JP6972741B2 - Inkjet ink composition for printing, ink set and recording method - Google Patents

Description

The present invention relates to an inkjet ink composition for printing, an ink set, and a recording method.

The inkjet recording method is a method in which small droplets of ink are ejected from a fine nozzle and adhered to a recording medium for recording. This method has a feature that a high-resolution and high-quality image can be recorded at high speed with a relatively inexpensive device. In the inkjet recording method, there are numerous study factors such as the properties of the ink used, the stability in recording, and the quality of the obtained image, and research on not only the inkjet recording device but also the ink composition to be used is active. be.

Further, the fabric and the like are also dyed (printed) by using an inkjet recording method. Conventionally, screen printing, roller printing, etc. have been used as printing methods for fabrics (woven fabrics and non-woven fabrics), but the inkjet recording method should be applied from the viewpoint of high-mix low-volume productivity and immediate printability. Has been studied in various ways because it is advantageous.

Various performances are also required for the ink composition used for textile printing inkjet recording, but from the viewpoint of dyeing the fabric, performances that are not required for ordinary ink compositions may be required. Therefore, there are many study factors in the inkjet ink composition for printing.

For example, reactive groups that react during printing may deteriorate during storage. On the other hand, Patent Document 1 describes monochlorotriazine-based reactive dyes and tris (hydroxymethyl) for the purpose of obtaining high temporal stability (storage stability) without causing decomposition of reactive groups that react during printing. ) A liquid composition containing aminomethane is disclosed.

Also, in inkjet printing, an ink set including four color dye inks of YMCK (yellow, magenta, cyan, and black) is often used. However, when such an ink set is used in the inkjet printing method, the hue range obtained by the screen printing method may not be completely reproduced. For example, Patent Document 2 intends to widen the color reproduction range, particularly the color reproduction range in the hue range of magenta-violet-blue-cyan. I. A cyan ink composition containing Reactive Blue 15: 1 and C.I. I. A reactive dye ink set for inkjet printing has been proposed comprising a magenta ink composition containing Reactive Red 245.

Japanese Unexamined Patent Publication No. 2002-241639 International Publication No. 2010/013649

In inkjet printing, it is required to improve the storage stability of ink and widen the color reproduction range of the printed matter as seen in the above patent documents. In addition, like the ink used for ordinary inkjet recording, the color development of the ink and the printed matter (sometimes referred to as the printed matter and the recorded matter) is improved, and the image fastness (light resistance, etc.) of the printed matter is improved. It is also required.

The inventors conducted a long-term outdoor exposure test of the printed material in inkjet printing, and as a result of extensively examining changes in color development, hue, etc., it was generated by mixing inks of multiple colors such as CMYK (hereinafter referred to as composite). There is.) It has been found that a change in hue with time is likely to occur in a specific hue. In particular, brown, brown (JIS customary color name of Japanese industrial standard), brown, chestnut, yellow brown (yellowish brown), red brown (reddish brown), dark brown, etc. (hue angle ∠h ° is about 15 ° or more) It has also been found that the hue of colors in the range of 80 ° or less) is likely to change by long-term field exposure tests of printed materials. The inventors presume that the change in hue is partly due to the difference in light resistance between the dyes contained in the plurality of inks.

One of the objects according to some aspects of the present invention is to be able to express a color having a hue angle ∠h ° in the range of 15 ° or more and 80 ° or less with good color development in a printed material without mixing a plurality of colors. Further, the present invention provides an inkjet ink composition for printing, an ink set, and a recording method, which can suppress a change in hue (light resistance) over time and have excellent ejection reliability (recovery from clogging and continuous ejection stability). There is something in it.

The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as the following aspects or application examples.

One aspect of the inkjet ink composition for printing according to the present invention is
With dyes
Cyclic amides that are liquid at room temperature and have a standard boiling point of 190 ° C or higher and 260 ° C or lower are 5% by mass or more and 30% by mass or less.
The hue angle ∠h ° defined in the CIELAB color space on the recording medium is in the range of 15 ° or more and 80 ° or less.

According to such an inkjet ink composition for printing, a color having a hue angle ∠h ° in the range of 15 ° or more and 80 ° or less can be expressed in a printed material with good color development without mixing a plurality of colors. It is possible to suppress the change in hue (light resistance) over time. Further, by containing the cyclic amide having a standard boiling point of 190 ° C. or higher and 260 ° C. or lower in an amount of 5% by mass or more and 30% by mass or less, the dye can be dissolved in a sufficient amount, so that the printed matter has good color development. Can be obtained. Then, colors in the range of hue angle ∠h ° of 15 ° or more and 80 ° or less can be expressed without mixing a plurality of colors, and hue change (light resistance) over time can be suppressed.

In the inkjet ink composition for printing according to the present invention, the hue angle ∠h ° defined in the CIELAB color space on the recording medium may be in the range of 20 ° or more and 75 ° or less.

According to such an inkjet ink composition for printing, for example, when the fabric to be printed is cotton, silk, wool, viscose (rayon), etc., the color in the range is a mixture of a plurality of colors. It can be expressed without any problem, and the change in hue (light resistance) over time can be further suppressed.

In the inkjet ink composition for printing according to the present invention.
The dye may be a dye having a maximum absorption wavelength in the range of 350 nm or more and 450 nm or less.

According to such an inkjet ink composition for printing, a color having a hue angle ∠h ° in the range of 15 ° or more and 80 ° or less can be expressed without mixing a plurality of colors.

In the inkjet ink composition for printing according to the present invention.
The dye is C.I. I. Reactive Orange 35, C.I. I. Reactive Orange 12, C.I. I. Reactive Orange 99, C.I. I. Acid Brown 298 and C.I. I. It may be one or more of acid orange 56.

Such an inkjet ink composition for printing has even better color development.

In the inkjet ink composition for printing according to the present invention.
The content of the dye may be 3% by mass or more and 15% by mass or less.

According to such an inkjet ink composition for printing, the content of the dye is sufficient and the color development property is further improved.

In the inkjet ink composition for printing according to the present invention.
The pH of the inkjet ink composition for printing may be 6 or more and 10 or less.

According to such an inkjet ink composition for printing, the color development property becomes better.

In the inkjet ink composition for printing according to the present invention.
The inkjet ink composition for printing contains an alkyl polyol having a standard boiling point of 180 ° C. or higher and 260 ° C. or lower.
The content of the alkyl polyol may be 10% by mass or more and 25% by mass or less.

According to such an inkjet ink composition for printing, even when a dye containing copper is likely to generate foreign substances due to drying, the moisturizing property of the alkyl polyol is enhanced, and as a result, clogging recovery and continuous ejection stability are achieved. The sex can be maintained high.

One aspect of the ink set according to the present invention includes the above-mentioned inkjet ink composition for printing.

According to such an ink set, colors in the range of hue angle ∠h ° of 15 ° or more and 80 ° or less can be expressed without mixing multiple colors, and at least of the colors in the range of the hue angle. It is possible to suppress the change in hue (light resistance) of the printed portion over time.

One aspect of the recording method according to the present invention is
A pretreatment step of applying a pretreatment composition containing at least one of an alkaline agent, an acid and a hydrotropy agent to the fabric, and a printing step of imprinting the fabric using the above-mentioned inkjet ink composition for printing. including.

According to such a recording method, a color having a hue angle ∠h ° in the range of 15 ° or more and 80 ° or less can be expressed with good color development in a printed material without mixing multiple colors, and the hue over time. Change (light resistance) can be suppressed.

C. I. Reactive Orange 35 (RO35), C.I. I. Reactive Orange 12 (RO12), C.I. I. Reactive Orange 99 (RO99), C.I. I. Acid Brown 298 (ABr298), and C.I. I. Absorption spectrum of acid orange 56 (AO56) in the visible light region.

