing, and a fabric.

The inkjet printing method is an image printing method in which fine droplets of ink are ejected from an inkjet recording head and adhered to a target recording medium. The ink jet method is advantageous in that its mechanism is relatively simple, inexpensive, and can form a high-definition and high-quality image.

On the other hand, the current fabric printing is performed by screen printing or the like. For these, it is necessary to prepare a printing copper plate or a screen plate prior to printing. Plate production takes time and manpower, is very expensive, and if it does not produce more than a certain amount, it will not be cost effective, so a plateless printing system for small-scale production or sample making purposes. Is desired.

On the other hand, ink jet printing using the above-described ink jet method capable of directly supplying a dye to a cloth has been proposed. Unlike conventional textile printing, inkjet textile printing has the advantage that it is not necessary to prepare a plate and can quickly form an image with excellent gradation. It has merits such as no. Further, since only a necessary amount of ink is used as a formed image, it can be said that this is an excellent image forming method having environmental advantages such as less waste liquid compared to the conventional method.

In textile printing, the type of dye used is limited depending on the type of fiber in the fabric, and in the case of forming an image on a fabric mainly composed of polyamide fibers such as silk, wool and nylon, a method using an acid dye is proposed. Has been.
In general, the following properties are required for ink for inkjet textile printing.
(1) The color is developed at a sufficient density. (2) The color reproducibility is excellent. (3) The formed image is blurred, and the non-image area and other fabrics are stained during the post-processing process and washing. (4) Do not clog the nozzles of the recording head (5) No change in physical properties (for example, viscosity) or solid precipitation during ink storage (6) Ejection even after storage for a long time (7) The formed image is excellent in fastness (water resistance).

In order to solve the problem (1), a method of increasing the dye concentration in the ink is generally used. However, in the case of a high-concentration dye ink, the viscosity is increased by evaporation of water or an aqueous organic solvent from the nozzle tip. Or the dye which is solid content precipitates, and it will result in causing the problem as described in said (4).
Therefore, as an attempt to obtain a high coloring power by using an oxonol dye having a high molar extinction coefficient and excellent thermal stability as a colorant, the solubility of a dye having a specific structure is enhanced and a hydrophobic polymer substance is colored by a printing method. Techniques have been proposed (see, for example, JP-T-2009-507083).

The problem (2) has been devised so that stable color reproducibility can be obtained when a printed matter having the same pattern is obtained by adjusting the hue of the dye to be used and the physical properties of the ink (for example, special features). Table 2004-515657, JP 2007-203741 A, and JP 2009-227895 A).

As for the above problem (3), an attempt has been made to improve the presence of a specific compound in the ink. However, in the case of a colorant having an insufficient color density, the solid content concentration in the ink inevitably increases. The problems (5) and (6) are inevitable. For example, as a method for causing a specific compound to be present in an ink, use of an acid dye is disclosed (see, for example, JP 2000-327976 A and JP 2007-247109 A). Note that, in applications other than textile printing, attempts have been made to improve the hue and fastness of an image (for example, JP-A-2002-371079, JP-A-2006-143789, and JP-A-2006-282749). And Japanese Patent Application Laid-Open No. 2007-84745).

As an improvement method for the above problem (4), a method using a specific aqueous solvent or the like has been proposed.
For example, a method of using trimethylolpropane and pentaethylene glycol as an aqueous organic solvent or a method of adding a specific polyoxyethylene alkyl ether to the ink has been proposed (see, for example, JP-A-2010-229251).

Improvements have also been made by applying a specific pretreatment agent to the fabric.
For example, a quaternary ammonium or amino group-containing compound (for example, see JP-A-6-192976), cationized starch (for example, see JP-A-7-173780), an aqueous synthetic polymer compound (for example, JP-A-20102010) A treatment of a fabric with a pretreatment liquid containing No. -163507 is proposed.

Special table 2009-507083 JP-T-2004-515657 JP 2007-203741 A JP 2009-227895 A JP 2000-327976 A JP 2007-247109 A JP 2002-371079 A JP 2006-143899 A JP 2006-282749 A JP 2007-84745 A JP 2010-229251 A JP-A-6-192976 JP 7-173780 A JP 2010-163507 A

However, for example, the technique disclosed in JP-T-2009-507083 is a technique for dissolving an anionic dye in a dissociated state in an organic solvent, so that the basic characteristic of water (water solubility) possessed by the chromophore of the oxonol dye Not only can be utilized, but also the color density per weight is lowered due to the introduced hydrophobic group. Therefore, in order to achieve a sufficient color density in ink jet printing, a suitable amount of dye having a high aqueous density and a high color density per weight is supplied to the fabric, and the dyeing property to the fiber after the post-treatment process is as high as possible. It is particularly important to develop agents.

When using the techniques shown in the aforementioned Japanese translations of PCT publication No. 2004-515657, Japanese Patent Application Laid-Open No. 2007-203741 and Japanese Patent Application Laid-Open No. 2009-227895, there are colorants with insufficient color density depending on the color. The current situation is that satisfactory results have not yet been obtained.
Even if the techniques disclosed in JP 2000-327976 A and JP 2007-247109 A are used, the fastness of the printed fabric is not excellent.

