JP2008266853A - Inkjet printing method and inkjet printed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet printing method which achieves considerably high whiteness degree on a printed part, which prevents a feeling of the fabric from being spoiled and which is excellent in durability of ink film and color fastness to washing even when a fabric is printed with white inkjet without discharging coloring matter on the fabric. <P>SOLUTION: The inkjet printing method includes the step of applying onto fabric a water-soluble polyvalent metal salt, nonionic resin emulsion having a glass transition temperature of 0°C or lower and a processing liquid containing a water medium and heating the fabric, and the step of printing (A) white pigment, (B) polymeric dispersing agent obtained by neutralizing anionic water-soluble resin having a glass transition temperature of 0-80°C with a basic compound, (C) nonionic resin emulsion (C-1) having a glass transition temperature of 20°C or lower and/or anionic resin emulsion (C-2) having a glass transition temperature of 0°C or lower, and (D) white ink composition for inkjet printing containing the water medium on a printed region of inkjet ink onto which the processing liquid are applied and heating the region. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the present invention, when a white ink-jet printing ink is printed without removing the color of the fabric, the texture of the fabric in the printed portion is not impaired, the whiteness is high, and the durability of the ink coating film is increased. The present invention relates to an ink-jet printing method and an ink-jet printed product having excellent washing fastness.

  Conventionally, as a textile printing method, hand-drawing and screen printing methods have been mainly used, but recently, an inkjet recording method that can be dyed even on a long fabric in a very simple manner is used. There is a lot to do.

In addition, the ink used is also a colorant that has a clear and reproducible color gamut, but has low light resistance, and instead of a dye that requires complicated post-processing such as fixing to fabric, washing with water, and waste liquid treatment, a pigment is used. The water-based ink used has attracted attention.

  For example, as an ink-jet printing method for performing dyeing on a fabric dyed in dark color using a pigment-type aqueous ink, the color of the fabric of the printed portion is previously removed using a discharging agent, and then the above pigment is used. The method of printing the water-based ink which has been used is mainly performed.

  In such an ink-jet textile printing method, since the color of the fabric itself, which is obtained by removing the pigment from the fabric, is regarded as white, there is a problem in that the image is not sharp when printed on that portion.

  Therefore, a white pigment is directly applied to a printed portion of a fabric treated with a treatment liquid containing a cationic compound such as a water-soluble polyvalent metal ion or a cationic resin without discharging even a dark fabric. There has been proposed a method of dyeing white using a mold-type water-based ink and clearly highlighting an image printed thereon (see, for example, Patent Documents 1 to 4).

  However, these methods have a problem that sufficient whiteness cannot be obtained, and performances such as fabric texture, resistance to ink coating, and fastness to washing are still insufficient.

  In order to solve this problem, the present inventors have directly applied a white pigment containing a resin emulsion to a fabric treated with a treatment liquid containing a cationic compound such as a water-soluble polyvalent metal ion or a cationic resin. A method of dyeing using a mold water-based ink has been proposed (see, for example, Patent Document 5).

  As a result, although the above problem is considerably improved, it is not yet sufficient, and further improvement has been demanded.

Japanese Patent Application Laid-Open No. 07-119047 JP 2000-226781 A JP 2001-098473 A JP 2005-320656 A Japanese Patent Application No. 2007-030358

  The problem of the present invention is that even when white inkjet ink is printed without removing the color of the fabric, the whiteness of the printed portion is very high and the texture of the fabric is not impaired, and the durability of the ink coating film In addition, the present invention relates to an ink jet printing method and an ink jet printed product having excellent washing fastness.

  As a result of intensive studies to solve the above problems, the present inventors have found that the fabric contains at least a water-soluble polyvalent metal salt, a nonionic resin emulsion having a glass transition temperature of 0 ° C. or less, and an aqueous medium. A polymer dispersant obtained by neutralizing an anionic water-soluble resin having a specific glass transition temperature with a basic compound after pretreatment with a liquid, and a nonionic property having a specific glass transition temperature It has been found that the above-mentioned problems can be solved by printing using a white ink composition for inkjet textile printing containing an anionic resin emulsion and / or heating, and the present invention has been completed.

