JP2020062783A - Image formation method and ink set - Google Patents

Abstract

To provide an image formation method for forming an image on a surface of fabric using ink, capable of suppressing bleeding after landing of color ink and strike-through and forming an image with optimal texture.SOLUTION: An image formation method comprises: a first step for adhering a white ink to a fabric; and a second step for adhering a color ink to a region where the white ink has been adhered on the fabric, where a viscosity of the white ink is 1.5 times or greater and 4.0 times or smaller of a viscosity of the color ink.SELECTED DRAWING: None

Description

  The present invention relates to an image forming method and an ink set for forming an image on a surface of a cloth using ink.

  Conventionally, a screen printing method, a roller printing method and the like have been widely used as a method for printing a fabric such as cotton, silk and polyester. These printing methods are not suitable for printing high-mix low-volume production because it is necessary to prepare a screen frame and engraving roller for each design. On the other hand, the inkjet printing method does not require plate making work such as a screen frame or engraving roller, and can change patterns and colors by simply changing digital data, so it is suitable for high-mix low-volume production. , Has been widely used in recent years.

  Patent Document 1 discloses an invention for preventing penetration and bleeding by screen-printing a white or light-colored ink having a considerably high viscosity on a cloth and inkjet-printing a UV ink on the cloth. .

  In Patent Document 2, as a means for obtaining an image excellent in color developability and washing fastness, it is specified that the material of the pretreatment liquid is specified and that the white ink and the color ink are printed in the order of application of the pretreatment liquid. The invention of the image forming method is disclosed.

  However, when high-viscosity ink is used, the original texture of the cloth is impaired, and when there is no difference between the viscosity of the white ink and the viscosity of the color ink, there is a problem that bleeding such as color bleeding occurs.

  SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method that suppresses strike-through and bleeding after landing of color ink and forms an image having an optimum texture.

The above problems can be solved by the image forming method according to the present invention as described below.
The first step of attaching white ink to the fabric,
A second step of applying color ink to the area of the cloth to which the white ink is applied,
An image forming method, wherein the viscosity of the white ink is 1.5 times or more and 4.0 times or less that of the color ink.

  According to the present invention, strikethrough and bleeding after landing of color ink are suppressed, and an image having an optimum texture can be obtained.

FIG. 1 is a perspective explanatory view showing an example of an inkjet recording apparatus. FIG. 2 is a perspective explanatory view showing an example of the main tank. FIG. 3 is a schematic view showing an example of heating means of the inkjet recording apparatus.

（但し、Ｒ_１はメチル基、エチル基、プロピル基、ブチル基を表し、Ｒ_２、Ｒ_３はアルキル基（Ｃ＝１〜６）を表す。）
（５）前記ホワイトインクの２５℃、１５ｍｓでの動的表面張力が前記カラーインクの２５℃、１５ｍｓでの動的表面張力の０．７倍より低い上記（１）乃至（４）のいずれかに記載の画像形成方法。
（６）布帛にインクを付着させて画像を形成するために用いられる、ホワイトインクとカラーインクとからなるインクセットであって、前記ホワイトインクの粘度が、前記カラーインクの粘度の１．５倍以上４．０倍以下であるインクセット。 The present invention relates to the image forming method described in (1) below, but since the following (2) to (6) are included as embodiments of the invention, these embodiments will be described together.
(1) a first step of attaching a white ink to the cloth,
A second step of applying color ink to the area of the cloth to which the white ink is applied,
An image forming method, wherein the viscosity of the white ink is 1.5 times or more and 4.0 times or less the viscosity of the color ink.
(2) The image forming method according to (1), wherein the white ink has a viscosity at 25 ° C. of 7 mPa · s or more.
(3) The image forming method according to (1) or (2), wherein the content ratio of the pigment in the white ink is higher than the content ratio of the pigment in the color ink.
(4) The image forming method according to any one of (1) to (3) above, wherein the white ink contains an amide compound represented by the following general formula (1) as a water-soluble organic solvent.

(However, R ₁ represents a methyl group, an ethyl group, a propyl group, and a butyl group, and R ₂ and R ₃ represent an alkyl group (C = 1 to 6).)
(5) Any one of the above (1) to (4), wherein the dynamic surface tension of the white ink at 25 ° C. and 15 ms is lower than 0.7 times the dynamic surface tension of the color ink at 25 ° C. and 15 ms. The image forming method described in 1 ..
(6) An ink set composed of a white ink and a color ink, which is used for forming an image by attaching the ink to a cloth, wherein the viscosity of the white ink is 1.5 times the viscosity of the color ink. The above ink set is 4.0 times or less.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Hereinafter, the “cloth” that is the recording medium may be referred to as the “base material”.
An image forming method according to an embodiment of the present invention uses a cloth as a recording medium, uses a first step of adhering white ink on at least one surface of the cloth, and adhering the white ink of the cloth. And a second step of forming an image by adhering color ink on the surface of the white ink, wherein the viscosity of the white ink is 1.5 times or more and 4.0 times or less than the viscosity of the color ink.
By the above, the fluidity of the white ink after landing on the substrate and the fixability on the substrate are promoted, strike-through and bleeding after landing of the color inks are suppressed, and an image having an optimum texture can be obtained. In particular, in the method of printing a fabric such as cotton, silk, polyester, etc., an optimum texture is required, and therefore it is preferable to set an upper limit to the viscosity of the color ink.
The texture is the feel of the fabric. However, since the touch of a person's hand varies from person to person, the values from various testing machines are often referred to as the judgment of goodness or badness. In the present invention, the texture is evaluated using JIS-L-1096.