By the way, the printed fabric is often washed when the fabric is used as clothing, and even if the fabric is exposed to intense rubbing (external load) or intense running water in the washing machine, the image is not displayed. Ruggedness that is difficult to remove is required. On the other hand, paper on which an image is formed, a color filter having a colored composition cured film formed on a substrate, and the like are never exposed to external loads or intense running water as in a washing machine. That is, in the present situation, the color composition used for printing paper or forming a color filter cannot achieve the fastness required for textile printing, and is disclosed in JP-A-2002-371079. The coloring compositions used in other fields other than the textile printing disclosed in JP-A-2006-143899, JP-A-2006-282749 and JP-A-2007-84745 are applied to textile printing. It is difficult.

When using the technique disclosed in JP-A-2006-143898, satisfactory results cannot be obtained except for a very specific combination of a dye to be used and an aqueous organic solvent, and particularly with a colorant having an insufficient color density. Since the solid content concentration in the ink inevitably increases, a great improvement effect cannot be expected.

Further, when the techniques disclosed in JP-A-2006-282749, JP-A-2007-84745, and JP-A-2010-229251 are used, depending on the structure of the dye used for each color, the action of the pretreatment agent may be increased. In some cases, it is not sufficient, and satisfactory results are not obtained from the viewpoint of color density.

As described above, in the conventional technical range, an ink-jet printing method capable of realizing a sufficient color density and having bleeding resistance has not yet been obtained, and in particular, an ink-jet printing method having a high color density and fastness of an image. Is currently waiting for development.

This invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, it is to provide an ink jet printing method and an ink composition for ink jet printing which can form an image having excellent fastness and high color density, and a fabric having excellent image fastness and high color density. .

Specific means for solving the above-mentioned problems are as follows.

<1> A printing step of applying an ink composition for inkjet printing containing a compound represented by the following general formula (1) and having a weight average molecular weight of 800 to 2000 to a fabric containing polyamide fibers by an inkjet method Inkjet printing method.

In General Formula (1), R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. R ² , R ³ , and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, sulfo group Or a carbamoyl group. However, R ² and R ³ are not hydrogen atoms at the same time.

<2> The inkjet printing method according to <1>, further including a pretreatment step in which a pretreatment agent including a paste and a hydrotropic agent is applied to the fabric in advance before the textile printing step.

That is, the ink jet textile printing method shown in <2> includes a “pretreatment step of applying a pretreatment agent containing a paste, a pH adjuster, and a hydrotropic agent to a fabric containing polyamide fibers; and the general formula (1) And an ink-jet printing method comprising: a step of applying an ink composition for ink-jet printing containing a compound having a weight average molecular weight of 800 to 2000 to the fabric subjected to the pretreatment step by an ink-jet method. It is.
Also,

<3> An ink composition for inkjet textile printing containing a compound represented by the following general formula (1) and having a weight average molecular weight of 800 to 2,000.

<4> The ink composition for ink jet textile printing according to <3>, wherein the compound has three or more sulfo groups in the molecule.

<5> A fabric printed by the inkjet printing method according to <1> or <2>.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided an ink jet printing method and an ink composition for ink jet printing capable of forming an image having excellent fastness and high color density, and a fabric having excellent image fastness and high color density. can do.

<Inkjet printing method>
The inkjet printing method of the present invention (sometimes simply referred to as “printing method”) contains a compound represented by the following general formula (1) and having a weight average molecular weight of 800 to 2000 (also referred to as “specific compound”). The ink composition for ink jet textile printing is configured to have a textile printing step for applying to a fabric containing polyamide fibers by an ink jet method.
The textile printing method of the present invention may further include a pretreatment step for applying a pretreatment agent containing a paste, a pH adjuster, and a hydrotropic agent to the fabric in advance prior to the textile printing step. In addition, after the printing step, a post-processing step of performing a treatment such as heating the printed fabric under saturated steam may be provided.

By setting the textile printing method of the present invention as described above, an image having excellent fastness and high color density can be formed on the fabric.
The specific compound used in the textile printing method of the present invention functions as a colorant, and although the reason is not clear, it is rich in color developability and can form an image with high color density on a fabric. The color density of the image is mainly caused by the chemical structure of the colorant, but is also largely caused by the amount fixed to the fabric. That is, the greater the amount immobilized on the fabric, the greater the contrast and the higher the color density.
By the way, textile printing is performed by applying a colorant to the cloth and fixing it to the cloth. The immobilization of the colorant on the fabric is considered to be based on the fact that the colorant molecule is physically or chemically attached or bonded to the fiber of the fabric from a more microscopic viewpoint. Here, as a place where the colorant molecule physically adheres or bonds to the fiber of the fabric, a polymer chain portion in an amorphous region of the polymer chain of the fiber is considered. It is considered that strong immobilization is achieved in a state where the colorant molecules enter and do not extract into the region holes and voids where the polymer chain filling rate is low at this place. The state in which the colorant molecule is chemically attached to or bonded to the fiber of the fabric is attributed to electrostatic properties, hydrogen bonds, intermolecular forces, or similar chemical structure. A state in which each group attracts each other and adheres, or groups such as an amino group and a hydroxy group are bonded to each other can be considered.