Hereinafter, some embodiments of the present invention will be described. The embodiments described below describe an example of the present invention. The present invention is not limited to the following embodiments, and includes various modifications implemented without changing the gist of the present invention. Not all of the configurations described below are essential configurations of the present invention.

1. 1. Inkjet ink composition for printing The inkjet ink composition for printing of the present embodiment (hereinafter, also referred to as an inkjet ink composition for printing, an ink composition, etc.) has a pretreatment composition of the present embodiment, which will be described later, adhered to a cloth. After that, the ink jet ink composition for printing is attached to the fabric by an inkjet method and used. First, the inkjet ink composition for printing will be described.

The inkjet ink composition for printing of the present embodiment contains a dye and a cyclic amide which is liquid at room temperature and has a standard boiling point of 190 ° C. or higher and 260 ° C. or lower in an amount of 5% by mass or more and 30% by mass or less. The hue angle ∠h ° defined in the CIELAB color space on the medium is in the range of 15 ° or more and 80 ° or less.

1.1. Dye The inkjet ink composition for printing of the present embodiment contains a dye.

1.1.1. Types of Dyes C .. I. Reactive Orange 35, C.I. I. Reactive Orange 12, C.I. I. Reactive Orange 99, C.I. I. Acid Brown 298, C.I. I. Acid orange 56 and the like can be mentioned.

C. I. Reactive Orange 35, C.I. I. Reactive Orange 12, C.I. I. Reactive Orange 99, C.I. I. Acid Brown 298 and C.I. I. The chemical structure of the acid orange 56 is shown in the following formulas (1), (2), formula (3), formula (4) and formula (5). In the present specification, in each chemical formula, the group represented by " _{-SO 3} Na" represents the case where the paired ion of " _{-SO 3} ^{− " is "Na +".} However, each of the formulas "-SO ₃ ^-" independently in groups, ion forming a pair is ^{"H +",} "Li ^+", or ^{"K +"} or the like.

C. I. Reactive Orange 35: Equation (1)

C. I. Reactive orange 12: Equation (2)

C. I. Reactive Orange 99: Equation (3)

C. I. Acid Brown 298: Equation (4)

C. I. Acid Orange 56: Equation (5)

When the ink jet ink composition for printing contains the above dye, good color development and hue stability over time (light resistance) can be obtained regardless of the type of fabric to be printed.

11.2. Hue angle ∠h ° defined in CIELAB color space
By using the inkjet ink composition for printing of the present embodiment for printing, the hue angle ∠h ° defined in the CIELAB color space on the recording medium is in the range of 15 ° or more and 80 ° or less.

Here, the hue angle ∠h ° defined in the CIELAB color space is a color space with a perceptually almost equal rate recommended by the International Commission on Illumination (CIE) in 1976. L ^* a ^* b ^* It is a parameter representing hue calculated by the following equation using the color coordinates a ^* and b ^{* of the color space.} "Hue angle ∠h ° = tan ^-1 (b ^* / a ^* )".

In addition, this hue angle ∠h ° is "4.2" in "3.6 CIELAB 1976ab hue angle" of "Color ^{measurement-Part 4: CIE1976L *} a ^* b ^{* color space" of the Japanese Industrial Standard JISZ8781-4: 2013.} It is also the amount of hue correlation calculated by the equation (11) of "quantities related to lightness, chroma and hue" (see also 03087 of JISZ8113), "CIE1976L ^* a ^* b ^* ", and "CIELAB". "Is said to be able to paraphrase each other.

The hue angle ∠h ° defined in the CIELAB color space “on the recording medium” of the inkjet ink composition for printing as defined herein is, for example, the Japanese Industrial Standard JISZ8722: 2009 “Color Measuring Method-Reflection”. And it can be obtained from the measurement by "5. Spectral color measurement method" of "Transparent object color". The measurement conditions at that time are as follows.

(1) Create an inkjet ink composition for printing (2) Apply ink to the fabric to be printed (3) React sufficiently by heating, steam, etc. (4) Wash the fabric (5) Spectral color measurement Then, from the obtained measurement results, the hue angle ∠h ° is calculated to be the hue angle ∠h ° defined in the CIELAB color space “on the recording medium” of the inkjet ink composition for printing.

As a method of adjusting the inkjet ink composition for printing so that the hue angle ∠h ° defined in the CIELAB color space on the recording medium is in the range of 15 ° or more and 80 ° or less, the dye itself is changed. There are several methods, such as mixing with dyes with different hue angles. More specifically, for a specific dye, a method of modifying the conjugated system by changing the number and type of aromatic rings and substituents, a method of modifying the central metal when present, and another dye. Examples include a method of mixing.

However, among these methods, when the hue angle is adjusted by mixing another dye with the ink jet ink composition for printing, it is preferable to add less of the other dye, for example, the inkjet ink for printing. 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass, based on the total composition. % Or less. By doing so, even if each dye causes fading over time, the change in the hue angle at the printing portion can be suppressed to be small. Further, when mixing other dyes, it is more preferable that the hue angles of the other dyes are close to each other, and in that case, the blending amount may be increased, for example, with respect to the entire inkjet ink composition for printing. In total, it is 2% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less.

Although a plurality of types of dyes can be mixed and used, it is preferable to mix a single type from the viewpoint of suppressing the change in the hue angle in the printed portion to be small. That is, it is more preferable to use the dye alone in the inkjet ink composition for printing of the present embodiment. In this case, other dyes may be contained as long as they can be regarded as impurities. The total amount of the dyes as impurities is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and further, with respect to the total amount of the dyes contained in the inkjet ink composition for printing. It is preferably 0.001% by mass or less, and particularly preferably 0.0001% by mass or less. In this way, printing can be performed with substantially only a single dye, and even if the dye causes fading over time, there is almost no change in the hue angle at the printing portion. Suitable.

The total content of the dyes in the inkjet ink composition for printing of the present embodiment is 2% by mass or more and 30% by mass or less, preferably 3% by mass or more and 15% by mass, based on the total mass of the inkjet ink composition for printing. % Or less, more preferably 4% by mass or more and 10% by mass or less.

Further, the dye to be blended in the inkjet ink composition for printing of the present embodiment is C.I. I. Reactive Orange 35, C.I. I. Reactive Orange 12, C.I. I. Reactive Orange 99, C.I. I. Acid Brown 298 and C.I. I. More preferably, it is at least one selected from the acid orange 56. Among these, C.I. I. Reactive Orange 35, C.I. I. It is particularly preferable to use Acid Brown 298. By selecting such a dye, colors in the range of hue angle ∠h ° of 15 ° or more and 80 ° or less can be expressed with good color development in the printed matter without mixing multiple colors, and over time. Hue change (light resistance) can be suppressed. That is, by containing at least these dyes, good color development can be obtained in the printed matter. And C.I. I. Reactive Orange 35 or C.I. I. When Acid Brown 298 is used, since the light resistance of the dye itself is better, it is possible to express a color in the range of hue angle ∠h ° of 20 ° or more and 75 ° or less without mixing multiple colors. , Hue change (light resistance) over time can be remarkably suppressed.

Furthermore, C.I. I. Reactive Orange 35 or C.I. I. When Acid Brown 298 is used, it is possible to express a color having a hue angle ∠h ° of 20 ° or more and 75 ° or less independently without mixing a plurality of colors. That is, the hue angle ∠h ° defined in the CIELAB color space on the recording medium may be in the range of 20 ° or more and 75 ° or less.