  In the above image forming method, the viscosity of the white ink at 25 ° C. is preferably 7 mPa · s or more. The above-mentioned constitution is preferable from the viewpoint of promoting the decrease in the fluidity of the white ink after landing on the substrate and the fixing property to the substrate, suppressing strike-through, and obtaining an image having an optimum texture.

  In the above image forming method, it is preferable that the content ratio of the pigment in the white ink is higher than the content ratio of the pigment in the color ink. The above configuration is preferable from the viewpoint of suppressing bleeding after landing of color ink and obtaining an image having an optimum texture.

（但し、Ｒ_１はメチル基、エチル基、プロピル基、ブチル基を表し、Ｒ_２、Ｒ_３はアルキル基（Ｃ＝１〜６）を表す。）
上記一般式（１）で表される化合物としてはＲ_１、Ｒ_２及びＲ_３が全てメチル基である３−メトキシ−Ｎ，Ｎ−ジメチルプロピオンアミドや、Ｒ_１がｎ−ブチル基であり、Ｒ_２及びＲ_３がメチル基である３−ブトキシ−Ｎ，Ｎ−ジメチルプロピオンを挙げることができるが、３−メトキシ−Ｎ，Ｎ−ジメチルプロピオンアミドが特に好ましい。商品名としてはＲ_１、Ｒ_２及びＲ_３が全てメチル基であるものとしてはエクアミドＭ１００（出光興産社製）を挙げることができ、Ｒ_１がｎ−ブチル基であり、Ｒ_２及びＲ_３がメチル基であるものとしてはエクアミドＢ１００（出光興産社製）を挙げることができる。 In the above image forming method, it is preferable that the white ink contains at least an amide compound represented by the following general formula (1) as a water-soluble organic solvent. The above configuration is preferable from the viewpoint of suppressing bleeding after landing of color ink and obtaining an image having an optimum texture.

(However, R ₁ represents a methyl group, an ethyl group, a propyl group, and a butyl group, and R ₂ and R ₃ represent an alkyl group (C = 1 to 6).)
Examples of the compound represented by the general formula (1) include 3-methoxy-N, N-dimethylpropionamide in which R ₁ , R ₂ and R ₃ are all methyl groups, and R ₁ is an n-butyl group, R ₂ and _{R 3} is a methyl group 3-butoxy -N, N-dimethyl-but-propionic can be exemplified, 3-methoxy -N, N-dimethyl propionamide are especially preferred. As a trade name, Examide M100 (manufactured by Idemitsu Kosan Co., Ltd.) can be mentioned as one in which R ₁ , R ₂ and R ₃ are all methyl groups, R ₁ is an n-butyl group, and R ₂ and R ₃ Examide B100 (manufactured by Idemitsu Kosan Co., Ltd.) can be mentioned as a compound having a methyl group.

  In the above image forming method, it is preferable that the dynamic surface tension of the white ink at 25 ° C. and 15 ms is lower than 0.7 times the dynamic surface tension of the color ink at 25 ° C. and 15 ms. The above-mentioned constitution is preferable from the viewpoint that the fluidity of the white ink after landing on the substrate and the fixing property to the substrate are promoted, bleeding after landing of the color ink is suppressed, and an image having an optimum texture is obtained.

<<<< ink >>>>
In the image forming method of the present invention, white ink and color ink are used.
Incidentally, the color ink in the present invention means, for example, any ink other than the white ink, including color materials such as black, cyan, magenta, yellow, green, orange, violet, and red, and bright color materials. Clear ink that does not substantially contain is included in the color ink. Each of these color inks may be used alone, or a plurality of them may be used. In the following, each component such as water, water-soluble organic solvent, pigment, and resin particles in the ink will be described in detail.

<Color material>
The colorant is not particularly limited, but a pigment can be mainly used.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used alone or in combination of two or more. Also, a mixed crystal may be used.
Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, luster color pigments such as gold and silver, and metallic pigments.

  As an inorganic pigment, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method. Can be used.

  Further, as the organic pigment, an azo pigment, a polycyclic pigment (for example, a phthalocyanine pigment, a perylene pigment, a perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, an indigo pigment, a thioindigo pigment, an isoindolinone pigment, a quinophthalone pigment, etc.) , Dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used. Among these pigments, those having a good affinity with the solvent are preferably used. In addition, hollow resin particles and hollow inorganic particles can also be used.

Specific examples of the pigment include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, or copper and iron (CI pigment black 11) for black. , Metal oxides such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).
Further, for color, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104. , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2,53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 11 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Quinacridone Magenta), 123, 146, 149, 166 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, and the like.

  The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass, from the viewpoints of improving the image density, good fixing property and ejection stability. It is the following.

To obtain an ink by dispersing the pigment, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of coating the surface of the pigment with a resin to disperse the pigment, and a method of dispersing using a dispersant are used. Method, etc.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) to make the pigment dispersible in water Is mentioned.
Examples of the method of coating the surface of the pigment with a resin to disperse the pigment include a method of incorporating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary for all the pigments mixed in the ink to be coated with the resin, and as long as the effect of the present invention is not impaired, uncoated pigments or partially coated pigments are dispersed in the ink. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low molecular type dispersant or polymer type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant or the like can be used depending on the pigment.
Takemoto Yushi Co., Ltd. RT-100 (nonionic surfactant) and naphthalene sulfonic acid Na formalin condensate can also be suitably used as the dispersant.
The dispersants may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with the pigment. Further, it is also possible to manufacture an ink by mixing a pigment and other materials such as water and a dispersant into a pigment dispersion and mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. A disperser may be used for dispersion.
There is no particular limitation on the particle size of the pigment in the pigment dispersion, but since the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high, the maximum frequency in terms of maximum number is 20 nm or more. It is preferably 500 nm or less, more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell KK).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, it is 0.1% by mass. % Or more and 50% by mass or less is preferable, and 0.1% by mass or more and 30% by mass or less is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