In the textile printing method of the present invention, it is considered that when the specific compound is applied to the fabric, the specific compound enters the voids of the fiber of the fabric and has a chemical action with the fiber of the fabric. The reason why an image having excellent fastness can be formed on the fabric is thought to be because the specific compound molecules that have entered the voids of the fibers are not easily separated from the voids. Usually, the size of a compound is due to the chemical structure and is roughly proportional to the molecular weight of the compound. Here, the specific compound has at least two heterocycles in the molecule and has a bulky structure. The weight average molecular weight (Mw) is 800 to 2000. Therefore, although the reason is not clear, it is considered that such a molecular structure and a range of molecular weight create a physical action that easily enters the voids of the fiber and is difficult to separate.
The textile for printing of the present invention is a textile containing polyamide fiber represented by nylon. The polyamide fiber has an amide bond in the molecule. As shown in the general formula (1), the specific compound is classified into primary to 3 by the presence of an N atom to which R ¹ is bonded, an N atom to which R ² and R ³ are bonded, and an N atom to which R ⁴ is bonded. Has at least three primary amino groups. Since the amide bond and the primary to tertiary amino groups have similar chemical structures and are easy to act, the polyamide fiber and the specific compound are easily attracted, and even if there is an external load, the specific compound is separated from the polyamide fiber. It seems difficult to leave.

As described above, in the textile printing method of the present invention, the specific compound having excellent color developability is fixed to the polyamide fiber by two actions of physical action and chemical action, so the color density is high and the fastness is also high. It is believed that an image can be formed on the fabric.
Hereafter, each process, such as a textile printing process and the pre-processing process which may be performed as needed, is demonstrated in detail.

[Printing process]
In the inkjet printing method of the present invention, the printing step includes a polyamide fiber by an inkjet method using an inkjet printing ink composition containing a compound represented by the general formula (1) and having a weight average molecular weight of 800 to 2000. This is a step of imparting to the fabric.
Here, the ink jet method is a method of printing an image by ejecting ink from an ink jet recording head and applying the ink to a fabric.

First, the ink composition for inkjet textile printing of the present invention and the compound (specific compound) represented by the general formula (1) and having a weight average molecular weight of 800 to 2000 will be described in detail.

(Ink composition for inkjet printing)
The ink composition for inkjet textile printing of the present invention contains at least a compound (specific compound) represented by the general formula (1) and having a weight average molecular weight of 800 to 2000. The ink composition for inkjet textile printing of the present invention may further contain water, an organic solvent, a surfactant and the like.
Hereinafter, the ink composition for ink jet textile printing of the present invention may be simply referred to as “ink composition”.

-Specific compounds-
The specific compound is represented by the following general formula (1) and has a weight average molecular weight of 800 to 2000. The specific compound functions as a colorant in the ink composition of the present invention.

As described above, the fixation of the colorant to the fabric is considered to be due to the colorant molecules entering the voids such as holes and holes of the fabric fibers and not coming out from the viewpoint of physical action. . If the weight average molecular weight (Mw) of the specific compound is less than 800, the colorant can easily enter the voids of the fiber, but it can easily come out, and the specific compound cannot be fixed to the fabric. On the other hand, if the weight average molecular weight (Mw) of the specific compound exceeds 2000, the colorant cannot be fixed to the fabric because the colorant cannot enter the voids in the first place.
The weight average molecular weight (Mw) of the specific compound is preferably 800 to 1,400.
Next, R ¹ to R ⁴ in the general formula (1) and the chemical structure of the specific compound will be described.

The alkyl groups represented by R ¹ to R ⁴ in the general formula (1) are each independently preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably the number of carbon atoms. 1-6 alkyl groups are preferred. For example, methyl, ethyl, butyl, isopropyl, t-butyl and the like can be mentioned.
In addition, each of the alkyl groups represented by R ¹ to R ⁴ may independently have a substituent.

The cycloalkyl group represented by R ¹ to R ⁴ in the general formula (1) is preferably each independently a cycloalkyl group having 5 to 12 carbon atoms. For example, cyclopentyl, cyclohexyl, cyclooctyl and the like can be mentioned.
Further, each of the cycloalkyl groups represented by R ¹ to R ⁴ may independently have a substituent.

The aralkyl groups represented by R ¹ to R ⁴ in the general formula (1) are each independently preferably an aralkyl group having 7 to 12 carbon atoms. Examples include benzyl group and 2-phenethyl.
In addition, the aralkyl groups represented by R ¹ to R ⁴ may each independently further have a substituent.

The alkenyl groups represented by R ¹ to R ⁴ in the general formula (1) are each independently preferably an alkenyl group having 5 to 12 carbon atoms. For example, a vinyl group, an allyl group, etc. are mentioned.
In addition, each of the alkenyl groups represented by R ¹ to R ⁴ may independently have a substituent.

The aryl groups represented by R ¹ to R ⁴ in the general formula (1) are each independently preferably an aryl group having 6 to 12 carbon atoms. For example, phenyl, p-tolyl, naphthyl and the like can be mentioned.
In addition, each of the aryl groups represented by R ¹ to R ⁴ may independently have a substituent.

The heterocyclic group represented by R ¹ to R ⁴ in the general formula (1) is preferably independently a 5-membered or 6-membered heterocyclic group. Examples include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-furyl group and the like.
In addition, each of the heterocyclic groups represented by R ¹ to R ⁴ may independently have a substituent.

The carboxyl groups represented by R ¹ to R ⁴ in the general formula (1) may each independently be a carboxylate group (—COONa, —COOK, etc.).