According to such an inkjet ink composition for printing, for example, when the fabric to be printed is cotton, silk, wool, viscose (rayon), PA (polyamide) elastomer, or the like, the range is such. Colors can be expressed without mixing multiple colors, and the hue change (light resistance) over time can be further suppressed. Further, by this, a brown hue is realized by combining a composite ink containing a plurality of kinds of dyes or an ink having a plurality of kinds of hues (for example: a brown hue is realized by using an ink set consisting of four colors of YMCK). ) It is possible to realize better light resistance (that is, suppression of change in hue with time) as compared with the conventional technique.

The dye contained in the inkjet ink composition for printing of the present embodiment is as described above, and the dye is more preferably a dye having a maximum absorption wavelength in the range of 350 nm or more and 450 nm or less. ..

Here, the maximum absorption wavelength is measured by preparing a solution in which the dye is dissolved in an appropriate solvent (water, an organic solvent or a mixture thereof) at an appropriate concentration, and measuring the absorption spectrum in the visible light region thereof. can do. The maximum absorption wavelength refers to a wavelength showing the maximum absorbance among the absorption spectra in the visible light region even when the absorption spectrum has, for example, a plurality of maximums. The maximum absorption wavelength of the dye can be measured even with an ink composition in which the dye is dissolved, and it may be appropriately determined depending on the dye concentration. However, a diluted solution of the ink composition diluted 500 to 2000 times with water is prepared. It can be measured by.

A dye having a maximum absorption wavelength in the range of 350 nm or more and 450 nm or less typically exhibits a color having a hue angle ∠h ° in the range of 15 ° or more and 80 ° or less. The above-mentioned C.I. I. Reactive Orange 35, C.I. I. Reactive Orange 12, C.I. I. Reactive Orange 99, C.I. I. Acid Brown 298 and C.I. I. The acid orange 56 has a maximum absorption wavelength in the range of 350 nm or more and 450 nm or less. C. I. Reactive Orange 35, C.I. I. Reactive Orange 12 and C.I. I. The maximum absorption wavelength of the reactive orange 99 is described.

C. I. Reactive Orange 35 Maximum absorption wavelength: 414 nm
C. I. Reactive Orange 12 Maximum absorption wavelength: 420nm
C. I. Reactive Orange 99 Maximum absorption wavelength: 420nm
C. I. Acid Brown 298 Maximum absorption wavelength: 362 nm
C. I. Acid Orange 56 Maximum absorption wavelength: 414 nm

Further, in FIG. 1, C.I. I. Reactive Orange 35, C.I. I. Reactive Orange 12, C.I. I. Reactive Orange 99, C.I. I. Acid Brown 298 and C.I. I. The absorption spectrum of acid orange 56 is illustrated. For the spectrum shown in FIG. 1, a double beam spectrophotometer U-3300 (trade name, manufactured by Hitachi High-Technologies Corporation) was used to prepare an aqueous solution having a dye concentration of 10 ppm using water as a solvent, and quartz having an optical path length of 10 mm. It is the result of measurement using the cell. The measurement of the absorption spectrum of the dye is not limited to such a method, and can be measured by an appropriate method.

1.2. Cyclic amide The inkjet ink composition for printing of the present embodiment contains a cyclic amide which is liquid at room temperature and has a standard boiling point of 190 ° C. or higher and 260 ° C. or lower. The cyclic amide has a function of easily dissolving the above-mentioned dye and suppressing solidification and drying of the inkjet ink composition for printing. Further, when the standard boiling point is 190 ° C. or higher and 260 ° C. or lower, the volatilization of the cyclic amide is sufficiently suppressed, and as a result, the moisturizing property is enhanced, and as a result, the effect of suppressing the solidification and drying of the inkjet ink composition for printing is obtained. More prominently obtained.

Examples of the cyclic amide include compounds having a ring structure containing an amide group, and examples thereof include compounds represented by the following formula (6).

・・・（６）
（式（６）中、Ｒ^１は、水素又は炭素数１〜４のアルキル基を表し、ｎは、１〜４の整数を表す。また係るアルキル基は直鎖状でも分岐状でもよい。）
式（６）で表される化合物としては、２−ピロリドン［２４５℃］、１−メチル−２−
ピロリドン［２０４℃］（Ｎ−メチル−２−ピロリドン）、１−エチル−２−ピロリドン［２１２℃］（Ｎ−エチル−２−ピロリドン）、Ｎ−ビニル−２−ピロリドン［１９３℃］、１−プロピル−２−ピロリドン、１−ブチル−２−ピロリドン等のγ−ラクタム類、β−ラクタム類、δ−ラクタム類等が挙げられる。括弧内の数値は標準沸点を表す。これらの環状アミドは、１種単独で用いてもよいし、２種以上併用してもよい。

... (6)
(In the formula (6), R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 to 4, and the alkyl group may be linear or branched.)
Examples of the compound represented by the formula (6) include 2-pyrrolidone [245 ° C.] and 1-methyl-2-.
Pyrrolidone [204 ° C] (N-methyl-2-pyrrolidone), 1-ethyl-2-pyrrolidone [212 ° C] (N-ethyl-2-pyrrolidone), N-vinyl-2-pyrrolidone [193 ° C], 1- Examples thereof include γ-lactams such as propyl-2-pyrrolidone and 1-butyl-2-pyrrolidone, β-lactams and δ-lactams. The numbers in parentheses represent the standard boiling point. These cyclic amides may be used alone or in combination of two or more.

Among the cyclic amide compounds, the compounds that are liquid at room temperature include 2-pyrrolidone (25 ° C.), 1-methyl-2-pyrrolidone (-24 ° C.), and 1-ethyl-2-pyrrolidone (-77 ° C.). , N-vinyl-2-pyrrolidone (14 ° C.) and the like. The numbers in parentheses represent the melting point. The melting point of 2-pyrrolidone is as high as 25 ° C, and at room temperature (for example, room temperature, 23 ° C, 25 ° C, etc.), it may be solid at the time of purchasing the reagent, but for example, with warm water of about 40 ° C. Once heated and melted, it can remain liquid at room temperature. The inventors presume that this phenomenon is caused by a supercooled state or a freezing point depression due to moisture or the like, but in the present invention, it is assumed that the liquid is liquid at room temperature including such a state.

The total content of the cyclic amide is 1% by mass or more and 30% by mass or less, preferably 5% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 25% by mass or less with respect to the total mass of the ink composition. More preferably, it is 7% by mass or more and 15% by mass or less.

When the total content of the cyclic amide is in the above range, the dye can be sufficiently dissolved and the blending amount (concentration) of the dye can be increased. That is, among various dyes, specific dyes (for example, CI reactive orange 35, CI reactive orange 12, CI reactive orange 99, CI acid brown 298 and C.I. I. Acid Orange 56, especially CI Reactive Orange 35 and CI Acid Brown 298), is not necessarily highly soluble when used in printing inkjet ink compositions, and thus increases the concentration. It is relatively difficult to achieve high color development. However, by using the cyclic amide, the blending amount of the dye can be increased, and as a result, the color development property of the printed matter can be further improved.

1.3. Other Components The inkjet ink composition for printing of the present embodiment may contain the following components in addition to the above components.

1.3.1. Alkyl polyol The inkjet ink composition for printing of the present embodiment may contain an alkyl polyol having a standard boiling point of 180 ° C. or higher and 260 ° C. or lower. By containing such an alkyl polyol, the moisturizing property of the inkjet ink composition for printing is further enhanced, the ejection stability by the inkjet method is improved, and the evaporation of water from the recording head during long-term standing is effectively suppressed. be able to. Further, as a result, even when a dye of a kind that easily causes clogging of the nozzle is used, it is possible to maintain good leaving recovery and continuous ejection stability.