  That is, the present invention includes (1) 1) at least a water-soluble polyvalent metal salt, a nonionic resin emulsion having a glass transition temperature of 0 ° C. or less, and an aqueous medium in at least the inkjet ink printing region, A step of applying a treatment liquid containing 2 to 13% by mass of a nonionic resin emulsion as a solid content, 2) a step of heating a fabric to which the treatment liquid is applied, and 3) a printing region of the inkjet ink to which the treatment liquid is applied, (A) a white pigment, (B) a polymer dispersant obtained by neutralizing an anionic water-soluble resin having a glass transition temperature in the range of 0 to 80 ° C. with a basic compound, and (C) a glass transition temperature of 20 A nonionic resin emulsion (C-1) having a temperature of 0 ° C. or lower and / or an anionic resin emulsion (C-2) having a glass transition temperature of 0 ° C. or lower, (D) containing an aqueous medium The step of printing the ink jet textile printing white ink composition, 4) relates to ink-jet printing process comprising the step of heating the printed fabric.

  The present invention further includes (2) the step of printing the color ink composition for inkjet printing other than white after the step of printing the white ink composition for inkjet printing of (2) above. The inkjet textile printing method as described in 2. above.

In the present invention, the mass ratio of (3) the polymer dispersant (B), the nonionic resin emulsion (C-1), and the anionic resin emulsion (C-2) is the following (1) to (3 The ink-jet printing method according to any one of (1) or (2), wherein the white ink composition for ink-jet printing is contained so as to satisfy the formula (1).
Formula (1) (B): [(C-1) + (C-2)] = 1: 3 to 1:10
Formula (2) (C-1) / (B) ≦ 8
Formula (3) (C-2) / (B) ≦ 10

  The present invention also relates to (4) an ink-jet printed product obtained by the ink-jet printing method according to any one of (1) to (3) above.

  Here, the glass transition temperature, acid value, and mass average molecular weight can be determined by the following methods.

<Glass transition temperature>
The glass transition temperature is a theoretical glass transition temperature obtained by the following wood equation.
Wood equation: 1 / Tg = W1 / Tg1 + W2 / Tg2 + W3 / Tg3 +
+ Wx / Tgx
(Wherein Tg1 to Tgx are the glass transition temperatures of the respective homopolymers of monomers 1, 2, 3,... X constituting the copolymer, and W1 to Wx are the monomers 1, 2, 3,. ..X each mass fraction, Tg represents the theoretical glass transition temperature (however, the glass transition temperature in the wood equation is an absolute temperature)

<Acid value>
The acid value is a theoretical acid value obtained by calculation from the copolymer composition.

<Mass average molecular weight>
The mass average molecular weight can be measured by a gel permeation chromatography (GPC) method. As an example, chromatography can be performed using Water 2690 (manufactured by Waters) as a GPC apparatus and PLgel 5μ MIXED-D (manufactured by Polymer Laboratories) as a column, and the weight average molecular weight in terms of polystyrene can be obtained.

  In the inkjet printing method of the present invention, even when white inkjet ink is printed without removing the color of the fabric, the whiteness of the printed portion is high, the texture of the fabric is not impaired, and the durability of the ink coating film is further improved. And an ink-jet printing method that gives a dyed product having excellent fastness to washing.

  Hereinafter, the present invention will be described in more detail.