The sulfo groups represented by R ¹ to R ⁴ in the general formula (1) may be each independently a sulfonate group (—SO ₃ Na, —SO ₃ K, etc.).

Examples of the sulfonyl group represented by R ² to R ⁴ in the general formula (1) independently include an alkylsulfonyl group typified by a methanesulfonyl group, an arylsulfonyl group typified by a phenylsulfonyl group, and the like. It is done.
In addition, each of the sulfonyl groups represented by R ² to R ⁴ may further have a substituent.

The acyl group represented by R ² to R ⁴ in the general formula (1) is preferably an acyl group having 1 to 12 carbon atoms. For example, an acetyl group, a benzoyl group, etc. are mentioned.
In addition, each of the acyl groups represented by R ² to R ⁴ may independently have a substituent.

The carbamoyl groups represented by R ² to R ⁴ in the general formula (1) may each independently have a substituent.

As described above, the groups other than the hydrogen atom, carboxyl group, and sulfo group represented by R ¹ to R ⁴ in the general formula 1 may each independently have a substituent. .
Examples of the substituent include a halogen atom, a linear or branched alkyl group, a cycloalkyl group, a linear or branched alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, Hydroxyl group, nitro group, ionic hydrophilic group (carboxy group, sulfo group, etc.), alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy , Amino groups (including anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl and arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups , F B-ring thio group, sulfamoyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino Group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group and the like.

The ionic hydrophilic group (carboxy group, sulfo group, etc.) is a salt, that is, a carboxylate group (—COONa, —COOK, etc.), a sulfonate group (—SO ₃ Na, —SO ₃ K, etc.), etc. There may be.

Among these, the substituent that the alkyl group represented by R ¹ to R ⁴ may have is preferably a hydroxy group, an alkoxy group, a cyano group, a halogen atom, or an ionic hydrophilic group. Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the ionic hydrophilic group include Examples thereof include a carboxy group (—COOH), a sulfo group (—SO ₃ H), a carboxylate group (—COONa, —COOK, etc.), a sulfonate group (—SO ₃ Na, —SO ₃ K etc.) and the like. Examples of the alkyl group having a substituent include hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl and the like.

The substituents that the cycloalkyl group, aralkyl group, and alkenyl group represented by R ¹ to R ⁴ may have are each independently a carboxy group (—COOH), a sulfo group (—SO ₃ H), a carboxylate group Ionic hydrophilic groups such as (—COONa, —COOK, etc.) and sulfonate groups (—SO ₃ Na, —SO ₃ K, etc.) are preferred.

The substituents that the aryl group represented by R ¹ to R ⁴ may have are each independently an alkyl group, alkoxy group, halogen atom, alkylamino group, amide group, carbamoyl group, sulfamoyl group, sulfonamide group, hydroxyl group , Ester groups, and ionic hydrophilic groups are preferred.
Examples of the aryl group having a substituent include p-methoxyphenyl, o-chlorophenyl, m- (3-sulfopropylamino) phenyl and the like.

The substituents that the heterocyclic group represented by R ¹ to R ⁴ may have are preferably each independently an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, or an ionic hydrophilic group. .

Preferred embodiments of R ¹ to R ⁴ shown above are as follows.
R ¹ is preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group. Here, Hammett's substituent constant σp value used in the present specification will be described briefly. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule.

The electron-withdrawing group of R ^{1 is} an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less. Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphospho group Group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group A halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, a heterocyclic group, a halogen atom, an azo group, a selenocyanate group, and another electron-withdrawing group having a σp value of 0.20 or more. Aryl group listed Preferably, they are a cyano group, a nitro group, and a halogen atom. The heterocyclic group may or may not be substituted with an electron withdrawing group.

R ² to R ⁴ are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, a sulfonyl group, an acyl group, or a heterocyclic group, and more preferably a sulfonyl group, an acyl group, or an aryl group. A heterocyclic group is most preferred.

The compound (specific compound) represented by the general formula (1) and having a weight average molecular weight of 800 to 2000 preferably has two or more ionic hydrophilic groups in the molecule. Examples of the ionic hydrophilic group include a carboxy group (—COOH) and a sulfo group (—SO ₃ H). The carboxy group and the sulfo group may form a salt. That is, it may be a carboxylate group (—COONa, —COOK, etc.) or a sulfonate group (—SO ₃ Na, —SO ₃ K, etc.). When the specific compound has two or more ionic hydrophilic groups, the ionic hydrophilic groups may be the same or different.
The number of ionic hydrophilic groups possessed by the specific compound is more preferably 3 or more, and even more preferably 3 to 4.

In particular, the specific compound preferably has three or more sulfo groups (including sulfonate groups) in the molecule, and all of the specific compounds may be sulfo groups or sulfonate groups. A group and a sulfonate group may be mixed.

Specific examples of specific compounds are shown below, but are not limited thereto.

In the ink composition of the present invention, among the specific compounds described above, only one type may be used, or two or more types may be used in combination.
The ink composition of the present invention may contain only the specific compound described above as a colorant, but further contains a colorant other than the specific compound as long as the effects of the present invention are not impaired. It may be.
When the ink composition of the present invention contains a colorant other than the specific compound, the content of the specific compound in the total colorant is preferably 50% by mass or more based on the total colorant mass, and 80 More preferably, it is at least mass%. Furthermore, the colorant contained in the ink composition of the present invention is particularly preferably 100% by mass of a specific compound.
The content of the specific compound in the ink composition of the present invention is from 0.1% by mass to the total mass of the ink composition in consideration of obtaining a sufficient color density and considering the storage stability of the ink composition. It is preferably 20% by mass, more preferably 0.2% by mass to 15% by mass.