  The resin particles improve the dispersibility of the particles in the ink, increase the hardness of the ink coating film, and improve the abrasion resistance. The minimum film forming temperature of the resin particles contained in the ink (hereinafter sometimes referred to as MFT (Minimum Film-Forming Temperature)) provides a metallic luster and provides the adhesion between the ink coating film and the recording medium. In addition, it is preferably 50 to 80 ° C., because the abrasion resistance can be obtained well. By adding resin particles having a minimum film forming temperature of 50 to 80 ° C. to the ink, an ink having a minimum film forming temperature of 50 to 80 ° C. can be easily manufactured.

  The volume average particle diameter of the resin particles contained in the ink is 10 to 30 nm. When the volume average particle diameter is in this range, the metallic gloss and the abrasion resistance of the coating film are best balanced and the discoloration can be suppressed.

  Examples of the resin in the resin particles include urethane resin, polyester resin, acrylic resin, styrene resin, butadiene resin, styrene-butadiene resin, acrylic styrene resin, and acrylic silicone resin. These may be used alone or in combination of two or more. Among these, urethane resin is preferable from the viewpoint of making the recorded matter more robust.

  Examples of the urethane resin include polycarbonate-based urethane resin, polyester-based urethane resin, and polyether-based urethane resin. Among these, polycarbonate-based urethane resins are preferable in terms of water resistance, heat resistance, abrasion resistance, weather resistance, and image scratch resistance due to the high cohesive force of the carbonate group.

  The content of the resin particles in the ink is preferably 0.01% by mass or more and 5.0% by mass or less, and more preferably 0.05% by mass or more and 2.0% by mass or less. Within this range, the storage stability of the ink, the ejection stability, and the metallic luster are improved and discoloration is suppressed.

  The resin particles may be a forced emulsification type used together with a dispersant, but a so-called self-emulsification type having an anion group in the molecular structure is preferable from the viewpoint of preventing the dispersant remaining in the coating film from lowering the strength. Is. The acid value of the anionic group of the self-emulsifying resin particles is preferably 5 mgKOH / g or more and 100 mgKOH / g or less, from the viewpoint of water dispersibility, abrasion resistance, and chemical resistance, and 5 mgKOH / mg or more and 50 mgKOH / mg or less. Is more preferable.

  Examples of the anionic group in the self-emulsifying resin particles include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. Among these, a carboxylate group and a sulfonate group partially or wholly neutralized with a basic compound or the like are preferable from the viewpoint of maintaining good water dispersion stability. In order to introduce such an anion group into the resin, the resin may be produced by polymerizing a monomer having an anion group.

  As a method for producing an aqueous dispersion of resin particles having an anion group, a basic compound for neutralizing an anion group may be added to a mixture of water and resin particles having an anion group.

  Examples of the basic compound for neutralizing the anion group include organic amines such as ammonia, triethylamine, pyridine and morpholine; alkanolamines such as monoethanolamine; metal base compounds containing Na, K, Li, Ca and the like. Is mentioned. These may be used alone or in combination of two or more.

  Examples of the dispersant used when an aqueous dispersion is produced using the forced emulsification type resin particles include surfactants such as nonionic surfactants and anionic surfactants. These may be used alone or in combination of two or more. Among these, nonionic surfactants are preferable from the viewpoint of water resistance.

  The above nonionic surfactants are, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, Includes sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkyl amines, alkyl alkanolamides, polyalkylene glycol (meth) acrylates, and the like. These may be used alone or in combination of two or more. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable.

  The above-mentioned anionic surfactants are, for example, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurilates, sulfosuccinates, ether sulfonates, ethers. Including a carboxylate, a fatty acid salt, a naphthalenesulfonic acid formalin condensate, an alkylamine salt, a quaternary ammonium salt, an alkylbetaine, and an alkylamine oxide. These may be used alone or in combination of two or more. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

  The content of these surfactants is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less, based on the total amount of the resin. When the content of the surfactant is 0.1% by mass or more and 30% by mass or less, the resin is preferably formed into a film, an ink having excellent adhesiveness and water resistance is obtained, and the recorded matter may be blocked. It is advantageous in that it does not exist.

<< organic solvent >>
The organic solvent used for the ink is not particularly limited, but it is preferable to include a water-soluble organic solvent as the organic solvent. Examples of the water-soluble organic solvent include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. To be

  Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butane. Diol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2- Polyhydric alcohols such as ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Monomethyl ether Polyhydric alcohol alkyl ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2 -Nitrogen-containing heterocyclic compounds such as -pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide , Amides such as N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine and triethylamine, dimethyl sulfoxide Sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, ethylene and the like carbonates.

  It is preferable that the ink of the present embodiment contains an organic solvent having a boiling point of 250 ° C. or lower, in addition to the function as a wetting agent and the good drying property. The organic solvent contained in the ink of the present embodiment is preferably composed only of a water-soluble organic solvent having a boiling point of 250 ° C. or less, and more preferably composed of only a water-soluble organic solvent having a boiling point of less than 220 ° C. Since the ink contains a water-soluble organic solvent having a boiling point of 250 ° C. or less, good drying property and high gloss can be obtained.

  A group containing 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol among organic solvents having a boiling point of 250 ° C. or lower. It is preferable to contain at least one selected from When these are used, the compatibility with the polycarbonate-based urethane resin is good, an ink having more excellent film-forming property can be obtained, and high gloss is easily obtained.