Specific examples of the alkyl polyol having a standard boiling point of 180 ° C. or higher and 260 ° C. or lower include 1,2-butanediol [194 ° C.], 1,2-pentanediol [210 ° C.], and 1,2-hexanediol [224 ° C.]. ], 1,2-Heptanediol [227 ° C], 1,3-propanediol [210 ° C], 1,3-butanediol [230 ° C], 1,4-butanediol [230 ° C], 1,5- Pentandiol [242 ° C], 1,6-hexanediol [250 ° C], 2-ethyl-2-methyl-1,3-propanediol [226 ° C], 2-methyl-2-propyl-1,3-propane Diol [230 ° C], 2-methyl-1,3-propanediol [214 ° C], 2,2-dimethyl-1,3-propanediol [210 ° C], 3-methyl-1,3-butanediol [203 ° C] ° C], 2-ethyl-1,3-hexanediol [244 ° C], 3-methyl-1,5-pentanediol [250 ° C], 2-methylpentane-2,4-diol [197 ° C], diethylene glycol [° C] 245 ° C.], dipropylene glycol [232 ° C.] and the like. The numerical value in parentheses indicates the standard boiling point. These alkyl polyols may be used alone or in combination of two or more.

When an alkyl polyol having a standard boiling point of 180 ° C. or higher and 260 ° C. or lower is contained, the content can be effective if it is 5% by mass or more based on the total mass of the inkjet ink composition for printing. It is preferably 5% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 27% by mass or less, and further preferably 10% by mass or more and 25% by mass or less.

The inkjet ink composition for printing according to the present embodiment preferably does not contain an alkyl polyol having a standard boiling point of 260 ° C. or higher. This is because an alkyl polyol having a standard boiling point of 260 ° C. or higher tends to hinder the dyeing property of the dye and cause deterioration of the color reproducibility and color development of the image. Specific examples of the alkyl polyol having a standard boiling point of 260 ° C. or higher include triethylene glycol [287 ° C.] and glycerin [290 ° C.].

In the present invention, "not containing A" does not only mean that A is not contained at all, but also means that A is not intentionally added when the composition is manufactured, and the composition is being manufactured. Alternatively, it may contain a small amount of A that is inevitably mixed or generated during storage. Specific examples of "not contained" include, for example, 1.0% by mass or more, preferably 0.5% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.05% by mass. % Or more, particularly preferably 0.01% by mass or more.

1.3.2. Surfactant The inkjet ink composition for printing according to the present embodiment may contain a surfactant. The surfactant can be used to reduce the surface tension of the inkjet ink composition for printing and to adjust and improve the wettability with a recording medium (permeability into a cloth or the like). As the surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, and these may be used in combination. Further, among the surfactants, acetylene glycol-based surfactants, silicone-based surfactants, and fluorine-based surfactants can be preferably used.

The acetylene glycol-based surfactant is not particularly limited, but for example, Surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-. F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all product names, manufactured by Air Products and Chemicals. Inc.), Orfin B, Y, P, A, STG, SPC , E1004, E1010, PD-001, PD-002W, PD-003, PD-004, PD-005, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all product names, manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol E00, E00P, E40, E100 (all product names, river) (Manufactured by Ken Fine Chemical Co., Ltd.).

The silicone-based surfactant is not particularly limited, but a polysiloxane-based compound is preferably mentioned. The polysiloxane-based compound is not particularly limited, and examples thereof include polyether-modified organosiloxanes. Examples of commercially available products of the polyether-modified organosiloxane include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (trade names, BYK-348).
KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X -22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.

As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, and specific examples thereof include BYK-340 (manufactured by Big Chemie Japan).

When a surfactant is blended in the printing inkjet ink composition, the total amount of the surfactant is 0.01% by mass or more and 3% by mass or less, preferably 0.05, based on the entire printing inkjet ink composition. It is preferably blended in an amount of% by mass or more and 2% by mass or less, more preferably 0.1% by mass or more and 1.5% by mass or less, and particularly preferably 0.2% by mass or more and 1% by mass or less.

Further, since the ink jet ink composition for printing contains a surfactant, the stability when ejecting ink from the head tends to increase. Also, the use of an appropriate amount of surfactant may improve permeability to the fabric and increase contact with the pretreatment composition.

1.3.3. pH adjuster In the ink composition of the present embodiment, a pH adjuster can be added for the purpose of adjusting the pH. The pH adjusting agent is not particularly limited, and examples thereof include an appropriate combination of an acid, a base, a weak acid, and a weak base. Examples of acids and bases used in such combinations include sulfuric acid, hydrochloric acid, nitric acid as inorganic acids, lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, dihydrogen phosphate as inorganic bases. Examples thereof include sodium, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, ammonia and the like, and examples of the organic base include triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine and trishydroxymethylaminomethane (trisopropanolamine). THAM) and the like, and examples of the organic acid include adipic acid, citric acid, succinic acid, lactic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid (BES), 4- (2-hydroxy). Ethyl) -1-piperazin ethanesulfonic acid (HEEPS), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis (2-ethanesulfonic acid) (PIPES), N- Good of (2-acetamide) -2-aminoethanesulfonic acid (ACES), coramine hydrochloride, N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid (TES), acetamide glycine, tricin, glycineamide, bicin, etc. A buffer, a phosphate buffer, a citrate buffer, a Tris buffer, or the like may be used. Further, among these, as a part or all of the pH adjuster, tertiary amines such as triethanolamine and triisopropanolamine, and carboxyl group-containing organic acids such as adipic acid, citric acid, succinic acid and lactic acid, Is preferable because the pH buffering effect can be obtained more stably.

1.3.4. Water The inkjet ink composition for printing according to the present embodiment may contain water. Examples of the water include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water, and ultrapure water from which ionic impurities have been removed as much as possible. Further, when water sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide or the like is used, the growth of bacteria and fungi can be suppressed when the inkjet ink composition for printing is stored for a long period of time.

The water content is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total amount of the inkjet ink composition for printing. be. The term "water" in the ink jet ink composition for printing includes, for example, a resin particle dispersion used as a raw material and water to be added. When the water content is 30% by mass or more, the ink jet ink composition for printing can have a relatively low viscosity. The upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less with respect to the total amount of the inkjet ink composition for printing. ..

1.3.5. Organic Solvent The inkjet ink composition for printing of the present embodiment may contain a cyclic amide having a standard boiling point of less than 190 ° C. or more than 260 ° C., a nitrogen-containing heterocyclic compound, or a water-soluble organic solvent. Examples of the cyclic amide having a standard boiling point of less than 190 ° C. or more than 260 ° C. include lactams such as ε-caprolactam [136 ° C.], and examples of the water-soluble organic solvent include lactones such as γ-butyrolactone [204 ° C.]. , Betaine compounds and the like. Further, it may contain glycol ether, which may control the wettability and permeation rate of the composition. Therefore, it may be possible to improve the color development of the image.

The glycol ether having a standard boiling point of 190 ° C. or higher and 260 ° C. or lower is selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. The glycol monoalkyl ether to be produced is preferred. More preferably, methyltriglycol (triethylene glycol monomethyl ether), butyltriglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether and the like can be mentioned, and diethylene glycol is a typical example. Monobutyl ether [230 ° C.] can be mentioned. The numbers in parentheses represent the standard boiling point.

A plurality of such organic solvents may be mixed and used. In addition, the blending amount of the organic solvent described in this item is the total amount with respect to the total amount of the inkjet ink composition for printing from the viewpoint of adjusting the viscosity of the inkjet ink composition for printing and preventing clogging due to the moisturizing effect. 0.2% by mass or more and 30% by mass or less, preferably 0.4% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, still more preferably 0.7% by mass or more and 10% by mass or less. It is as follows.