The ink composition of the present invention may further contain water, if necessary, and may contain components such as an organic solvent and a surfactant in addition to the specific compound described above.

-water-
The water that can be contained in the ink composition of the present invention is not particularly limited, and may be ion-exchanged water or tap water.
When the ink composition of the present invention contains only the specific compound described above in addition to water, the water content is the balance obtained by subtracting the specific compound content from the total mass of the ink composition. However, when it contains the component mentioned later, it is the remainder which deducted the total content of a specific compound and the said other component.

-Organic solvent-
The organic solvent that can be contained in the ink composition of the present invention is preferably an aqueous organic solvent. For example, in addition to polyhydric alcohols such as diethylene glycol and glycerin, amines, monohydric alcohols, polyhydric alcohol alkyls, and the like. And ethers. Further, each compound exemplified as an example of the water-miscible organic solvent described in paragraph [0076] of JP-A No. 2002-371079 is preferable.
The content of the organic solvent in the ink composition of the present invention is preferably 10% by mass or more and 60% by mass or less with respect to the total mass of the ink composition for inkjet textile printing.

-Surfactant-
In the ink composition of the present invention, various surfactants can be used from the viewpoint of enhancing storage stability, ejection stability, ejection accuracy, and the like. As the surfactant, any of cationic, anionic, amphoteric, and nonionic surfactants can be used. Examples of the cationic surfactant include aliphatic amine salts and aliphatic quaternary compounds. And ammonium salts. Further, each cationic surfactant mentioned as an example of the surface tension adjusting agent described in paragraph [0073] of JP-A-2002-371079 is preferable.

Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, and the like. Further, each anionic surfactant mentioned as an example of the surface tension adjusting agent described in paragraph [0073] of JP-A No. 2002-371079 is preferable.

Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, acetylene glycol, acetylene alcohol and the like. Further, each nonionic surfactant mentioned as an example of the surface tension adjusting agent described in paragraph [0073] of JP-A-2002-371079 is preferable.

When using each of these surfactants, the surfactant may be used alone or in combination of two or more.
The content of the surfactant in the ink composition of the present invention is preferably in the range of 0.001% by mass to 1.0% by mass with respect to the total mass of the ink composition. It is preferable to arbitrarily adjust the surface tension of the object.

-Antiseptic, antifungal agent-
The ink composition of the present invention may contain at least one of an antiseptic and an antifungal agent in order to maintain long-term storage stability. Examples of the antiseptic and antifungal agent include aromatic halogen compounds (for example, Preventol CMK; manufactured by LANXESS), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL). ; Manufactured by Arch Chemicals Co., Ltd.).

-Various additives-
The ink composition of the present invention may contain other conventionally known additives. For example, pH adjusters such as acid bases and buffers, fluorescent brighteners, antifoaming agents, lubricants, thickeners, antistatic agents, matting agents, antioxidants, specific resistance adjusting agents, rust preventing agents, inorganic Pigments, reduction inhibitors and the like.

In the textile printing process, the ink composition containing the specific compound described above is applied to a fabric containing polyamide fibers by an ink jet method.
Here, the ink jet method is a method of printing an image by ejecting ink from an ink jet recording head and applying the ink to a fabric.
Moreover, the fabric (fabric for textile printing) used by the textile printing method of this invention is demonstrated.

-Cloth (-Fabric for printing)-
A fabric used in the inkjet printing method of the present invention, that is, a fabric that has not completed the printing process is referred to as a “printing fabric”.
The type of fabric for printing is not particularly limited as long as it is a fabric containing at least polyamide fibers. Specifically, nylon, silk and wool are preferable as the polyamide fiber. The polyamide fiber may be in any form such as a woven fabric, a knitted fabric, or a non-woven fabric.

From the standpoint of fully exhibiting the effects of the present invention, the fabric containing polyamide fibers is preferably 100% polyamide fibers, but may contain materials other than polyamide fibers. When the fabric includes fibers other than polyamide fibers, the blend ratio of polyamide fibers is preferably 30% or more, and more preferably 50% or more. The material other than the polyamide fiber may be, for example, a blended woven fabric or a blended nonwoven fabric with rayon, cotton, acetate, polyurethane, acrylic fiber or the like.

There are suitable ranges for the physical properties of yarns composed of polyamide fibers constituting the fabric (polyamide fibers and other fibers when fibers other than polyamide fibers are used). For example, in the case of nylon, the average of nylon fibers The thickness is controlled to 1 to 10 d (denier), more preferably 2 to 6 d, and the average thickness of the nylon yarn composed of the nylon fiber is 20 to 100 d, more preferably 25 to 80 d, more preferably , 30 to 70d are preferably used. In the case of silk, as a characteristic of the fiber itself, the average thickness of the silk fiber is controlled to 2.5 to 3.5d, and more preferably 2.7 to 3.3d. The average thickness is controlled to 14 to 147d, more preferably 14 to 105d, and fabrics made by a known method are preferably used.