  The total amount of the water-soluble organic solvent contained in the entire ink is preferably in the range of 20 to 70% by mass, more preferably 30 to 60% by mass. When the total amount is 20% by mass or more, the ink is difficult to dry, and thus sufficient ejection stability is obtained, and when the total amount is 70% by mass or less, the viscosity does not become too high and the ejection stability is obtained.

<< water >>
Water is the main solvent or dispersion medium for ink. As the water, pure water such as ion exchanged water, ultrafiltered water, reverse osmosis water, distilled water, or ultrapure water is preferably used for the purpose of reducing ionic impurities as much as possible. Further, it is preferable to use water that has been sterilized by UV irradiation, addition of hydrogen peroxide, or the like, because it is possible to prevent the generation of mold and bacteria when the ink is stored for a long period of time. The content of water in the ink is appropriately selected depending on the intended purpose without any limitation, but it is preferably 25% by mass or more and 75% by mass or less, and more preferably 30% by mass or more and 60% by mass or less. Within this range, the environmental load of ink is reduced.

<Additives>
If necessary, a surfactant, a defoaming agent, an antiseptic / antifungal agent, an anticorrosive agent, a pH adjusting agent and the like may be added to the ink.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone surfactant is not particularly limited and can be appropriately selected according to the purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and side-chain both-end modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound having a polyalkylene oxide structure introduced into the side chain of the Si moiety of dimethylsiloxane.
Examples of the fluorinated surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphoric acid ester compound, a perfluoroalkyl ethylene oxide adduct and a perfluoroalkyl ether group in the side chain. A polyoxyalkylene ether polymer compound is particularly preferable because it has a low foaming property. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salts. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in its side chain include a sulfuric acid ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in its side chain and a perfluoroalkyl ether group in its side chain. Examples thereof include salts of polyoxyalkylene ether polymers. As counter ions of the salt in these fluorine-based surfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) are used. _{3 and the} like.
Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan. Examples thereof include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and salt of polyoxyethylene alkyl ether sulfate.
These may be used alone or in combination of two or more.

（但し、一般式（Ｓ−１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ−６１８、ＫＦ−６４２、ＫＦ−６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ−ＳＳ−５６０２、ＳＳ−１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ−２１０５、ＦＺ−２１１８、ＦＺ−２１５４、ＦＺ−２１６１、ＦＺ−２１６２、ＦＺ−２１６３、ＦＺ−２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ−３３、ＢＹＫ−３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and side-modified polydimethylsiloxane. Examples thereof include polydimethyl siloxane modified at both chain ends, and a polyether modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group shows good properties as an aqueous surfactant. preferable.
As such a surfactant, those synthesized appropriately may be used, or commercially available products may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Kagaku Co., Ltd., and the like.
The polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the general formula (S-1) may be represented by dimethylpolyethylene. Examples thereof include those introduced into the side chain of the Si portion of siloxane.
As such a surfactant, those synthesized appropriately may be used, or commercially available products may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Kagaku Co., Ltd., and the like.
The polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the general formula (S-1) may be dimethylpolyethylene. Examples thereof include those introduced into the side chain of the Si portion of siloxane.

(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R ′ represents an alkyl group.)
As the above polyether-modified silicone-based surfactant, commercially available products can be used, for example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-. 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc. are mentioned.

上記一般式（Ｆ−１）で表される化合物において、水溶性を付与するためにｍは０〜１０の整数が好ましく、ｎは０〜４０の整数が好ましい。
一般式（Ｆ−２）
Ｃ_ｎＦ_{２ｎ＋１−}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ａ−Ｙ
上記一般式（Ｆ−２）で表される化合物において、ＹはＨ、又はＣｍＦ_２ｍ＋１でｍは１〜６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−ＣｍＦ_２ｍ＋１でｍは４〜６の整数、又はＣｐＨ_２ｐ＋１でｐは１〜１９の整数である。ｎは１〜６の整数である。ａは４〜１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。 この市販品としては、例えば、サーフロンＳ−１１１、Ｓ−１１２、Ｓ−１１３、Ｓ−１２１、Ｓ−１３１、Ｓ−１３２、Ｓ−１４１、Ｓ−１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ−９３、ＦＣ−９５、ＦＣ−９８、ＦＣ−１２９、ＦＣ−１３５、ＦＣ−１７０Ｃ、ＦＣ−４３０、ＦＣ−４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ−４７０、Ｆ−１４０５、Ｆ−４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ−１００、ＦＳＮ、ＦＳＯ−１００、ＦＳＯ、ＦＳ−３００、ＵＲ、キャプストーンＦＳ−３０、ＦＳ−３１、ＦＳ−３１００、ＦＳ−３４、ＦＳ−３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ−１３６Ａ，ＰＦ−１５６Ａ、ＰＦ−１５１Ｎ、ＰＦ−１５４、ＰＦ−１５９（オムノバ社製）、ユニダインＤＳＮ−４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ−３１００、ＦＳ−３４、ＦＳ−３００、株式会社ネオス製のＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ、オムノバ社製のポリフォックスＰＦ−１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ−４０３Ｎが特に好ましい。 The fluorine-based surfactant is preferably a fluorine-substituted compound having 2 to 16 carbon atoms, and more preferably a fluorine-substituted compound having 4 to 16 carbon atoms.
Examples of the fluorinated surfactant include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has a low foaming property, and is particularly preferably a fluorine-based compound represented by the general formula (F-1) or the general formula (F-2). Surfactants are preferred.

