JP2009235598A - Inkjet printing method and printed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet printing method by which insufficiency of color reproductivity, and difference in hue between an ink-imparted surface and an opposite surface of the ink-imparted surface are hardly caused, and to provide a printed product printed by the method. <P>SOLUTION: The inkjet printing method of a fabric for combined application, constituted of a polytrimethylene terephthalate fiber, and/or a polybutylene terephthalate fiber and a polyethylene terephthalate fiber and/or cation-dyeable polyester fiber includes carrying out the inkjet printing on the fabric for the combined application by using a disperse dye having a melting point of 160°C as a coloring material for blue and red inks, and heat-treating the resultant fabric with a superheated steam at 140-160°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method of inkjet printing a mixed fabric composed of polytrimethylene terephthalate fiber and / or polybutylene terephthalate fiber, polyethylene terephthalate fiber and / or cationic dyeable polyester fiber, and a printed matter printed by the method.

  Polytrimethylene terephthalate (PTT) fibers and polybutylene terephthalate (PBT) fibers have better texture and stretchability than polyethylene terephthalate (PET) fibers, and various studies have been made on their use. Has been put to practical use.

  In Patent Document 1, in printing PTT fibers, a carrier agent is used in combination with color paste, and after printing, heat treatment is performed in superheated steam of 150 ° C. or lower or saturated steam of 110 ° C. or lower, thereby fading the color in the print. There is disclosed a printing method for PTT fibers that has a clear color developability, has a high fastness, and has excellent texture and stretch recovery properties. Also, the printing of PBT fibers is performed in substantially the same process as the printing conditions for the PTT fibers, and the heat treatment temperature is set to be about 10 to 20 ° C. lower than the printing conditions for PET fibers.

  At present, PTT fibers and PBT fibers are not configured as a fabric by themselves, but are often mixed with other fibers. Other fibers that are used in combination are nylon fibers, polyurethane fibers, PET fibers, CDP fibers, etc. Among them, they are the same polyester fibers and can be dyed with the same dye (dispersion dye). Therefore, many mixed use with PET fiber and CDP fiber is seen.

  In addition, for the purpose of giving further added value to the mixed fabrics, it is also made to arrange colors, patterns, patterns, etc. on a part or the whole of the fabrics by inkjet printing. When a mixed fabric composed of polytrimethylene terephthalate fiber and / or polybutylene terephthalate fiber and polyethylene terephthalate fiber and / or cationic dyeable polyester fiber is to be printed by an ink jet method, a disperse dye ink is usually used as the ink. Is selected.

  As a problem in that case, in the coloring process after ink jet printing, due to the dispersion of the disperse dye ink into the mixed fabric, there is a color reproducibility failure or a hue difference between the ink application surface of the fabric and the opposite surface of the ink application surface. It sometimes happens. It has been found by experiments of the present inventors that this phenomenon is remarkable particularly when an intermediate color such as gray or beige is expressed using blue ink or red ink.

  About this cause, the disperse dye having a melting point lower than the temperature of the color development step is dissolved in the disperse dye printed on the fabric by the heat of 140 to 160 ° C. applied in the subsequent color development step, so that the inside of the fabric. This is presumably because of the rapid penetration. In particular, the fact that this phenomenon is prominent in gray and beige colors using blue ink and red ink is because disperse dyes of blue ink and red ink often have melting points below the temperature of the color development step. It is thought that.

JP 2002-371482 A

  In view of the above circumstances, the present invention provides poor color reproducibility when ink-jet printing a mixed fabric composed of polytrimethylene terephthalate fiber and / or polybutylene terephthalate fiber, polyethylene terephthalate fiber and / or cationic dyeable polyester fiber. An object of the present invention is to provide an ink jet printing method and a printed matter printed by the method in which there is no difference in hue between the ink application surface and the opposite surface of the ink application surface of the fabric.

  With respect to the above problems, the object of the present invention can be achieved by the following configuration. That is, this invention is the following inkjet printing method and the printed matter printed by this method.

  1) A method for inkjet printing a mixed fabric composed of polytrimethylene terephthalate fiber and / or polybutylene terephthalate fiber and polyethylene terephthalate fiber and / or cationic dyeable polyester fiber, wherein blue and An inkjet printing method in which after performing inkjet printing using a disperse dye having a melting point of 160 ° C. or higher as a coloring material for red ink, heat treatment is performed with superheated steam at 140 to 160 ° C.