  The present invention includes 1) at least a water-soluble polyvalent metal salt, a nonionic resin emulsion having a glass transition temperature of 0 ° C. or less, and an aqueous medium in a printing region of an inkjet ink of a fabric, and the nonionic resin emulsion is solidified A step of applying a treatment liquid containing 2 to 13% by weight as a fraction, 2) a step of heating a fabric coated with the treatment liquid, 3) a printing region of an inkjet ink coated with the treatment liquid, (A) a white pigment, (B) a polymer dispersant obtained by neutralizing an anionic water-soluble resin having a glass transition temperature in the range of 0 to 80 ° C. with a basic compound, and (C) a nonionic resin having a glass transition temperature of 20 ° C. or less. Emulsion (C-1) and / or anionic resin emulsion (C-2) having a glass transition temperature of 0 ° C. or lower, (D) White ink for ink jet printing containing an aqueous medium A step of printing a click composition, 4) an inkjet printing fee method comprising the step of heating the printed fabric.

<Materials used in the inkjet printing method of the present invention>
First, the cloth may be any conventionally used cloth, for example, a cloth made of cotton, silk, hemp, rayon, acetate, nylon or polyester fibers, a blended cloth made of two or more of these fibers, etc. Can be used.

  Next, as the treatment liquid, a water-soluble polyvalent metal salt, a nonionic resin emulsion having a glass transition temperature of 0 ° C. or lower, and a treatment liquid containing an aqueous medium can be used.

Examples of water-soluble polyvalent metal salts include dissociable salts of alkaline earth metals such as Ca and Mg, and typical examples of such compounds include, for example, CaCl ₂ , Ca (OH) ₂ , ( CH ₃ COO) ₂ Ca, MgCl ₂ , Mg (OH) ₂ , (CH ₃ COO) ₂ Mg and the like. Among these, Ca salts are preferable.

  The content of the water-soluble polyvalent metal salt in the treatment liquid is not particularly limited, and is, for example, about 0.1 to 40% by mass of the water-soluble polyvalent metal salt in the treatment liquid.

  Examples of nonionic resin emulsions having a glass transition temperature of 0 ° C. or lower include those of acrylic resins, styrene-acrylic resins, urethane resins, polyester resins, olefin resins, vinyl acetate resins and the like as resin components. be able to. These may be used alone or in combination of two or more. When higher water resistance and washing fastness are required, it is preferable to introduce a crosslinking component that is crosslinked by heat to the nonionic resin emulsion so long as the texture does not decrease.

  When the glass transition temperature is higher than 0 ° C., the texture of the fabric is lowered.

  Moreover, content in the processing liquid of nonionic resin emulsion is 2-13 mass% as solid content of nonionic resin emulsion in a processing liquid. When the content of the nonionic resin emulsion is less than 2% by mass, the effect of improving the whiteness is reduced. On the other hand, when the content exceeds 13% by mass, the texture of the fabric is lowered.

  The aqueous medium is not particularly limited, and water conventionally used as a processing liquid for ink jet printing methods or a mixture of water and a water-miscible solvent can be used. Specific examples of the water-miscible solvent include lower alcohols such as ethanol and propanol, polyhydric alcohols such as glycerol, (poly) alkylene glycols such as (poly) ethylene glycol and (poly) propylene glycol, and alkyl ethers thereof. Etc., and these may be used alone or in combination of two or more.

  In addition, the treatment liquid of the present invention may contain a water-soluble polymer that has been conventionally used in a treatment liquid for inkjet printing methods.

  Examples of water-soluble polymers include starch materials such as corn and wheat, cellulose materials such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, sodium alginate, arabic gum, locust bean gum, tragacanth gum, guar gum, tamarind seeds, and the like, Known natural water-soluble polymers such as protein substances such as gelatin and casein, tannin substances, and lignin substances can be used. Examples of the synthetic polymer include known polyvinyl alcohol compounds, polyethylene oxide compounds, acrylic acid-based water-soluble polymers, and maleic anhydride-based water-soluble polymers.

  The treatment liquid of the present invention can be obtained by adding a water-soluble polyvalent metal salt, a nonionic resin emulsion having a glass transition temperature of 0 ° C. or lower, and a water-soluble polymer as necessary to an aqueous medium and stirring. it can.