In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or CmF _{2m + 1} and m is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ —CmF _{2m + 1} and m is 4 to 6. An integer, or CpH _{2p + 1} and p is an integer of 1 to 19. n is an integer of 1-6. a is an integer of 4-14.
A commercially available product may be used as the above-mentioned fluorine-based surfactant. Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250. FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (Omnova Corporation) , Manufactured by Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) and the like. Among these, good printing quality, especially color development, penetrability into paper, wettability, and leveling property are remarkably improved. Chemours FS-3100, FS-34, FS-300, Neos FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, OMNOVA Poly. Fox PF-151N and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable.

  The content of the surfactant in the ink is appropriately selected depending on the intended purpose without any limitation, but it is 0.001 mass% from the viewpoint of excellent wettability and ejection stability and improving image quality. % Or more and 5 mass% or less is preferable, and 0.05 mass% or more and 5 mass% or less is more preferable.

<Antifoam>
The defoaming agent is not particularly limited, and examples thereof include a silicone defoaming agent, a polyether defoaming agent, and a fatty acid ester defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because of its excellent foam breaking effect.

<Antiseptic and fungicide>
The antiseptic / antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<Rust preventive>
The rust preventive agent is not particularly limited, and examples thereof include acid sulfite and sodium thiosulfate.

<PH adjuster>
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or higher, and examples thereof include amines such as diethanolamine and triethanolamine.

<Ink manufacturing method>
Examples of the method for producing the ink include a method of stirring and mixing the above water, the organic solvent, the first resin particles, the second resin particles, and, if necessary, other components. As the stirring and mixing, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using ordinary stirring blades, a magnetic stirrer, a high speed disperser and the like can be used.

The physical properties of the ink are not particularly limited and may be appropriately selected depending on the purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, from the viewpoint that the printing density and character quality are improved, and that good ejection properties can be obtained, and 5 mPa · s or more and 25 mPa · s or less are preferable. More preferable. Here, as the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. The measurement conditions are 25 ° C., standard cone rotor (1 ° 34 ′ × R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less at 25 ° C., and more preferably 32 mN / m or less at 25 ° C., since the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, and more preferably 8 to 11 from the viewpoint of preventing the corrosion of the metal member with which the ink comes into contact.

<Ink set>
The combination of the white ink and the color ink used in the image forming method of the present invention can suppress the strike-through and the bleeding after landing of the color ink to form an image having an optimum texture when attached to the surface of the fabric. Therefore, it is suitable as an ink set for forming an image on the surface of a cloth by inkjet.

<Recording medium>
A cloth is used as the recording medium. In particular, plant fibers are cotton, hemp, animal fibers are silk, wool, alpaca, angora, cashmere, mohair, regenerated fibers are rayon, cupra, polynosic, semi-synthetic fibers are acetate, triacetate, promix, synthetic fibers are nylon. Examples include polyester, acrylic, polyvinyl chloride and polyurethane.

<Ink cartridge>
The ink cartridge used in this embodiment has a container that contains the ink of this embodiment. The ink cartridge includes, in addition to a container that stores ink, other members that are appropriately selected as necessary.

  The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film or the like can be used. The thing which it has is mentioned.

<Inkjet recording method and inkjet recording apparatus>
The ink jet recording apparatus according to the present embodiment has an ink ejecting unit and, if necessary, other appropriately selected unit such as a heating unit. The inkjet recording method of the present embodiment has an ink ejection step, and further includes other steps appropriately selected, such as a heating step, if necessary.

  The inkjet recording method of the present embodiment can be preferably implemented by the inkjet recording apparatus of the present embodiment. The ink discharging step can be suitably performed by an ink discharging means. The heating step can be suitably carried out by a heating means. In addition, other steps can be suitably performed by other means.

<Ink ejection step and ink ejection means>
The ink ejection step is a step in which the ink ejection means applies a stimulus to the ink of the present embodiment and ejects the ink to form an image. The ink ejecting means is not particularly limited, and examples thereof include an inkjet head.

  As an ink jet head, a piezoelectric element is used as a pressure generating unit that pressurizes ink in the ink flow path, and the diaphragm that forms the wall surface of the ink flow path is deformed to change the internal volume of the ink flow path and eject ink droplets. A so-called piezo type, a so-called thermal type that heats ink in the ink flow path to generate bubbles by using a heating resistor, and a diaphragm and an electrode that form the wall surface of the ink flow path are arranged to face each other, Any case such as an electrostatic type in which the vibrating plate is deformed by the electrostatic force generated between the vibrating plate and the electrode to change the internal volume of the ink flow path to eject the ink droplets is included.

  The stimulus described above can be generated by, for example, a stimulus generation unit. The stimulus is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thermal energy (temperature); mechanical energy such as pressure and vibration; and light. These may be used alone or in combination of two or more. Of these, heat and pressure are preferable.

  The mode of ejecting the ink is not particularly limited and differs depending on the kind of the stimulus. For example, when the stimulus is “heat”, thermal energy corresponding to a recording signal is applied to the ink in the inkjet head by, for example, thermal. There is a method in which the ink is applied using a head or the like, bubbles are generated in the ink by the thermal energy, and the ink is ejected and ejected as droplets from the nozzle holes of the inkjet head by the pressure of the bubbles. When the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in the ink flow path in the inkjet head, the piezoelectric element bends, and the volume of the pressure chamber is reduced. There is a method of reducing and ejecting and ejecting the ink as droplets from a nozzle hole of an inkjet head.