  2) The blue ink is C.I. I. Disperse blue 56, 60, 77, 165, 214 and 284 containing one or more disperse dyes selected from the group consisting of I. The inkjet printing method according to 1) above, which contains one or more disperse dyes selected from the group consisting of Disperse Red 60, 86, 152, 177, 179 and 343.

  3) Printed matter printed by the inkjet printing method described in 1) or 2) above.

  According to the inkjet printing method of the present invention, there is provided an inkjet printing method and a printed matter printed by the method, in which there is no color reproducibility failure or hue difference between the ink-applied surface of the fabric and the opposite surface of the ink-applied surface. can do.

  The blue and red ink coloring materials used in the inkjet printing method of the present invention are disperse dyes having a melting point of 160 ° C. or higher. When the disperse dye contained in the blue and red inks is a disperse dye having a melting point of 160 ° C. or higher, poor color reproducibility or a difference in hue between the ink application surface of the fabric and the ink application surface may occur. Absent. Most of the disperse dyes contained in yellow ink have a melting point of 160 ° C. or higher. Actually, yellow is a color reproducibility defect or on the opposite side of the ink application surface and the ink application surface of the fabric. Therefore, there is no need to pay particular attention to the selection of disperse dyes. The melting point of the disperse dye can be easily measured by thermal analysis using a differential scanning calorimeter (DSC).

  As for blue and red inks having a melting point of 160 ° C. or higher, specifically, for blue, C.I. I. When one or more disperse dyes selected from the group consisting of Disperse Blue 56, 60, 77, 165, 214 and 284 are red, C.I. I. One or more disperse dyes selected from the group consisting of Disperse Red 60, 86, 152, 177, 179 and 343 are preferred.

  In addition to the three primary color inks of red, blue, and yellow, inks installed in the ink jet printer include neutral color inks such as gray, beige, and brown, black ink, and the like. Many of the disperse dyes contained in these inks have a high melting point, and it is not necessary to select them as strictly. However, if a higher effect is desired, all disperse dyes contained in these inks It is preferable that the melting point is 160 ° C. or higher.

  The content of the disperse dye in the ink is preferably 0.05 to 20% by weight with respect to the total amount of the ink. If the content is less than 0.05% by weight, sufficient coloring cannot be obtained, and if it exceeds 20% by weight, it becomes excessive and the cost is increased.

  The average particle size of the disperse dye in the ink is preferably 0.01 to 0.35 μm, and more preferably 0.02 to 0.30 μm. This is because the discharge from the inkjet nozzle can be stably performed within this range.

  The ink contains at least a disperse dye, a dispersant, and an aqueous solvent.

  As the dispersant, any of an anionic compound containing an anionic surfactant and a nonionic compound containing a nonionic surfactant can be used. Examples of the anionic compound include fatty acid salts, alkyl sulfate salts, alkylbenzene sulfones. Acid salts, alkyl naphthalene sulfonates, lignin sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates and substituted derivatives thereof, etc. as nonionic compounds Is polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alcohol Triethanolamine, glycerol fatty acid ester, and an oxyethylene oxypropylene block polymer and their substituted derivatives.

  The content of the dispersant in the ink is preferably 0.1 to 15% by weight and more preferably 0.5 to 10% by weight with respect to the total amount of the ink. When the content of the dispersant is less than 0.1% by weight, it cannot be adsorbed to the entire disperse dye particles present in the water-soluble dye, and the disperse particles exhibit aggregation, and the coarsened particles are settled. If the amount exceeds 15% by weight, the dispersant present without adsorbing to the dispersed particles in the ink may precipitate and agglomerate to reduce the stability of the ink. is there.

  The aqueous solvent can contain an auxiliary solvent in addition to water. Examples of the auxiliary solvent include water-compatible organic solvents, and examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, diethylene glycol, and glycerin.

  The ink used in the present invention may further contain a preservative and an antifoaming agent. Preservatives include imidazole compounds such as 2- (4-thiazolyl) benzimidazole, methyl 2-benzimidazole carbamate, 1,2-benzthiazoline-3-one, 2-n-octyl-isothiazoline-3-one And other compounds such as iodo, nitrile, phenol, haloalkylthio, pyridine, triazine, and bromine. Examples of antifoaming agents include organic polar compounds such as lower alcohols, oleic acid, polypropylene glycol, and silicone resins.

  Various dispersers such as conventionally known ball mills, sand mills, roll mills, line mills and sand grinders can be used as the dispersers used when the disperse dye is converted into ink.

  The form of the mixed fabric to be subjected to inkjet printing according to the present invention may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric, and is not particularly limited.