  Next, the white ink composition for ink-jet printing is obtained by neutralizing (A) a white pigment and (B) an anionic water-soluble resin having a glass transition temperature in the range of 0 to 80 ° C. with a basic compound. Polymer dispersant, (C) Nonionic resin emulsion (C-1) having a glass transition temperature of 20 ° C. or lower and / or anionic resin emulsion (C-2) having a glass transition temperature of 0 ° C. or lower, (D) Aqueous medium Inkjet textile white ink compositions containing can be used.

  As the white pigment (A), a white pigment having a high shielding property such as titanium dioxide or zinc oxide is used. Among these, titanium dioxide is preferable from the viewpoint of obtaining high light shielding properties. Titanium dioxide is conventionally used in ink jet inks. Various types of titanium dioxide such as rutile type and anatase type are used as alumina / silica (mass ratio) = 100/0 to 33.3 / 66.7. Those having an average particle diameter of 0.21 to 0.28 μm and an oil absorption of 15 to 33 ml / 100 g, which are surface-coated with the above surface treatment agent, are preferred. Here, the oil absorption is an oil absorption defined in JIS K5101.

  In the present invention, the content of the white pigment is preferably in the range of 10 to 30% by mass in the white ink composition for inkjet printing.

  As the polymer dispersant (B), a polymer dispersant obtained by neutralizing an anionic water-soluble resin with a glass transition temperature of 0 to 80 ° C. with a basic compound can be used.

  Examples of the anionic water-soluble resin include carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, and citraconic acid monoalkyl ester. One type or two or more types of unsaturated monomers (including acid anhydride group-containing unsaturated monomers that ring-open to give carboxyl groups) and styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, etc. Aralkyl methacrylate or acrylate such as benzyl methacrylate, benzyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl acrylate, butyl acrylate, 2-ethyl One or more unsaturated monomers selected from alkyl methacrylates such as syl acrylate, stearyl acrylate, lauryl acrylate or the like, or two or more types are selected so as to have a glass transition temperature of 0 to 80 ° C. Examples of the copolymer obtained by reacting a mixture of

  In addition, when the glass transition temperature of the anionic aqueous resin is less than 0 ° C., fusion between the pigment-dispersed particles is likely to occur, and storage stability and ejection stability are deteriorated. The texture of is reduced.

  Further, among these anionic water-soluble resins, those having an acid value of 100 to 300 mg KOH / g are preferred from the viewpoint of solubility in an aqueous medium and water resistance of the dyed product obtained, From the viewpoint of pigment dispersion stability, those having a weight average molecular weight of 5,000 to 30,000 are preferred.

  Specific examples of such anionic water-soluble resin include (meth) acrylic acid alkyl ester- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (Meth) acrylic acid alkyl ester copolymer, styrene-maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene-maleic acid half ester copolymer, styrene-maleic acid half ester-alkyl (meth) acrylate Examples thereof include ester copolymers, styrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester-benzyl (meth) acrylate copolymers, and the like.

  Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic basic compounds such as triethylamine, monoethanolamine, triethanolamine, and triethylenediamine. These may be used alone or in combination of two or more.

  The amount of the polymer dispersant used is 10 to 40 parts by mass, preferably 15 to 30 parts by mass with respect to 100 parts by mass of the white pigment. When the amount of the polymer dispersant used is less than 10 parts by mass, the dispersibility of the pigment in the aqueous medium decreases. On the other hand, when it exceeds 40 parts by mass, the viscosity increases. Since the blending amount of the water-soluble resin emulsion and the blending amount of the aqueous medium to be described later are limited, the fastness to washing and the discharge stability are lowered.

  As the nonionic resin emulsion of (C-1), one having a glass transition temperature of less than 20 ° C. can be used, and as the anionic resin emulsion of (C-2), one having a glass transition temperature of less than 0 ° C. can be used.

  When the glass transition temperature of the nonionic resin emulsion is higher than 20 ° C., when the glass transition temperature of the anionic resin emulsion is higher than 0, the texture of the fabric is lowered.