  The droplet size of the ink to be ejected is, for example, preferably 3 pl or more and 40 pl or less, the speed of the ejection and ejection thereof is preferably 5 m / s or more and 20 m / s or less, the driving frequency thereof is preferably 1 kHz or more, and the resolution thereof is It is preferably 300 dpi or more.

<Heating process and heating means>
The heating step is a step in which the heating means heats the recording medium on which the image is recorded. According to the inkjet recording method, it is possible to record an image of high image quality on a non-permeable recording medium as a recording medium, but it is possible to form an image having higher image quality, abrasion resistance, and high adhesion to the recording medium, and high speed. It is preferable to heat the non-permeable recording medium after recording in order to be able to meet the recording condition of (1). When the heating step is provided after recording, the film formation of the resin contained in the ink is promoted, so that the image hardness of the recorded matter can be improved.

  As the heating means, many known devices can be used, and examples thereof include devices such as forced air heating using warm air generating means, radiant heating, conduction heating, high frequency drying, and microwave drying. To be These may be used alone or in combination of two or more.

  The heating temperature can be changed according to the type and amount of the water-soluble organic solvent contained in the ink, and the minimum film-forming temperature of the resin particles to be added, and also depending on the type of recording medium to be printed. be able to.

  The heating temperature is preferably as high as possible from the viewpoint of drying property and film forming temperature so as not to damage the impermeable recording medium, and specifically, it is preferably 40 ° C. or higher and 120 ° C. or lower, and 50 ° C. or higher. 90 ° C or lower is more preferable. When the heating temperature is 40 ° C. or higher and 120 ° C. or lower, damage to the non-permeable recording medium due to heat can be prevented, and it is possible to suppress non-ejection due to warming of the inkjet head.

<Other steps and other means>
Examples of other steps include a stimulus generation step by a stimulus generation means and a control step by a control means.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor. And the like, a thermal actuator that utilizes a phase change due to film boiling of a liquid using an electrothermal conversion element, a shape memory alloy actuator that uses a metal phase change due to a temperature change, an electrostatic actuator that uses an electrostatic force, and the like.
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose, and examples thereof include equipment such as a sequencer and a computer.

  As an example of the image forming method of the present embodiment, after the white ink is attached to the cloth, black, cyan, magenta, yellow, green, orange, and violet are used as color inks in the area where the white ink is attached to the cloth. , A color ink such as red, or an ink containing a glittering color material may be attached, and if necessary, a clear ink containing no pigment may be attached. Further, a plurality of color inks may be applied to the same place, or may be applied to some common places.

  The method of using the ink is not limited to the ink jet recording method and can be widely used. In addition to the inkjet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method and the like can be mentioned.

<Recorded matter>
The ink recorded matter of the invention has an image formed by using the ink of the invention on a recording medium.
A recorded matter can be obtained by recording with an inkjet recording apparatus and an inkjet recording method.

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording apparatuses using an inkjet recording method, such as printers, facsimile machines, copying machines, printer / fax / copier composite machines, and three-dimensional modeling apparatuses. In the present invention, the recording device and the recording method are a device capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of recording using the device. The recording medium means a medium to which ink or various treatment liquids can be attached even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices such as a pre-processing device and a post-processing device. .
The recording device and the recording method may have a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printing surface or the back surface of the recording medium. The heating means and the drying means are not particularly limited, but, for example, a warm air heater or an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording device and the recording method are not limited to those in which a significant image such as a character or a figure is visualized by ink. For example, the thing which forms patterns, such as a geometric pattern, and the thing which models a three-dimensional image are also included.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head unless otherwise limited.
Further, this recording device is not limited to a desktop type, and can be used as a wide recording device capable of printing on an A0 size recording medium, or for example, a continuous paper wound in a roll as a recording medium. It also includes a continuous form printer.
An example of the recording device will be described with reference to FIGS. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism section 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminate film. It is formed of a member. The ink container 411 is housed in a container case 414 made of plastics, for example. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus body is opened. The main tank 410 is detachably attached to the cartridge holder 404. As a result, the ink discharge ports 413 of the main tank 410 communicate with the ejection heads 434 for the respective colors via the supply tubes 436 for the respective colors, and ink can be ejected from the ejection heads 434 to the recording medium.

The inkjet recording apparatus shown in FIG. 1 preferably has a heating means.
FIG. 3 is a schematic view showing an example of heating means of the apparatus of FIG. As shown in FIG. 3, by driving the recording head in accordance with the image signal while moving the carriage 133, ink droplets are ejected onto the recording medium 142 which is stopped to record an image. Warm air is generated in the image formed on the recording medium 142 that is conveyed on the conveyor belt 151 that is a guide member 153 that holds down the recording medium and that is stretched between the conveyor roller 157 and the tension roller 158. As a part, it is dried by blowing warm air 202 with a heating fan 201.
A heater group 203 is provided on the opposite side of the conveyor belt 151 from the recording medium 142, and the recording medium 142 can be heated during printing.
Further, not only during printing but also before and after printing, a drying step may be included.

  Further, in the terms of the present invention, image formation, recording, printing, printing and the like are synonymous.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "part" in an example shows a "mass part", and "%" shows the "mass%."

  First, preparation examples of the pigment dispersion and the resin emulsion will be described.