In the ink jet textile printing method of the present invention, the ink composition containing the specific compound described above is printed by applying ink to the fabric, and then the printed fabric is wound, and the fabric is heated to cause color development. It is desirable to wash and dry.
In textile printing by the ink jet method, by following the above procedure, an ink is printed on a fabric and the specific compound is sufficiently dyed as compared with the case where the ink is left as it is. Obtainable. In particular, when printing is continued for a long time while transporting a long fabric with a roller or the like, the printed fabric will be transported endlessly and the fabric printed on the floor will overlap. There is. Therefore, it is preferable to perform an operation of winding the printed fabric after printing in order not only to save space but also to be unsafe and to prevent unexpected contamination. During this winding operation, a medium not related to printing, such as paper, cloth, or vinyl, may be sandwiched between the cloths. However, when the printed fabric is cut in the middle or when the printed fabric is short, it is not always necessary to wind it.

In the ink jet textile printing method of the present invention, when the ink composition is applied to the fabric, the textile fabric is pretreated before the textile printing step so that the specific compound is more firmly fixed to the textile. Alternatively, after the textile printing process, the fabric to which the ink composition is applied may be subjected to a post-treatment.
That is, the inkjet textile printing method of the present invention can be configured to include a pretreatment process, the above-described textile printing process, and a post-treatment process. (1) Pretreatment process, (2) Textile process, ( 3) What is necessary is just to perform each process in order of a post-processing process.
Hereinafter, the details of the pre-processing step for performing the pre-processing and the post-processing step for performing the post-processing will be described.

[Pretreatment process]
The pretreatment step is a step of applying a pretreatment agent containing a paste and a hydrotropic agent to a fabric containing a polyamide fiber (printing fabric before application of the ink composition).
Since the ink jet textile printing method of the present invention has a pretreatment step, when the ink composition adheres to the fabric before the ink composition is applied to the fabric, the ink composition tends to aggregate or the ink composition By preliminarily applying a pretreatment agent containing a component that makes the specific compound and the fabric easily adhere to the fabric, it is possible to enhance the immobilization of the specific compound on the fabric.
The pretreatment agent may further contain a pH adjuster, an aqueous (water-soluble) metal salt, a water repellent, a surfactant, and the like, if necessary, in addition to the paste and the hydrotropic agent.

(Pretreatment agent)
-Hydrotropic agent-
In the present invention, the hydrotropic agent generally serves to increase the color density of an image when the fabric to which the ink composition is applied is heated under steam. For example, urea, alkylurea, ethyleneurea, propyleneurea, thiourea, guanidate, halogen-valent tetraalkylammonium, etc. are usually mentioned.
The content of the hydrotropic agent with respect to the total mass of the pretreatment agent is preferably 0.01% by mass to 20% by mass.

-Glue-
A water-soluble polymer is used as the paste. The water-soluble polymer may be a natural polymer or a synthetic polymer.
Examples of the aqueous polymer include starch substances such as corn and wheat, cellulose substances such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; And known natural aqueous polymers such as protein substances such as casein, tannin substances, and lignin substances.
Examples of the synthetic aqueous polymer include known polyvinyl alcohol compounds, polyethylene oxide compounds, acrylic acid aqueous polymers, and maleic anhydride aqueous polymers. Of these, polysaccharide polymers and cellulose polymers are preferred.

The pretreatment agent may be prepared so that the paste and the hydrotropic agent are mixed so as to have the above-described content, and water is further added to be 100% by mass.
The pretreatment agent may further impart a pH adjuster, an aqueous metal salt, a water repellent, a surfactant and the like. The pretreatment agent may contain any or all of the following components.

-PH adjuster-
The pH adjuster generally plays a role of enhancing the fixation reaction of the colorant to the fabric.
The pH adjuster refers to a compound or composition that adjusts the liquidity (pH) of the aqueous coloring composition for printing applied to the fabric. In addition to components that change the liquidity of the aqueous coloring composition for printing. In addition, a component such as a pH buffer that suppresses a change in liquid properties of the aqueous coloring composition for printing is also included.

Examples of the pH adjuster include alkali (base), acid, or a combination of alkali and acid, and components having pH buffering action such as acid ammonium salt. Examples of the acid ammonium salt include ammonium sulfate and ammonium tartrate.
The content of the pH adjusting agent with respect to the total mass of the pretreatment agent is preferably 0.01% by mass to 20% by mass.

-Aqueous metal salt-
Examples of the aqueous (water-soluble) metal salt include compounds that form typical ionic crystals and have a pH of 4 to 10, such as alkali metal and alkaline earth metal halides.
Typical examples of such compounds include NaCl, Na ₂ SO ₄ , KCl, and CH ₃ COONa for alkali metals, and examples of alkaline earth metals include CaCl ₂ and MgCl ₂ . Of these, Na, K, and Ca salts are preferred.

-Water repellent-
Examples of water repellents include paraffinic, fluorine-based compounds, pyridinium salts, N-methylolalkylamides, alkylethyleneurea, oxalin derivatives, silicone-based compounds, triazine-based compounds, zirconium-based compounds, or mixtures thereof. However, it is not particularly limited. Among these water repellents, paraffin-based and fluorine-based water repellents are particularly preferable in terms of prevention of bleeding and concentration. The water repellent is preferably added in an amount of 0.05% to 40% by mass, more preferably 0.5% to 10% by mass, based on the total mass of the fabric. This is because if the content is less than 0.05% by mass, the effect of preventing excessive penetration of the ink is small, and even if the content exceeds 40% by mass, there is no significant change in performance.