Moreover, the usage-amount (mass ratio) of nonionic resin emulsion (C-1) and anionic resin emulsion (C-2) with respect to the said polymer dispersing agent (B) of following formula (1)-(3). It is preferable to use it so as to satisfy the range. Here, the usage-amount of nonionic resin emulsion (C-1) and anionic resin emulsion (C-2) is not zero simultaneously.
Formula (1) (B): [(C-1) + (C-2)] = 1: 3 to 1:10
Formula (2) (C-1) / (B) ≦ 8
Formula (3) (C-2) / (B) ≦ 12

  When the total amount of the nonionic resin emulsion (C-1) and the anionic resin emulsion (C-2) used for the polymer dispersant (B) is less than 3 with respect to the former 1, sufficient washing fastness is obtained. On the other hand, when the latter is larger than 10 with respect to the former 1, sufficient pigment concentration cannot be ensured due to ink viscosity restrictions, or aggregation and precipitation with respect to the processing liquid become insufficient, and high image density can be obtained. There is a tendency to disappear. Moreover, when the usage-amount of nonionic resin emulsion (C-1) with respect to a polymeric dispersing agent (B) is larger than 8 with respect to the former 1, or anionic resin emulsion (with respect to a polymeric dispersing agent (B) ( Even when the usage amount of C-2) is larger than 12 for the former 1, there is a tendency that a high image density cannot be obtained for the same reason.

  Examples of such nonionic resin emulsions and anionic resin emulsions include resin components such as acrylic resins, styrene-acrylic resins, urethane resins, polyester resins, olefin resins, and vinyl acetate resins. be able to. These may be used alone or in combination of two or more. When higher water resistance and washing fastness are required, it is preferable to introduce a crosslinking component that is crosslinked by heat to the nonionic resin emulsion so long as the texture does not decrease.

  The aqueous medium is not particularly limited, and water or a mixture of water and a water-miscible solvent that has been conventionally used in the ink jet field can be used. Specific examples of the water-miscible solvent include lower alcohols such as ethanol and propanol, polyhydric alcohols such as glycerol, (poly) alkylene glycols such as (poly) ethylene glycol and (poly) propylene glycol, and alkyl ethers thereof. Can be exemplified, and these may be used alone or in combination of two or more.

  In the white ink for ink-jet printing of the present invention, the total solid content of the white pigment, polymer dispersant, nonionic resin emulsion, and anionic resin emulsion is in the range of 25 to 45% by mass in the white ink for ink-jet printing. Preferably there is. When the total solid content of the white pigment, polymer dispersant, nonionic resin emulsion, and anionic resin emulsion is less than 25% by mass, the print density of the printed matter on the fabric is reduced. If it exceeds 45% by mass, the viscosity tends to increase and the ejection stability tends to decrease.

  Moreover, various additives, such as surfactant, a viscosity modifier, an antifoamer, and a film-forming auxiliary agent, can also be added to the white ink for inkjet textile printing of the present invention as necessary.

  The production of the white ink for ink jet textile printing of the present invention using the constituent materials can be performed by a conventionally used method, for example, a white pigment, a polymer dispersant, an aqueous medium, and, if necessary, an interface. Mixing activator, viscosity modifier, antifoaming agent, etc., various dispersing / stirring machines, such as bead mill, ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, ultra high pressure homogenizer, A method of obtaining a white ink for inkjet printing having a viscosity of 5 to 20 mPa · s by dispersing using a pearl mill or the like, and further adding and mixing the remaining anionic resin emulsion and / or nonionic resin emulsion, etc. It is done.

<Inkjet textile printing method of the present invention>
Next, the ink jet textile printing method of the present invention will be described based on its preferred embodiment.