1.3.6. Ureas Ureas may be used as a moisturizer for the inkjet ink composition for printing or as a dyeing aid for improving the dyeing property of the dye. Specific examples of ureas include urea, ethylene urea, tetramethylurea, thiourea, 1,3-dimethyl-2-imidazolidinone and the like. When ureas are contained, the content thereof can be 1% by mass or more and 10% by mass or less with respect to the total mass of the ink composition.

1.3.7. Sugars Sugars may be used for the purpose of suppressing solidification and drying of the inkjet ink composition for printing. Specific examples of the saccharide include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbit), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like.

1.3.8. Chelating Agent A chelating agent may be used for the purpose of removing unnecessary ions in the ink jet ink composition for printing. Examples of the chelating agent include ethylenediaminetetraacetic acid and salts thereof (ethylenediaminetetraacetic acid dihydrogen disodium salt, or ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, metaphosphate, etc.) and the like. Be done.

1.3.9. Preservatives and Antifungal Agents Inkjet ink compositions for printing may use preservatives and antifungal agents. Examples of preservatives and antifungal agents include sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzoisothiazolin-3-one (Zeneca). Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL.2, Proxel TN, Proxel LV), 4-chloro-3-methylphenol (Bayer's Preventol CMK, etc.) and the like can be mentioned.

1.3.10. Other components other than the above may include additives that can be usually used in ink composition for inkjet, such as rust preventives, antioxidants, ultraviolet absorbers, oxygen absorbers, and solubilizing agents. good.

1.4. PH of inkjet ink composition for printing
The ink composition for inkjet printing of the present embodiment has a pH of 5.8 or more and 10.5 or less, preferably 6.0 or more and 10.0 or less, more preferably 6.0 or more and 9.5 or less, and further preferably 7. It is preferably 0.0 or more and 8.5 or less. When the pH of the inkjet ink composition for printing is in this range, the storage stability of the dye in the ink composition is improved, and the color development and the hue of the obtained image are unlikely to change. It can be reproduced well.

The pH of the inkjet ink composition for printing is, for example, the liquidity of the above-mentioned dye, the type of counterion when the dye is ionic, their balance, or the selection of the type of pH adjuster or the adjustment of the amount added. Therefore, it can be adjusted to the above range.

1.5. Manufacture and Physical Characteristics of Ink Composition The ink composition according to the present embodiment is obtained by mixing the above-mentioned components in an arbitrary order and, if necessary, filtering or the like to remove impurities. As a method of mixing each component, a method of sequentially adding materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirring and mixing is preferably used.

The ink composition according to the present embodiment preferably has a surface tension of 20 to 40 mN / m, preferably 22 to 35 mN / m, from the viewpoint of a balance between printing quality and reliability as an ink jet printing ink. Is more preferable. From the same viewpoint, the viscosity of the ink composition at 20 ° C. is preferably 1.5 to 10 mPa · s, more preferably 2 to 8 mPa · s. In order to keep the surface tension and viscosity within the above ranges, the types of the above-mentioned water-soluble solvent and surfactant, the amount of these and water added, and the like may be appropriately adjusted.

1.6. Action Effect According to the inkjet ink composition for printing of the present embodiment, colors in the range of hue angle ∠h ° of 15 ° or more and 80 ° or less can be expressed with good color development in the printed matter without mixing multiple colors. Moreover, it is possible to suppress the change in hue (light resistance) over time. That is, by containing the cyclic amide having a standard boiling point of 190 ° C. or higher and 260 ° C. or lower in an amount of 5% by mass or more and 30% by mass or less, the dye can be dissolved in a sufficient amount, thereby providing good color development in the printed matter. Obtainable. Then, colors in the range of hue angle ∠h ° of 30 ° or more and 65 ° or less can be expressed without mixing a plurality of colors, and hue change (light resistance) over time can be suppressed.

2. 2. Ink set The above-mentioned inkjet ink composition for printing according to the present embodiment includes an inkjet ink composition for printing containing a dye of any other color, a pretreatment composition described later, and any number of compositions. Ink sets that are combined by the number of colors can be configured.

According to the ink set of the present embodiment, colors in the range of hue angle ∠h ° of 15 ° or more and 80 ° or less can be expressed in a printed matter with good color development without mixing a plurality of colors, and over time. Hue change (light resistance) can be suppressed. Furthermore, C.I. I. Reactive Orange 35 or C.I. I. When Acid Brown 298 is used, it is possible to express colors in the range of hue angle ∠h ° of 20 ° or more and 75 ° or less, more preferably 25 ° or more and 70 ° or less, without mixing multiple colors. It is possible to remarkably suppress various hue changes (light resistance).

Further, the inkjet ink composition for printing of the present embodiment can be an ink set containing the pretreatment composition described later, and by using the pretreatment composition, even better printing can be realized.

According to the ink set of the present embodiment, colors in the range of hue angle ∠h ° of 15 ° or more and 80 ° or less can be expressed without mixing a plurality of colors, and at least colors in the range of the hue angle can be expressed. It is possible to suppress the change in hue (light resistance) of the printed portion over time.

3. 3. Recording method (printing method)
The recording method according to the present embodiment includes a step of printing the above-mentioned inkjet ink composition for printing on a fabric (hereinafter, also referred to as a “printing step”). Hereinafter, the steps included in the recording method according to the present embodiment and the steps that can be included will be described for each step.

3.1. Recording medium The inkjet ink composition for printing of the present embodiment is used by adhering it to a recording medium. The recording medium is not particularly limited, and examples thereof include various fabrics. The material constituting the fabric is not particularly limited, and is, for example, natural fibers such as cotton, linen, wool and silk, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide and polyurethane, and biodegradability such as polylactic acid. Examples thereof include fibers, and these blended fibers may be used. As the cloth, the fibers listed above may be in any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Of these, the fabric used in the present embodiment is more preferably formed of fibers containing cellulose such as cotton and linen. By using such a cloth, it is possible to obtain better dyeing property of the inkjet ink composition for printing.

The basis weight of the fabric used in the present embodiment is 1.0 oz (ounce) or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8.0 oz or less, still more preferable. Is in the range of 4.0 oz or more and 7.0 oz or less.

3.2. Pretreatment Step The recording method according to the present embodiment may include a pretreatment step of imparting a pretreatment composition containing at least one of an alkaline agent, an acid and a hydrotropy agent to the fabric. This further improves the dyeing property of the dye.

Examples of the method of applying the pretreatment composition to the fabric include a method of immersing the fabric in the pretreatment composition, a method of applying the pretreatment composition with a roll coater or the like, and a method of injecting the pretreatment composition (for example). , Inkjet method, spray method) and the like, and any method can be used.

<Pretreatment composition>
The pretreatment composition contains at least one of an alkaline agent, an acid and a hydrotropy agent. The content of these components in the pretreatment composition can be appropriately set according to the type of fabric and the like, and is not particularly limited.

When an alkaline agent is used, the alkaline agent is preferably used from the viewpoint of further improving the dyeing property of the reactive dye. Specific examples of the alkaline agent include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, trisodium phosphate, sodium acetate and the like.

When an acid dye is used, the acid is preferably used from the viewpoint of further improving the dyeing property of the dye. As specific examples of the acid, a carboxylic acid having a carboxyl group in the molecule, an organic acid such as a sulfonic acid having a sulfo group, or an ammonium salt of a strong acid is generally used, and among them, ammonium sulfate is particularly used. Is preferable.