  It is preferable to pre-process the mixed fabric before inkjet printing the mixed fabric composed of PTT fibers and / or PBT fibers and PET fibers and / or CDP fibers according to the present invention. As the pretreatment agent used for such pretreatment, a water-soluble polymer, a water-insoluble inert organic compound, a flame retardant, an ultraviolet absorber, a reduction inhibitor, an antioxidant, a pH adjuster, a hydrotrope agent, an antifoaming agent, Penetration agents, microporous forming agents, and the like can be exemplified.

  Examples of water-soluble polymers include carboxymethyl cellulose, sodium alginate, guar gum, locust bean gum, gum arabic, crystal beer gum, methyl cellulose, polyacrylamide, starch, sodium polyacrylate, sodium polystyrene sulfonate, hydroxyethyl cellulose, and polyvinyl alcohol. A functional polymer.

  When the surface of the blended fabric is pretreated with a water-insoluble inert organic compound, the surface of the blended fabric becomes smooth and the surface of the fibers can be uniformly hydrophobicized, so that the ink can be uniformly applied to the fabric surface. it can. For this reason, a water-insoluble inert organic compound can be used more preferably. As the water-insoluble inert organic compound, an organic monomer, oligomer or low molecular weight polymer having a melting point of 40 to 150 ° C. is used. These number average molecular weights are usually 10,000 or less, preferably 5000 or less, and more preferably 100 to 2000.

  Examples of such water-insoluble inert organic compounds include low molecular weight synthetic resins, hydrocarbon wax compounds, natural wax compounds, higher fatty acid amide compounds, higher alcohol compounds, polyhydric alcohol higher fatty acid ester compounds, and the like. Preferably, lower alkylene polymer compounds such as polyethylene, paraffin wax and polyethylene wax, hydrocarbon wax compounds such as petrochemical synthetic waxes such as microcrystalline wax, petrolatum, and Fischer-Tropsch wax, ethylene bis stearamide , Stearic acid amide, oleic acid amide, methylol stearamide, higher fatty acid amide compounds such as 12-hydroxystearic acid amide, glycerin oleic acid ester, glycerin steari Esters, propylene glycol monostearate, ethylene glycol monostearate, polyhydric alcohol such as 12-hydroxystearic acid ester - Le higher fatty acid ester-based compounds. Of these, a mixture of a hydrocarbon wax and the other is particularly preferable because of its excellent emulsifying dispersibility.

  Examples of the flame retardant include a halogen flame retardant, a phosphorus flame retardant, and an inorganic flame retardant. Examples of the ultraviolet absorber include benzotriazole and benzophenone. Examples of the reduction inhibitor include nitrobenzene sulfonate and benzene sulfonic acid derivatives. Examples of the antioxidant include hindered amines and hindered phenols.

  Examples of pH adjusters include acidic adjusters such as malic acid, citric acid, acetic acid, ammonium citrate, and potassium dihydrogen phosphate, and alkaline adjusters such as sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate, and sodium acetate. Is mentioned. By finely adjusting the pH by changing the addition amount of the pH adjuster, it is possible to finely control the dyeing property of each fiber constituting the mixed fabric, which is preferable.

  Examples of hydrotropes include urea, polyethylene glycol, thiourea and the like. Examples of the antifoaming agent include organic polar compounds such as lower alcohols, oleic acid, and polypropylene glycol, and silicone resins. Examples of the penetrant include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and butyl oleate, and nonionic surfactants such as nonylphenol and lauryl alcohol.

  As the microporous forming agent, a liquid obtained by uniformly emulsifying and dispersing a low boiling liquid having a boiling point of 105 to 200 ° C. in a fine particle state in water is preferably used. Such low boiling point liquids include hydrocarbon-based toluene, xylene, halogenated hydrocarbon-based perchlorethylene, monochlorobenzene, dichloropentane, butyl acetate, butyl acrylate, and the like.

  Examples of the method for applying the pretreatment agent containing the above components to the mixed fabric include a pad method, a spray method, a dipping method, a coating method, a laminating method, a gravure method, and an ink jet method, and any method can be used. Can do.

  The ink jet recording apparatus used in the ink jet printing method of the present invention is not particularly limited. For example, a continuous method such as a charge modulation method, a micro dot method, a charge ejection control method and an ink mist method, an on-demand method such as a piezo method, a bubble jet (registered trademark) method, and an electrostatic suction method can be used. .