  In the inkjet textile printing method of the present invention, (1) the treatment liquid of the present invention is applied to at least the inkjet ink printing region of the fabric, heated, and then used as a recording signal by using the inkjet printing white ink with the inkjet recording head. A white image is formed by performing corresponding printing, and further, an image is formed on the white image by performing printing corresponding to a recording signal using an ink for ink jet textile printing other than white, and then (2) Applying the treatment liquid of the present invention to at least the inkjet ink printing region of the fabric, heating, and then printing using the white ink for inkjet printing with the inkjet recording head, and printing corresponding to the recording signal Examples of the method include forming an image by performing heating and then heating.

Examples of the method of applying the treatment liquid of the present invention to the fabric include a method of immersing the fabric in the treatment liquid, a method of applying the entire surface or part of the fabric (printing area of the inkjet ink) with various coating machines, inkjet printers, and the like. Can be mentioned. The main purpose of heating the fabric to which the treatment liquid of the present invention has been applied is drying, and the heating conditions are not particularly limited, and can be performed, for example, at about 150 to 180 ° C. The amount of treatment solution applied is suitably in the range of 10 to 50 g / m ^{2 by} weight after drying. If the application amount of the treatment liquid is less than the above range, the whiteness is not sufficiently improved, and the water resistance and washing fastness tend to be insufficient. On the other hand, if it exceeds the above range, the texture tends to be impaired.

  As the ink jet printer, a known ink jet printer can be used. For example, there is an apparatus that applies energy corresponding to a recording signal to ink in a chamber of an ink jet recording head and generates droplets by the thermal energy.

  Moreover, the fabric on which the image is formed by the method of the present invention may be heated, for example, at about 150 to 180 ° C. for about 30 to 120 seconds, thereby fixing the image on the fabric. The fabric can be heated by appropriately using known heating means such as a heat press, a dryer, and a dryer.

  The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “mass%” and “part” means “part by mass”.

<Characteristic value of titanium dioxide>
(Average primary particle size)
Measurements were made with an image analyzer based on transmission electron micrographs.

(Oil absorption)
It measured based on JIS K5010.

<Preparation of treatment liquid of example>
(Processing liquid 1)
78.9 parts of water, 5 parts of calcium chloride, 5 parts of polyethylene glycol having a weight average molecular weight of 1,000, and a nonionic acrylic resin emulsion having a glass transition temperature of -30 ° C (trade names: Mobile 966A, Nichigo Movinyl Co., Ltd.) Manufactured, 45% solids) 11.1 parts was added and stirred to obtain Treatment Liquid 1.

(Processing liquid 2)
85.5 parts of water, 5 parts of calcium chloride, 5 parts of polyethylene glycol having a weight average molecular weight of 1,000, and a nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade names: Mobile 966A, Nichigo Mobile, Ltd.) Manufactured, 45% solids) was added and stirred to obtain Treatment Liquid 2.

(Processing liquid 3)
67.8 parts of water, 5 parts of calcium chloride, 5 parts of polyethylene glycol having a weight average molecular weight of 1,000, and a nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade names: Mobile 966A, Nichigo Mobile, Ltd.) Product, solid content 45%) 22.2 parts was added and stirred to obtain treatment liquid 3.

(Processing liquid 4)
79.1 parts of water, 5 parts of calcium chloride, 5 parts of polyethylene glycol having a weight average molecular weight of 1,000, and a nonionic acrylic resin emulsion having a glass transition temperature of 0 ° C. (trade names: Movinyl 731, manufactured by Nichigo Movinyl Co., Ltd.) 10.9 parts of a solid content of 46%) was added and stirred to obtain a treatment liquid 4.

<Preparation of treatment liquid of comparative example>
(Processing liquid 5)
To 90 parts of water, 5 parts of calcium chloride and 5 parts of polyethylene glycol having a weight average molecular weight of 1,000 were added and stirred to obtain treatment liquid 5.