-Surfactant-
As the surfactant, anionic, nonionic or amphoteric surfactants can be used.
In particular, it is preferable to use a nonionic surfactant of HLB 12.5 or more, preferably 14 or more.

A betaine type etc. can be used as an amphoteric surfactant.
The surfactant is preferably added to the fabric in an amount of 0.01 to 30% by mass. Furthermore, it is preferable to add additives such as a reducing agent, an antioxidant, a leveling agent, a deep dyeing agent, a carrier, a reducing agent and an oxidizing agent depending on the characteristics of the dye used.

In the pretreatment, it is preferable to put the pretreatment agent within a range of 5% to 150%, preferably 10% to 130%.
In the pretreatment, the method for incorporating each of the above pretreatment agents into the fabric is not particularly limited, and examples thereof include a commonly performed dipping method, pad method, coating method, spray method, and ink jet method.

[Post-treatment process]
The fabric that has undergone the textile printing process is preferably subjected to a post-treatment to promote the fixation of the specific compound to the fiber.
The post-treatment step preferably includes a step of sufficiently removing the specific compound that has not fixed to the fabric, the other colorant, components other than the colorant, and the pretreatment agent.
The post-processing can be configured by, for example, performing a preliminary drying process, a steam process, a cleaning process, and a drying process in this order.
Hereinafter, each process preferable as a post-processing process will be described.

-Predrying process-
First, after the textile printing step, it is preferable to leave the fabric, to which the ink composition containing the specific compound is applied, at room temperature to 150 ° C. for 0.5 to 30 minutes to pre-dry the ink. This preliminary drying can improve the printing density and effectively prevent bleeding. The preliminary drying includes that the ink penetrates into the fabric.

According to the ink jet textile printing method of the present invention, preliminary drying can be performed by heating in a continuous process. The fabric is rolled and supplied to an ink jet printing machine for printing (printing and printing), and then dried using a dryer before winding the printed fabric. The dryer may be directly connected to the printing machine or separated. The printed fabric is preferably dried at room temperature to 150 ° C. for 0.5 to 30 minutes in a dryer. Moreover, as a preferable drying method, an air convection method, a heating roll direct attachment method, an irradiation method, etc. are mentioned.

-Steam process-
The steam process is a process of promoting immobilization of a specific compound on a fabric by exposing the fabric to which ink has been applied to saturated steam and heating the fabric.
According to the inkjet textile printing method of the present invention, it is preferable that the steam process in the post-treatment is changed in conditions, particularly in the time, depending on the type of fabric.
For example, when the fabric is wool, the time for the steam process is preferably 1 minute to 120 minutes, more preferably about 3 minutes to 90 minutes. When the fabric is silk, the time is preferably 1 minute to 40 minutes, more preferably about 3 minutes to 30 minutes. Further, when the fabric is nylon, it is preferably about 1 minute to 90 minutes, more preferably about 3 minutes to 60 minutes.

-Washing process-
In this way, most of the ink ink jet recorded on the fabric adheres to the fabric, but some of the colorant does not adhere to the fiber. This unfixed colorant is preferably washed away. A conventionally known cleaning method can be employed to remove the unfixed colorant. For example, it is preferable to use water in the range of room temperature to 100 ° C. or warm water, or an anionic or nonionic soaping agent. By completely removing the unfixed coloring material, good results can be obtained in various water resistances such as washing fastness and sweat fastness.

-Drying process (drying after washing)-
Drying is required after washing the printed fabric. After the washed fabric is squeezed or dehydrated, it is dried or dried using a dryer, heat roll, iron or the like.

<Ink composition for inkjet textile printing>
The ink composition for inkjet textile printing of the present invention comprises a compound represented by the general formula (1) described above and having a weight average molecular weight of 800 to 2,000.
In ink jet textile printing, by using the ink composition having the above-described structure, it is possible to obtain a cloth printed with an image having excellent fastness and high color density.
The compound (specific compound) represented by the general formula (1) contained in the ink composition for ink jet textile printing of the present invention and having a weight average molecular weight of 800 to 2000 is a compound (specific compound) having three or more sulfo groups in the molecule. Compound S) is preferred. In particular, the use of the specific compound S as the specific compound is suitable as an ink for ink jet recording having a restriction in the amount of the colorant supplied onto the fabric because the color density is further increased and the fastness is excellent.
The contents of the specific compound (including the specific compound S) and the water in the ink composition for ink jet printing of the present invention are described as the content of the specific compound in the ink composition used in the ink jet printing method of the present invention. A range is preferable. In addition to the specific compound S, components that can be contained in the ink composition for ink jet printing of the present invention are the same as those that can be contained in the ink composition used in the ink jet printing method of the present invention, and preferred embodiments are also the same.

<Fabric>
The fabric of the present invention is not particularly limited as long as it includes a polyamide fiber printed by the inkjet printing method of the present invention, and the type of the fabric is the same as the type of the fabric for printing described above, and a preferred embodiment Is the same.
Since the fabric of the present invention is printed using an ink composition for ink jet printing containing a specific compound, an image formed by printing has excellent fastness and a high color density.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.