  Furthermore, in the inkjet printing method of the present invention, after inkjet printing on a fabric, the fabric is heat-treated with superheated steam at 140 to 160 ° C. for the purpose of dyeing disperse dyes and coloring. If the temperature is lower than 140 ° C, the dye may be poorly developed. If the temperature is higher than 160 ° C, the fabric may be yellowed or deteriorated, and the stretchability may be reduced. The heat treatment time is 0.5 to 60 minutes. If the time is shorter than 0.5 minutes, color unevenness may occur, and if it exceeds 60 minutes, the dye may fade. As heat treatment conditions, it is more preferable to heat-treat with superheated steam at 150 to 160 ° C. for 5 to 30 minutes.

  After the heat treatment, the printed matter of the present invention can be obtained by generally washing and drying the ink-jet printed fabric.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Preparation of ink 18 parts by weight of the disperse dyes listed in Table 1 below, 14 parts by weight of a dispersant (lignin sulfonate, anionic surfactant), and a preservative (Suneye Back IT20, manufactured by Sanai Oil Co., Ltd.) 0.1 part by weight, 0.05 part by weight of antifoaming agent (Shin-Etsu Silicone KM-70, manufactured by Nissin Chemical Industry Co., Ltd.) and 67.85 parts by weight of pure water were mixed, and in the presence of glass beads, After wet pulverization with a sand mill for 10 hours to form fine particles, the glass beads were removed by suction filtration to prepare inkjet inks (B1 to R3, R1 to 3, Y1 and Y2) shown in Table 1 below.

  The melting point of the disperse dyes described in Table 1 was measured using a differential scanning calorimeter (manufactured by Bruker AXS).

Pretreatment of blended fabric A pretreatment agent prepared by the following formulation was applied to the blended fabric before inkjet printing by the dip nip method. After the dip nip treatment, the fabric was dried at 120 ° C. for 130 seconds by a tenter dryer.

Preparation of pretreatment agent Carboxymethylcellulose (water-soluble polymer, fine gum HE, Daiichi Kogyo Seiyaku Co., Ltd.) 5.0 parts by weight, malic acid (pH adjuster, Fuso Chemical Industry Co., Ltd.) 0. 3 parts by weight, 2.0 parts by weight of MS-liquid (reduction inhibitor, manufactured by Meisei Chemical Industry Co., Ltd.) and 92.7 parts by weight of pure water were mixed to prepare a pretreatment agent.

Ink-jet printing method Using an on-demand type serial scanning ink-jet method, a 5 × 5 cm pattern was printed so that the amount of ink applied to the fabric was 20 nl / mm ² .

Example 1
Against PTT fiber 70 parts by weight of PET fibers, 30 parts by weight of the pre-processing performed was Blended Fabric (knit), ink B1 9nl / mm ^2, the ink R1 7nl / mm ^2, applied with ink Y1 nl / mm ² And expressed a gray color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

Example 2
The mixed fabric (knitted fabric) composed of 70 parts by weight of PBT fiber and 30 parts by weight of PET fiber and subjected to the above pretreatment was applied with ink B2 6 nl / mm ² , ink R2 7 nl / mm ² , and ink Y2 7 nl / mm ² . And expressed a beige color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

Example 3
Against PTT fiber 80 parts by weight consists of CDP fiber 20 parts by weight of the pre-processing performed was Blended Fabric (knit), ink B1 9nl / mm ^2, the ink R1 7nl / mm ^2, applied with ink Y1 nl / mm ² And expressed a gray color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

Example 4
To the mixed fabric (knitted fabric) comprising 80 parts by weight of PBT fiber and 20 parts by weight of CDP fiber and subjected to the above pretreatment, it is applied with ink B2 6 nl / mm ² , ink R2 7 nl / mm ² , and ink Y2 7 nl / mm ² . And expressed a beige color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

Comparative Example 1
Against PTT fiber 70 parts by weight of PET fibers, 30 parts by weight of the pre-processing performed was Blended Fabric (knit), the ink B3 9nl / mm ^2, the ink R1 7nl / mm ^2, applied with ink Y1 nl / mm ² And expressed a gray color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

Comparative Example 2
The mixed fabric (knitted fabric) composed of 70 parts by weight of PBT fiber and 30 parts by weight of PET fiber and subjected to the above pretreatment was applied with ink B2 6 nl / mm ² , ink R3 7 nl / mm ² , and ink Y2 7 nl / mm ² . And expressed a beige color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

Comparative Example 3
Against PTT fiber 80 parts by weight consists of CDP fiber 20 parts by weight of the pre-processing performed was Blended Fabric (knit), the ink B3 9nl / mm ^2, the ink R1 7nl / mm ^2, applied with ink Y1 nl / mm ² And expressed a gray color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

Comparative Example 4
To the mixed fabric (knitted fabric) comprising 80 parts by weight of PBT fiber and 20 parts by weight of CDP fiber and subjected to the above pretreatment, it was applied with ink B2 6 nl / mm ² , ink R3 7 nl / mm ² , and ink Y2 7 nl / mm ² . And expressed a beige color. The fabric was then heat-treated at 150 ° C. for 15 minutes, and then washed and dried by a conventional method to obtain a printed matter.