(Processing liquid 6)
Nonionic acrylic resin emulsion (trade name: Mobile 742A, Nichigo Mobile Vinyl Co., Ltd.) with 59.7 parts of water, 5 parts of calcium chloride, 5 parts of polyethylene glycol having a weight average molecular weight of 1,000, and a glass transition temperature of 45 ° C. Product, solid content 48.5%) 10.3 parts was added and stirred to obtain treatment liquid 6.

(Processing liquid 7)
56.7 parts of water, 5 parts of calcium chloride, 5 parts of polyethylene glycol having a weight average molecular weight of 1,000, and a nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade names: Mobile 966A, Nichigo Mobile) Product, solid content 45%) 33.3 parts was added and stirred to obtain treatment liquid 7.

<Preparation of white ink for inkjet printing of Examples and Comparative Examples>
[Preparation of polymer dispersant solution]
<Preparation of polymer dispersant solution 1>
25 parts of a solid acrylic acid / n-butyl acrylate / benzyl methacrylate / styrene copolymer having a glass transition temperature of 40 ° C., a weight average molecular weight of 10,000, and an acid value of 150 mg KOH / g are mixed with 3.2 parts of sodium hydroxide and 71.8 of water. A polymer dispersant solution 1 having a solid content of 25% was obtained by dissolving in a part of the mixed solution.

<Preparation of polymer dispersant solution 2>
25 parts of a solid acrylic acid / n-butyl acrylate / benzyl methacrylate / styrene copolymer having a glass transition temperature of 0 ° C., a weight average molecular weight of 10,000, and an acid value of 150 mg KOH / g was added to 3.2 parts of sodium hydroxide and 17.8 water. A polymer dispersant solution 2 having a solid content of 25% was obtained by dissolving in a part of the mixed solution.

<Preparation of Polymer Dispersant Solution 3>
25 parts of a solid acrylic acid / n-butyl acrylate / benzyl methacrylate / styrene copolymer having a glass transition temperature of 60 ° C., a weight average molecular weight of 10,000 and an acid value of 150 mg KOH / g was added to 3.2 parts of sodium hydroxide and 71.8 of water. A polymer dispersant solution 3 having a solid content of 25% was obtained by dissolving in a part of the mixed solution.

<Preparation of polymer dispersant solution 4>
25 parts of a solid acrylic acid / methyl methacrylate / styrene copolymer having a glass transition temperature of 100 ° C., a weight average molecular weight of 10,000 and an acid value of 150 mg KOH / g are mixed in a mixed solution of 3.2 parts of sodium hydroxide and 71.8 parts of water. Dissolved to obtain a polymer dispersant solution 4 having a solid content of 25%.

<Preparation of polymer dispersant solution 5>
25 parts of a solid acrylic acid / n-butyl acrylate / benzyl methacrylate copolymer having a glass transition temperature of −40 ° C., a weight average molecular weight of 10,000, and an acid value of 150 mg KOH / g, 3.2 parts of sodium hydroxide and 71.8 parts of water To obtain a polymer dispersant solution 5 having a solid content of 25%.

[Preparation of white ink base for inkjet printing]
<Preparation of white ink base 1 for inkjet printing>
19 parts of water was added to 36 parts of the polymer dispersant solution 1 and mixed to prepare a resin varnish for dispersing titanium oxide, and further treated with titanium oxide (CR-90, treated with alumina silica (alumina / silica ≧ 33.3 / 66). 0.7 mass ratio), average primary particle size 0.25 μm, oil absorption 21 ml / 100 g, manufactured by Ishihara Sangyo Co., Ltd.) 45 parts, mixed with stirring, kneaded with wet circulation mill, white for inkjet printing Ink base 1 was obtained.

<Preparation of white ink base 2 for inkjet printing>
To 36 parts of the polymer dispersant solution 2, 19 parts of water was added and mixed to prepare a resin varnish for titanium oxide dispersion, and 45 parts of titanium oxide (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) was added and stirred. After mixing, the mixture was kneaded with a wet circulation mill to obtain a white ink base 2 for inkjet printing.