Hydrotropy agents are preferably used because they improve the color development of the recorded image. Examples of the hydrotropy agent include ureas exemplified in the above section of the inkjet ink composition for printing.

The pretreatment composition of the present embodiment may contain water. The water is the same as described in the above-mentioned inkjet ink composition for printing. The content of water is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more, based on the total amount of the pretreatment composition.

The pretreatment composition of the present embodiment may contain a water-soluble organic solvent. The water-soluble organic solvent may be able to improve the wettability of the pretreatment composition with respect to the recording medium. Examples of the water-soluble organic solvent include at least one of esters, alkylene glycol ethers, cyclic esters and alkoxyalkylamides. Further, as the water-soluble organic solvent, nitrogen-containing compounds, saccharides, amines and the like other than these may be used. Further, the pretreatment composition may contain a water-soluble organic solvent that can be used in the above-mentioned inkjet ink composition for printing.

The pretreatment composition may contain a plurality of water-soluble organic solvents. When the water-soluble organic solvent is contained, the total content of the water-soluble organic solvent with respect to the whole pretreatment composition is 0.1% by mass or more and 20% by mass or less, preferably 0.3% by mass or more and 15% by mass or less. , More preferably 0.5% by mass or more and 10% by mass or less, still more preferably 1% by mass or more and 7% by mass or less.

The pretreatment composition may contain a glue. Examples of the glue include starch substances such as corn and wheat, cellulosic substances such as carboxymethyl cellulose and hydroxymethyl cellulose, polysaccharides such as sodium alginate, arabia gum, locust bean gum, tranth gum, guar gum, and tamarind seeds, gelatin and casein. Examples thereof include natural water-soluble polymers such as proteins, tannins and lignins, and synthetic water-soluble polymers such as polyvinyl alcohol-based compounds, polyethylene oxide-based compounds, acrylic acid-based compounds, and maleic anhydride-based compounds.

The pretreatment composition of the present embodiment may contain a surfactant. The surfactant is the same as described in the above-mentioned inkjet ink composition for printing. When a surfactant is added to the pretreatment composition, the total amount of the surfactant is 0.01% by mass or more and 3% by mass or less, preferably 0.05% by mass or more, based on the entire pretreatment composition. It is preferably blended in an amount of% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less, and particularly preferably 0.2% by mass or more and 0.5% by mass or less. When the pretreatment composition contains a surfactant, it is possible to control the permeability and wettability of the ink applied on the pretreated fabric, improve the color development property of the printed material, and suppress bleeding.

The pretreatment composition of the present embodiment includes water, antioxidants, preservatives, fungicides, chelating agents, pH adjusters, surfactants, viscosity regulators, antioxidants, fungicides, etc. in printing. Ingredients commonly used in pretreatment compositions may be included.

Further, the pretreatment composition may be adhered to the fabric by an inkjet method, and in such a case, the viscosity at 20 ° C. is preferably 1.5 mPa · s or more and 15 mPa · s or less. It is more preferably 1.5 mPa · s or more and 5 mPa · s or less, and more preferably 1.5 mPa · s or more and 3.6 mPa · s or less.

On the other hand, the pretreatment composition may be used by a method other than the inkjet method. As such a method, a method of applying the pretreatment composition to the cloth using various sprays, a method of immersing the cloth in the pretreatment composition and applying it, a method of applying the treatment liquid to the cloth by a brush or the like, etc. Non-contact type, contact type, or a combination thereof can be mentioned.

When the pretreatment composition is attached to the fabric by a method other than the inkjet method, the viscosity at 20 ° C. may be higher than that by the inkjet method, for example, 1.5 mPa · s or more and 100 mPa ·. It is preferably s or less, preferably 1.5 mPa · s or more and 50 mPa · s or less, and more preferably 1.5 mPa · s or more and 20 mPa · s or less. The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), raising the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

3.3. Printing Step The recording method according to the present embodiment includes a printing step of printing the above-mentioned inkjet ink composition for printing on a cloth. Specifically, the ink droplets ejected by the inkjet recording method are attached to the cloth to form an image on the cloth. The inkjet recording method may be any method, and examples thereof include a charge deflection method, a continuous method, and an onden mand method (piezo type, bubble jet (registered trademark) type). Among these inkjet recording methods, a method using a piezo type inkjet recording device is particularly preferable.

3.4. Heat Treatment Step The recording method according to the present embodiment may include a heat treatment step of heat-treating the fabric on which the above ink composition is printed. By performing the heat treatment step, the dye is satisfactorily dyed on the fiber. As the heat treatment step, a conventionally known method can be used, and examples thereof include an HT method (high temperature steaming method), an HP method (high pressure steaming method), and a thermosol method.

The temperature in the heat treatment step is preferably in the range of 90 ° C. or higher and 110 ° C. or lower from the viewpoint of reducing damage to the fabric.

3.5. Cleaning Step The recording method according to the present embodiment may include a cleaning step of cleaning the printed material. The cleaning step is preferably performed after the above heat treatment step, and the dye not dyed on the fibers can be effectively removed. The washing step can be performed using, for example, water, and soaping treatment may be performed if necessary.

3.6. Other Steps The recording method according to the present embodiment includes a drying step of the pretreatment composition for drying the pretreatment composition applied to the fabric after the above-mentioned pretreatment step and before the above-mentioned printing step. You may go out. The pretreatment composition may be dried by natural drying, but it is preferably dried with heating from the viewpoint of improving the drying rate. When heating is involved in the drying step of the pretreatment composition, the heating method is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a thermofix method. Further, the heat source for heating is not limited to the following, and examples thereof include infrared rays (lamps).

3.7. Action Effect According to the recording method of the present embodiment, by using the above-mentioned inkjet ink composition for printing in the printing step, a plurality of colors having a hue angle ∠h ° in the range of 15 ° or more and 80 ° or less can be produced. It is possible to express good color development in printed matter without color mixing, suppress hue change (light resistance) over time, and improve discharge reliability (clogging recovery and continuous discharge stability). can.

4. Examples and Comparative Examples Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

4.1. Preparation of Inkjet Ink Composition for Printing Example and each component are placed in a container so as to have the composition shown in Table 1, mixed and stirred with a magnetic stirrer for 2 hours, and then filtered with a membrane filter having a pore size of 5 μm. An ink composition according to a comparative example was obtained. The numerical values in Table 1 indicate mass%, and ion-exchanged water was added so that the total mass of the ink composition was 100% by mass.

表１において、化合物名以外で記載した成分は次の通りである。

In Table 1, the components described other than the compound names are as follows.

・ C. I. Reactive Orange 35 Maximum absorption wavelength: 414 nm
・ C. I. Reactive Orange 12 Maximum absorption wavelength: 420nm
・ C. I. Reactive Orange 99 Maximum absorption wavelength: 420nm
・ C. I. Reactive Yellow 2 Maximum absorption wavelength: 404 nm
・ C. I. Reactive Red 31 Maximum absorption wavelength: 546nm
・ C. I. Acid Brown 298 Maximum absorption wavelength: 362 nm
・ C. I. Acid Orange 56 Maximum absorption wavelength: 414 nm
・ C. I. Acid Red 289 Maximum absorption wavelength: 527nm
・ C. I. Acid Yellow 79 Maximum absorption wavelength: 402 nm
BES (N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid: reagent)
-Orphin PD-002W (trade name, manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol-based surfactant)
・ Proxel XL2 (trade name, manufactured by Arch Chemicals)
In the name of the dye, those with "reactive" were classified as reactive dyes, and those with "acid" were classified as acid dyes.