〔Evaluation methods〕
The printed materials obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated by the following evaluation methods.

Color Reproducibility Each of Examples 1 to 4 and Comparative Examples 1 to 4 was processed twice under the same conditions, and the two printed products thus obtained were subjected to a color measurement (CM2600, Konica Minolta). The color difference (ΔE) of the two printed materials was calculated using a color measurement using Sensing Co., Ltd. Here, the color difference is a color difference in the L ^* a ^* b ^* color system (JIS Z 8729) and is defined by the following formula.
ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
Here, L ^* represents lightness, and a ^* and b ^* represent chromaticity indicating hue and saturation. ΔL ^* and Δa ^* and Δb ^* represent a lightness difference and a chromaticity difference between the two printed products obtained for each of the examples and comparative examples.

The color reproducibility was evaluated according to the following criteria. The evaluation results are shown in Table 2.
○: △ E <0.2
Δ: 0.2 ≦ ΔE ≦ 0.5
×: 0.5 <△ E
When the color difference (ΔE) is a smaller value, the color reproducibility is good, and when ΔE is a larger value, the color reproducibility is poor.

Hue difference The color of the ink-applied surface of the obtained printed matter and the color of the opposite surface of the ink-applied surface are measured using a colorimeter (CM2600, manufactured by Konica Minolta Sensing Co., Ltd.) The hue difference on the surface opposite to the ink application surface was calculated. Here, the hue difference is a chromaticity difference (Δa ^* , Δb ^* ) in the L ^* a ^* b ^* color system (JIS Z 8729), and was obtained for each example and comparative example. It represents the chromaticity difference between the ink application surface of the printed material and the opposite surface of the ink application surface. Further, a ^* and b ^* represent chromaticity indicating hue and saturation.

Evaluation of the hue difference was performed according to the following criteria. The evaluation results are shown in Table 2.
○: | Δa ^* | <5 and | Δb ^* | <5
Δ: | Δa ^* |> 5 and | Δb ^* | <5, or | Δa ^* | <5 and | Δb ^* |> 5
×: | Δa ^* |> 5 and | Δb ^* |> 5
When the chromaticity difference (Δa ^* , Δb ^* ) is a smaller value, the printed product is a good printed product with little color difference between the ink-applied surface of the printed product and the opposite surface of the ink-applied surface. When a ^* and Δb ^* ) are larger values, it means that the printed matter is an unfavorable printed matter having a large color difference between the ink-applied surface of the printed matter and the opposite surface of the ink-applied surface.

  From the evaluation results shown in Table 2, the color reproducibility and hue difference are good for Examples 1 to 4 in which inkjet printing was performed using a disperse dye having a melting point of 160 ° C. or higher as a color material for blue and red inks. The result is obtained. On the other hand, in Comparative Examples 1 to 4 in which ink jet printing was performed using a disperse dye having a melting point of less than 160 ° C. as a color material for blue and red inks, good results were not obtained. The result was a strong bluishness on the opposite side of the surface, and conversely in Comparative Examples 2 and 4, a strong redness on the opposite side of the ink application surface.

Claims (3)

A method for inkjet printing a mixed fabric composed of polytrimethylene terephthalate fiber and / or polybutylene terephthalate fiber and polyethylene terephthalate fiber and / or cationic dyeable polyester fiber, wherein blue and red inks are applied to the mixed fabric. An ink-jet printing method, comprising: performing dissipative dye having a melting point of 160 ° C. or higher as a coloring material and heat-treating with superheated steam at 140 to 160 ° C. The blue ink is C.I. I. Disperse blue 56, 60, 77, 165, 214 and 284 containing one or more disperse dyes selected from the group consisting of I. The ink-jet printing method according to claim 1, further comprising at least one disperse dye selected from the group consisting of Disperse Red 60, 86, 152, 177, 179 and 343. A printed matter printed by the ink jet printing method according to claim 1.