<Preparation of pigment dispersion>
-Preparation of titanium dioxide pigment dispersion-
In a beaker, 37.5 parts of an acrylic copolymer (DISPERBYK-2008: manufactured by BYK, 60 mass% of active ingredient) was dissolved in 100.0 parts of high pure water, and titanium oxide (JR-600A: manufactured by Teika (primary particle diameter 250 nm, surface treatment : Al)) 30.0 parts is added, and the mixture is stirred with an Excel Auto Homogenizer manufactured by Nippon Seiki Seisakusho at 5000 rpm for 30 minutes, dispersed until there is no lump, and the rotation speed is gradually increased and stirred at 10000 rpm for 30 minutes. went.
While water-cooling the obtained titanium dioxide pigment dispersion, it was treated with an ultrasonic homogenizer US-300T (tip φ26) manufactured by Nippon Seiki Seisakusho at 200 μA for 1 hour, and filtered with a 5 μm membrane filter (cellulose acetate membrane). A [titanium dioxide pigment dispersion] having a titanium dioxide pigment of 17.9% was obtained.

-Preparation of yellow pigment dispersion-
Monoazo yellow pigment (CI Pigment Yellow 74, manufactured by Dainichiseika Kogyo Co., Ltd.) 30.0 parts, polyoxyethylene styrene phenyl ether (nonionic surfactant, manufactured by Dai-ichi Kogyo Seiyaku Co., Neugen EA-177, HLB value = 15.7) 10.0 parts and ion-exchanged water 60.0 parts were prepared.
First, the nonionic surfactant was dissolved in ion-exchanged water, and when the pigment was mixed and sufficiently moistened, zirconia beads having a diameter of 0.5 mm were placed in a wet disperser (Dyno Mill KDL A type, manufactured by WAB). It was filled and dispersed at 2,000 rpm for 2 hours to obtain a primary pigment dispersion.
Then, in the primary pigment dispersion, as a water-soluble polymer compound aqueous solution, a water-soluble polyurethane resin (Takelac W-5661, manufactured by Mitsui Takeda Chemical Co., Ltd., active ingredient 35.2%, acid value 40 mgKOH / g, weight average molecular weight 18 2,000) 4.26 parts and sufficiently stirred to obtain a yellow pigment dispersion having a solid content of 20%.

<Preparation Example of Polycarbonate Urethane Resin Emulsion A>
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 1500 parts of polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate) and 2,2-dimethylolpropionic acid (hereinafter referred to as DMPA) 220 parts and N-methylpyrrolidone (hereinafter sometimes referred to as NMP) 1347 parts were charged under a nitrogen stream and heated to 60 ° C. to dissolve DMPA.

  Then, 1445 parts of 4,4′-dicyclohexylmethane diisocyanate and 2.6 parts of dibutyltin dilaurylate (catalyst) were added to a reaction vessel, heated to 90 ° C., and urethanization reaction was carried out for 5 hours to obtain an isocyanate terminal. A urethane prepolymer was obtained. Then, the reaction mixture containing the isocyanate-terminated urethane prepolymer was cooled to 80 ° C., and 4340 parts were taken out of the mixture in which 149 parts of triethylamine were added and mixed, and 5400 parts of water and 15 parts of triethylamine were mixed with vigorous stirring. Added into the solution. Next, 1500 parts of ice was added, 626 parts of a 35% aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction, and the solvent was distilled off so that the solid content concentration became 30%. A urethane resin emulsion containing urethane resin particles as the second resin particles was obtained.

Next, a preparation example of white ink will be described.
[Preparation of Ink W-1]
Using [Titanium dioxide pigment dispersion liquid] obtained above, the mixture was mixed and stirred according to the following formulation, and then filtered through a 0.2 μm polypropylene filter to prepare ink 1-1.

・界面活性剤（ソフタノールＥＰ−５０３５）・・・・・・・・・・・・・２部
・１，４−ブタンジオール（ｂｐ２３０℃）・・・・・・・・・・・・・１５部
・防腐防黴剤プロキセルＬＶ（アビシア社製）・・・・・・・・・・・０．１部
・イオン交換水・・・・・・・・・・・・・・・・・・・・・・・・１０．９部 ・ Titanium dioxide pigment dispersion: 45 parts ・ Polycarbonate-modified urethane resin emulsion A: 25 parts Dipropylene glycol dimethyl ether (bp171 ° C) 0.9 parts included)
・ Amide compound represented by the following structural formula (1): 2 parts

・ Surfactant (Softanol EP-5035) ・ ・ ・ ・ ・ ・ ・ ・ 2 parts ・ 1,4-Butanediol (bp 230 ° C) ・ ・ ・ ・ ・ ・ ・ ・ 15 Part ・ Antiseptic and antifungal agent Proxel LV (manufactured by Abyssia) ・ ・ ・ ・ ・ ・ ・ ・ 0.1 part ・ Ion-exchanged water ・ ・ ・ ・ ・..... 10.9 copies

The viscosity (η) of the obtained ink W-1 was measured using a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) under the measurement conditions of 25 ° C., standard cone rotor (1 ° 34 ′ × R24), sample. It was measured at a liquid volume of 1.2 mL and a rotation speed of 50 rpm for 3 minutes.
The dynamic surface tension (mN / m) of each ink at 25 ° C. was measured by the maximum bubble pressure method using a dynamic surface tensiometer SITA DynoTester (manufactured by SITA Mestechnik).
Table 1 shows each measurement result.

[Preparation of Ink W-2 to Ink W-7]
Inks W-2 to W-7 were prepared in the same manner as in Preparation Example of Ink W-1, except that the composition of the ink was changed as shown in Table 1 in Preparation Example of Ink W-1.
The numerical values for each ink component in Table 1 are% by mass.
Further, the viscosity (η) and the dynamic surface tension (γ) were measured in the same manner as the ink W-1.

Next, an example of preparing a color ink (yellow ink) will be described.
[Preparation of Ink Y-1]
Ink Y-1 was prepared in the same manner as Ink W-1, except that 45 parts of the above titanium dioxide pigment dispersion was changed to 20 parts of the above yellow pigment dispersion. Further, the viscosity (η) and the dynamic surface tension (γ) were measured in the same manner as the ink W-1.