For the maximum absorption wavelength of the dye, a double beam spectrophotometer U-3300 (trade name, manufactured by Hitachi High-Technologies Corporation) was used to prepare an aqueous solution having a dye concentration of 10 ppm using water as a solvent, and quartz having an optical path length of 10 mm. Measured using cells. Moreover, the spectral spectra of some of the dyes thus obtained are already shown in FIG. The maximum absorption wavelength of the dye can be measured even with an ink composition in which the dye is dissolved, and it may be appropriately determined depending on the dye concentration. However, a diluted solution obtained by diluting the ink composition with water 500 to 2000 times is prepared. This can be measured by the above-mentioned device.

4.2. Ink set An ink set as shown in Table 2 was configured. The ink set was a set consisting of four types of ink: ink 1, ink 2, ink 3, and ink 4. Inks 1 to 4 correspond to brown, magenta, yellow, and black inks, respectively. Then, the ink sets of Examples 21 to 25 are inked with the ink jet ink compositions for printing of Examples 1, 2, 3, 18, and 19, respectively, and the inks differing only in the colorant density (5% by mass). The ink set was set. Further, the ink set of Comparative Example 6 was an ink set in which ink 1 was used as ink 1 having a color material density different from that of the inkjet ink composition for printing of Comparative Example 1 (5% by mass). Further, in the ink set of Comparative Example 7, the ink set of the inkjet ink composition for printing of Comparative Example 5 has one color material type (CI Acid Yellow 79), and the inks have different color material densities (5% by mass). Was set as ink 1. The inks 2 to 4 of each example of the ink set were inks having a different color material type (shown in Table 2) and density (5% by mass) from the inkjet ink composition for printing of Example 1 above.

Some of the dyes that first appeared in Table 2 are as follows.
・ C. I. Reactive Blue 15 Maximum absorption wavelength: 672 nm
・ C. I. Reactive Black 39 Maximum absorption wavelength: 610 nm
・ C. I. Acid Blue 112 Maximum absorption wavelength: 589 nm
・ C. I. Acid Black 172 Maximum absorption wavelength: 573 nm

4.3. Preparation of pretreatment composition (1) Preparation method of pretreatment liquid when using reactive dye Polyoxyethylene diisopropyl ether (oxyethylene = 30 mol) by 5 parts by mass, etherified carboxymethyl cellulose by 5 parts by mass, urea (hydrotropy) Agent) 100 parts by mass and 10 parts by mass of sodium m-nitrobenzene sulfonate are mixed well, and then the mixture is stirred at 60 ° C. for 30 minutes while adding little by mass to 1000 parts by mass of ion-exchanged water. Then, 30 parts by mass of sodium carbonate (alkaline agent) was further added to the stirred solution and stirred for 10 minutes, and this solution was filtered through a membrane filter having a pore size of 10 μm to obtain a pretreatment composition.

(2) Preparation method of pretreatment liquid when using acid dyes Except for the fact that ammonium sulfate was used instead of sodium carbonate, which is an alkaline agent, and that sodium m-nitrobenzene sulfonate was not added, the above-mentioned before using reactive dyes. A pretreatment liquid for acid dyes was prepared in the same manner as in the preparation of the treatment liquid.

4.4. Evaluation method 4.4.1. Hue angle evaluation of printed matter The hue angle ∠h ° of the printed matter was evaluated as follows for the inkjet ink composition for printing of Examples 1 to 20 and the inkjet ink composition for printing of Comparative Examples 1 to 5. ..
Using a fabric (100% cotton, viscose, silk, wool or PA elastomer) having a whiteness L * in the range of 85 to 95, the pretreatment composition obtained as described above is applied to the fabric. , Squeezed with a mangle at a pickup rate of 80% and dried. After that, the cartridge of the inkjet printer PX-G930 (manufactured by Seiko Epson Corporation) was filled with the inkjet ink composition for printing prepared above, and the pretreated cloth was charged with an ink injection amount of 23 mg at a resolution of 1440 dpi × 720 dpi. Under the condition of / inch ² , each printing inkjet ink composition was adhered and an image was recorded (printed).

Next, the fabric on which the image was recorded was steamed at 102 ° C. for 10 minutes, and then 90 ° C. was used with an aqueous solution containing 0.2% by mass of Laccol STA (surfactant manufactured by Meisei Kagaku Co., Ltd.). Was washed for 10 minutes and dried to obtain each evaluation sample. The obtained evaluation sample was evaluated according to the following criteria by determining the hue angle ∠h ° according to the method of JISZ8722: 2009. The whiteness L * is Spectrolino (X-RITE colorimeter, measurement condition: light source D65).
, Filter D65, φ2 degrees). The evaluation results are shown in Table 3.
A: Hue angle ∠h ° was 20 ° or more and 75 ° or less B: Hue angle ∠h ° was 15 ° or more and less than 20 ° or more than 75 ° and 80 ° or less C: Hue angle ∠h ° was 15 Less than ° and above 80 °

4.4.2. Light resistance evaluation The light resistance evaluation of the inkjet ink composition for printing of Examples 1 to 20 and the inkjet ink composition for printing of Comparative Examples 1 to 5 was performed as follows.
Using the evaluation sample obtained in the above "4.4.1. Hue angle evaluation of printed matter", it was carried out according to ISO 105 B02, and the result was evaluated according to the following criteria. The evaluation results are shown in Table 3. In this evaluation, discoloration and fading are examined to determine the fastness, and the hue angle is not directly measured, but at least discoloration can be determined.
A: Light resistance is 5th grade or higher B: Light resistance is 4th grade or higher and lower than 5th grade C: Light resistance is 3rd grade or higher and lower than 4th grade D: Light resistance is lower than 3rd grade E: Hue angle h ° of printed matter is 30 ° Not subject to evaluation because it does not fall within the range of 65 ° or more.

4.4.3. Evaluation of color development (color development density) The above "4.4.1. An evaluation sample was obtained in the same manner as in "Evaluation of hue angle". The evaluation of color development is performed by measuring the OD value of the image (color development density: the sum of the OD value of the yellow component and the OD value of the magenta component) with a colorimeter (trade name "Spectrolino, manufactured by X-RITE"). The image was evaluated based on the measured OD value. The evaluation criteria are shown below. The evaluation results are shown in Table 3.

A: OD value is 2.7 or more B: OD value is 2.5 or more and less than 2.7 C: OD value is 2.3 or more and less than 2.5 D: OD value is less than 2.3

4.4.4.4. Evaluation of Clogging Reliability The cartridge of the inkjet printer PX-G930 (manufactured by Seiko Epson Corporation) was filled with the above-mentioned inkjet ink composition for printing. After filling, print the nozzle check pattern to confirm that there is no filling defect or nozzle clogging, and then return the head to the home position (that is, with the head cap on the head nozzle surface). It was left for one week in an environment of ° C./40% RH. After leaving, the nozzle check pattern was printed and the ejection state of the nozzle was observed to evaluate the clogging recovery property of the ink jet head of the ink composition. The evaluation criteria are shown below. The evaluation results are shown in Table 3.

A: Ink composition was normally ejected from all nozzles with one cleaning operation B: Ink composition was normally ejected from all nozzles within the range of 2 to 5 cleaning operations C: Cleaning operation Ink composition was normally ejected from all nozzles within the range of 6 to 10 times. D: Cleaning operation was required 11 times or more before the ink composition was normally ejected from all nozzles, or cleaning. There was a nozzle that did not eject normally even if the operation was performed 11 times or more.

4.4.5. Continuous ejection stability evaluation After filling the cartridge of the inkjet printer PX-G930 (manufactured by Seiko Epson Corporation) with the above inkjet ink composition for printing, 1000 sheets of continuous solid printing are performed on A4 plain paper, and no cleaning operation is performed. The average value of the number of sheets that can be printed continuously was obtained and evaluated by the following test methods and criteria. The evaluation results are shown in Table 3.