[Examples 1 to 6 and Comparative Examples 1 to 3]
<Pretreatment process>
-Preparation of pretreatment agent A to pretreatment agent C-
(1) Glue: Guar gum [Nippon Co., Ltd. MEYPRO GUM NP]
(2) Hydrotrope: Urea (manufactured by Wako Pure Chemical Industries, Ltd.)
(3) pH adjuster: ammonium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.)
(4) Water

The components shown in (1) to (4) above were mixed in the amounts [%] shown in Table 1 to prepare Pretreatment Agent A to Pretreatment Agent C.

-Fabric for printing-
Silk fabric and nylon fabric were prepared as textiles for printing.
The silk fabric used was a silk feather double 14 mm (made by Color Dye), and the nylon fabric used was nylon-6 taffeta (made by Toray Industries) and nylon-6,6 (made by Color Dye).

Using the obtained pretreatment agent A to pretreatment agent C, a silk fabric and a nylon fabric were put and naturally dried to obtain a treated fabric.
The drawing ratio was 80% to 100% for silk fabrics and 10% to 30% for nylon fabrics.

<Printing process>
(Preparation of ink composition)
Inks 1 to 4 and inks 101 to 103 were prepared by mixing the components according to the following composition and filtering the resulting mixture with a membrane filter having a pore size of 10 μm.

・ Dye 3% shown in Table 2
・ Glycerin [Wako Pure Chemical Industries, Ltd.] (aqueous organic solvent) 10%
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) (aqueous organic solvent) 10%
・ Orphine E1010 (manufactured by Nissin Chemical Co., Ltd.) (acetylene glycol surfactant) 1%
・ Urea 2%
・ 74% of water

In Table 2, “X” in the column of “General Formula (1)” means that the dye has a molecular structure included in General Formula (1), and “Y” It means that the molecular structure is not included in the general formula (1). “Mw” is the weight average molecular weight of each dye.

Note that the dyes (specific compounds) of the specific examples used in the inks 1 to 4 shown in Table 1 were synthesized with reference to JP-A No. 2002-371079.

Each of the obtained inks (inks 1 to 4 or 101 to 103) was set in an ink jet printer (manufactured by Dimatics, DMP-2381), and a solid image was printed on the obtained pretreated fabric.
Table 3 shows combinations of pretreatment agents and inks used for textiles for printing (silk cloth, nylon 6 cloth, or nylon 6,6 cloth).

<Post-processing process>
After the printed fabric was dried, it was steamed in saturated steam at 100 ° C. in a steam process, and the silk fabric was steamed for 8 minutes and the nylon fabric was steamed for 30 minutes to fix the dye to the fibers of the fabric. Thereafter, the fabric was washed with cold water for 10 minutes and warm water at 60 ° C. for 5 minutes, and then naturally dried.

<Evaluation>
1. Evaluation of Color Density For each solid image formed on each fabric, the color density (OD value; Optical Density value) was measured with a reflection densitometer (Xrite 938, manufactured by Xrite).

2. Fastness Evaluation Each fabric on which a solid image was formed was evaluated for light fastness, sweat fastness and washing fastness. The nylon 6 and 6 fabrics were evaluated only for light fastness.
Light fastness, sweat fastness, and wash fastness were each evaluated by a method based on the following JIS test method, and evaluated by an evaluation method based on the test method.
(1) Light fastness: JIS-L0842
(2) Sweat resistance: JIS-L0848
(3) Washing fastness: JIS-L0844 A-2

Table 3 shows the results of evaluation in each example and comparative example obtained as described above.

In the evaluation results of the robustness shown in Table 3, “4/5” indicates that the evaluation result was between 4 and 5. The same applies to “3/4” and “2/3”.

As can be seen from Table 3, according to the ink jet printing method of the examples, the printed fabric has a color density (OD value) of more than 1 for both silk, nylon 6, and nylon 6,6, and The fastness of light, sweat resistance and washing resistance was 4 or more.

On the other hand, the inks 101 to 103 using the conventional colorant may have insufficient fastness or may not be able to be printed even if the color density increases.
Thus, in the textile printing by the ink jet textile printing method shown in the comparative example, it was impossible to achieve both high color density and high fastness.

The disclosure of Japanese application 2012-045598 and the disclosure of Japanese application 2012-104719 are incorporated herein by reference in their entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims

Inkjet printing method comprising a printing step in which an ink composition for inkjet printing containing a compound represented by the following general formula (1) and having a weight average molecular weight of 800 to 2000 is applied to a fabric containing polyamide fibers by an inkjet method .

[In General Formula (1), R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. R 2 , R 3 , and R 4 are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, sulfo group Or a carbamoyl group. However, R 2 and R 3 are not hydrogen atoms at the same time. ]
The ink-jet printing method according to claim 1, further comprising a pretreatment step of applying a pretreatment agent containing a glue and a hydrotropic agent to the fabric in advance before the textile printing step.
An ink composition for ink-jet printing comprising a compound represented by the following general formula (1) and having a weight average molecular weight of 800 to 2,000.

[In General Formula (1), R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. R 2 , R 3 , and R 4 are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, sulfo group Or a carbamoyl group. However, R 2 and R 3 are not hydrogen atoms at the same time. ]
The ink composition for ink-jet printing according to claim 3, wherein the compound has three or more sulfo groups in the molecule.
A fabric printed by the ink jet printing method according to claim 1 or 2.