[Preparation of Ink Y-2 to Ink Y-7]
Inks Y-2 to Y-7 were prepared in the same manner as the ink Y-1 except that the composition of the ink was as shown in Table 2 in the preparation of the ink Y-1.
In addition, the numerical value about each ink component in Table 2 shows the mass%.
Further, the viscosity (η) and the dynamic surface tension (γ) were measured in the same manner as the ink W-1.

[Example 1]
As the cloth, Printstar 5.6 oz heavy weight (100% cotton, white, manufactured by TMS) was used.
The ink W-1 was discharged onto the cloth at 25 ° C. using an inkjet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.) to obtain a solid image of 3 × 3 cm as a recorded matter. Then, using the ink Y-1, a solid image of 2 × 2 cm was obtained as a recorded matter on the solid image of the ink W-1, and the image of Example 1 was obtained.
The obtained images were evaluated for color bleed, strike-through, scratch resistance, and texture using the evaluation methods described below. The evaluation results are shown in Table 3.

[Examples 2 to 5, Comparative Examples 1 and 2]
In the same manner as in Example 1, white ink and color ink were combined as shown in Table 1 to form images in the same manner as in Example 1 to obtain images in Examples 2 to 5 and Comparative Examples 1 and 2. It was

<Evaluation>
(Color bleed)
The boundary between the solid image of white ink and the solid image of yellow ink was observed, and compared with the rank sample, the image quality was evaluated according to the following criteria.

〔Evaluation criteria〕
Rank A: There is no color mixture.
Rank B: Mixed colors, but practically no problem.
Rank C: Color mixture is slightly large.
Rank D: Many mixed colors.

(Strike through)
A solid image was formed so that the density measured using a reflective color spectrophotometric densitometer (manufactured by X-Rite Co.) was 1.0. This image was visually observed from the back side and evaluated according to the following criteria.
〔Evaluation criteria〕
Rank A: When visually observed from the back side, the boundary between the solid image and the white background is completely unclear (the solid image cannot be recognized from the back side), and it is at a level that can be used for double-sided printing.
Rank B: When visually observed from the back surface, the boundary between the solid image and the white background is almost unclear (almost no solid image can be recognized from the back surface), and it is at a level that can be used for double-sided printing.
Rank C: When visually observed from the back surface, the colorant of the solid image did not come out to the back surface, but the boundary between the solid image and the white background part was slightly unclear (a slightly solid image can be recognized from the back surface). It is a level that can be used for double-sided printing.
Rank D: When visually observed from the back surface, the colorant of the solid image is removed to the back surface (the solid image can be recognized even from the back surface), and the level cannot be used for double-sided printing.

<< Evaluation of scratch resistance of printed image >>
The solid image was rubbed with a dry cotton cloth (Kanakin No. 3) under a load of 400 g, and the scratch resistance was judged according to the following criteria.
〔Evaluation criteria〕
Rank A: The image does not change even after rubbing 50 times or more.
Rank B: Some scratches remain after rubbing 50 times, but the image brightness is not affected,
There is no problem in actual use.
Rank C: The image brightness is reduced during the abrasion of 21 to 50 times.
Rank D: The image brightness is reduced by rubbing less than 20 times.

(Texture)
Each recorded material obtained was measured with a Daiei Kagaku Seiki Seisakusho HOM-200 handlometer in accordance with JIS-L-1096, and a total of four measurement values (slit 20 mm) of the front and back 1/3 portion of the cloth of 20 cm x 20 cm was measured. did.
〔Evaluation criteria〕
Rank A: 30-40
Rank B: 41-100
Rank C: 101 to 130
Rank D: 131-

133 carriage 142 recording medium 151 conveying belt 153 guide member 157 conveying roller 158 tension roller 201 heating fan 202 hot air 203 heater group 400 image forming apparatus 401 image forming apparatus exterior 401c apparatus body cover 404 cartridge holder 410 main tanks 410k, 410c , 410m, 410y Main tanks for each color of black (K), cyan (C), magenta (M), and yellow (Y) 411 Ink storage section 413 Ink discharge port 414 Storage container case 420 Mechanism section 434 Discharge head 436 Supply tube

JP2012-183794A Japanese Patent No. 5110404

Claims (6)

The first step of attaching white ink to the fabric,
A second step of applying color ink to the area of the cloth to which the white ink is applied,
An image forming method, wherein the viscosity of the white ink is 1.5 times or more and 4.0 times or less the viscosity of the color ink.   The image forming method according to claim 1, wherein the viscosity of the white ink at 25 ° C. is 7 mPa · s or more.   The image forming method according to claim 1, wherein the content ratio of the pigment in the white ink is higher than the content ratio of the pigment in the color ink. The image forming method according to claim 1, wherein the white ink contains an amide compound represented by the following general formula (1) as a water-soluble organic solvent.

(However, R ₁ represents a methyl group, an ethyl group, a propyl group, and a butyl group, and R ₂ and R ₃ represent an alkyl group (C = 1 to 6).)   The image forming method according to claim 1, wherein a dynamic surface tension of the white ink at 25 ° C. and 15 ms is lower than 0.7 times a dynamic surface tension of the color ink at 25 ° C. and 15 ms. .   3. An ink set composed of a white ink and a color ink, which is used for forming an image by attaching the ink to a cloth, wherein the viscosity of the white ink is 1.5 times or more the viscosity of the color ink. An ink set that is 0 times or less.

Images