Test method (1): Printing is interrupted at the stage where printing defects (dot disorder, omission, bending) occur during printing, and a cleaning operation is performed to recover. If multiple cleanings are required for recovery, the multiple cleaning operations are combined and regarded as one deficiency.

Test method (2): If printing is temporarily stopped due to the ink end of the ink cartridge, or if there is a printing defect that can be clearly determined to be caused by the ink end, no count is set, and the ink cartridge is promptly replaced to print. Resume.
(Evaluation criteria)
A: Average number of continuous prints is 80 or more B: Average number of continuous prints is 40 or more and less than 80 C: Average number of continuous prints is 20 or more and less than 40 D: Average number of continuous prints is less than 20

4.4.6. Evaluation of Ink Sets The light resistance of the ink sets of Examples 21 to 25 and Comparative Examples 6 and 7 shown in Table 2 was evaluated as follows. Using each ink set, the amount of ink applied is controlled at a resolution of 1440 dpi x 720 dpi or 720 dpi x 720 dpi so that the hue angle ∠h ° of the obtained stamped image is 15 ° or more and 80 ° or less. The evaluation was carried out by the same evaluation method as the above-mentioned light resistance evaluation of the inkjet ink composition for printing, except that the printing was performed. The printing was performed on 100% cotton fabrics, viscose, silk, wool, and PA elastomer fabrics.

4.5. Evaluation Results Looking at the results of the printing inkjet ink compositions of each example, all dyes have a hue angle ∠h ° defined in the CIELAB color space on the recording medium in the range of 20 ° or more and 75 ° or less. By including 5% by mass or more and 30% by mass or less of the cyclic amide which is liquid at room temperature and has a standard boiling point of 190 ° C. or more and 260 ° C. or less, the hue angle ∠h ° is 20 ° or more and 75 ° or less. It has been found that the colors in the above range can be expressed with good color development in the printed matter without mixing a plurality of colors, and the hue change (light resistance) with time can be suppressed.

This means that since the cyclic amide having a standard boiling point of 190 ° C. or higher and 260 ° C. or lower is contained in an amount of 5% by mass or more and 30% by mass or less, the dye can be dissolved in a sufficient amount, so that good color development can be obtained in the printed matter. I think it shows that it can be done. From the results of the examples, it is possible to express colors in the range of hue angle ∠h ° of 20 ° or more and 75 ° or less without mixing multiple colors, so that it is possible to suppress the change in hue (light resistance) over time. There was found.

On the other hand, in Comparative Example 1 using a dye having a hue angle ∠h ° outside the range of 15 ° or more and 80 ° or less, it was not possible to print a predetermined hue angle. Further, in Comparative Example 2, the light resistance was poor due to the color mixing. Further, the clogging recovery and discharge stability of Comparative Examples 1 and 2 were insufficient, but this was done by using reactive yellow 2 and reactive red 31 as coloring materials and further adding an alkyl polyol. Is an excess amount of 18% by mass, so it can be inferred that it is easy to thicken. The details of this mechanism are not clear at this time, but it is considered that one of the causes is that the ease of thickening at the time of water evaporation changes depending on the combination of the type and / or the amount of the coloring material and the alkyl polyol added.

Further, in Comparative Example 3, the color-developing property was poor, which is considered to be due to the small content of the nitrogen-containing cyclic compound. Further, from Comparative Example 4, it was found that when the addition amount of 2-pyrrolidone exceeded 30% by mass, the color-developing property was lowered. This is considered to be due to the increased permeability of the ink to the fabric. Further, in Comparative Example 4, the clogging reliability and ejection stability are remarkably lowered, which is considered to be because impurities from the members of the ink flow path are dissolved in the ink and precipitated as foreign matter. Regarding Comparative Example 5 using an acid dye, it was found that when the amount of 2-pyrrolidone added exceeded 30% by mass, the color-developing property was lowered.

On the other hand, looking at Examples 2 and 3 for each example, it was found that there was a slight difference in light resistance due to the difference in dye type, and RO35 was the best. Further, from the results of Examples 13 and 14, it was found that when the pH range was out of the range of 6 to 10, the color-developing property was slightly lowered. It is considered that this is partly because the reactivity of the dye is lowered. Further, in Example 4, no decrease in light resistance was observed even when the three dyes were used in combination. This is C.I. I. It is considered that this is due to the fact that the amount of reactive orange 35 added is sufficient. Therefore, C.I. I. When it becomes necessary to fine-tune the hue of the printed matter printed with only the reactive orange 35, another dye (CI reactive orange 12, CI reactive orange 99) is added in total to 1. It was found that the light resistance level could be maintained even when finely adjusted by adding about% by mass.

Further, from the results of Examples 15 and 16, it can be seen that when the amount of the alkyl polyol added is out of the range of 10% by mass or more and 25% by mass or less, the clogging recovery property and / or the continuous discharge stability tends to decrease. Was done. It is considered that this is because in Example 15 in which the amount of the alkyl polyol added is less than 10% by mass, it is difficult to secure the moisturizing property and it is easy to dry. Further, in Example 16 in which the amount of the alkyl polyol added is larger than 25% by mass, it is considered that the viscosity tends to increase during drying. Further, looking at Example 17 using an alkyl polyol having a high boiling point, there is a tendency that the recovery from clogging and / or the continuous discharge stability is lowered, which is also considered to be one of the causes of the thickening. ..

Further, from the results in Table 2, the ink sets of each example are more different than those of Comparative Examples 6 and 7 in which a composite ink containing a plurality of dyes or an ink having a plurality of hues is combined to realize a brown hue. It was found to show excellent light resistance (that is, suppression of changes in hue over time).

The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, the present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. Further, the present invention includes a configuration having the same action and effect as the configuration described in the embodiment or a configuration capable of achieving the same object. Further, the present invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (8)

C. I. Reactive Orange 35, C.I. I. Reactive Orange 99, C.I. I. Acid Brown 298 and C.I. I. With more than one type of acid orange 56 ,
Cyclic amides that are liquid at room temperature and have a standard boiling point of 190 ° C or higher and 260 ° C or lower are 5% by mass or more and 30% by mass or less.
An inkjet ink composition for printing, wherein the hue angle ∠h ° defined in the CIELAB color space on a recording medium is in the range of 15 ° or more and 80 ° or less. In claim 1,
An inkjet ink composition for printing in which the hue angle ∠h ° defined in the CIELAB color space on a recording medium is in the range of 20 ° or more and 75 ° or less. In claim 1 or 2,
An inkjet ink composition for printing, wherein the dye is a dye having a maximum absorption wavelength in the range of 350 nm or more and 450 nm or less. In any one of claims 1 to 3 ,
An inkjet ink composition for printing, wherein the content of the dye is 3% by mass or more and 15% by mass or less. In any one of claims 1 to 4 ,
An inkjet ink composition for printing, wherein the pH of the inkjet ink composition for printing is 6 or more and 10 or less. In any one of claims 1 to 5 ,
The inkjet ink composition for printing contains an alkyl polyol having a standard boiling point of 180 ° C. or higher and 260 ° C. or lower.
An inkjet ink composition for printing, wherein the content of the alkyl polyol is 10% by mass or more and 25% by mass or less. An ink set comprising the inkjet ink composition for printing according to any one of claims 1 to 6. The pretreatment step of applying a pretreatment composition containing at least one of an alkaline agent, an acid and a hydrotropy agent to a fabric, and the inkjet ink composition for printing according to any one of claims 1 to 6. A recording method comprising a printing step of printing on the fabric using the cloth.

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