<Preparation of white ink base 3 for inkjet printing>
To 36 parts of the polymer dispersant solution 3, 19 parts of water was added and mixed to prepare a resin varnish for titanium oxide dispersion, and 45 parts of titanium oxide (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) was added and stirred. After mixing, the mixture was kneaded with a wet circulation mill to obtain a white ink base 3 for inkjet printing.

<Preparation of white ink base 4 for inkjet printing>
19 parts of water was added to 36 parts of the polymer dispersant solution 4 and mixed to prepare a resin varnish for dispersing titanium oxide. Further, 45 parts of titanium oxide (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) was added and stirred. After mixing, the mixture was kneaded with a wet circulation mill to obtain a white ink base 4 for inkjet printing.

<Preparation of white ink base 5 for inkjet printing>
19 parts of water is added to 36 parts of the polymer dispersant solution 5 and mixed to prepare a resin varnish for dispersing titanium oxide, and further 45 parts of titanium oxide (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) are added and stirred. After mixing, the mixture was kneaded with a wet circulation mill to obtain a white ink base 5 for inkjet printing.

<White ink for ink-jet textile printing of Examples>
(White ink for inkjet printing 1)
Nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) is added to 33.3 parts of the white base 1 for inkjet printing. 3 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were stirred and mixed to obtain a white ink 1 for inkjet printing.

(White ink 2 for inkjet printing)
A nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) 20 is added to 33.3 parts of the water-based white ink base 1 for inkjet printing. 1 part of glycerin, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 25.7 parts of water were mixed with stirring to obtain a white ink 2 for inkjet printing.

(White ink 3 for inkjet printing)
Nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) 53 is added to 33.3 parts of the aqueous white ink base 1 for inkjet printing. .3 parts, 12.4 parts of glycerin and 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) were mixed with stirring to obtain a white ink 3 for inkjet printing.

(White ink 4 for inkjet printing)
Nonionic acrylic resin emulsion having a glass transition temperature of 0 ° C. (trade name: Movinyl 731, manufactured by Nichigo Movinyl Co., Ltd., solid content 46%) is added to 33.3 parts of the aqueous white ink base 1 for inkjet printing. 6 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylene glycol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 13.1 parts of water were mixed with stirring to obtain an aqueous white ink 4 for inkjet printing.

(White ink 5 for inkjet printing)
Nonionic acrylic resin emulsion having a glass transition temperature of 20 ° C. (trade name: Movinyl 780, manufactured by Nichigo Movinyl Co., Ltd., solid content 46%) is added to 33.3 parts of the aqueous white ink base 1 for inkjet textile printing. 6 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylene glycol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 13.1 parts of water were mixed with stirring to obtain an aqueous white ink 5 for inkjet printing. .

(White ink 6 for inkjet printing)
Nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) is added to 33.3 parts of the white base 2 for inkjet printing. 3 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were stirred and mixed to obtain a white ink 6 for inkjet printing.

(White ink 7 for inkjet printing)
33 of nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) is added to 33.3 parts of the white base 3 for inkjet textile printing. 3 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were stirred and mixed to obtain a white ink 7 for inkjet printing.

(White ink 8 for inkjet printing)
Nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) is added to 33.3 parts of the white base 1 for inkjet textile printing. 0 part, anionic acrylic resin emulsion having a glass transition temperature of -38 ° C. (trade name: Movinyl 952, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) 13.3 parts, glycerin 20 parts, acetylenol E100 (acetylene diol) 1 part of ethylene oxide adduct (manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were mixed with stirring to obtain a white ink 8 for inkjet printing.

(White ink 9 for inkjet printing)
33.3 parts of the white ink base 1 for ink jet textile printing, 33.3 parts of an anionic acrylic resin emulsion having a glass transition temperature of -38 ° C. (trade name: Movinyl 952, manufactured by Nichigo Mobile, solid content 45%) Then, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were stirred and mixed to obtain white ink 9 for inkjet printing.

<White ink for inkjet printing of comparative example>
(White ink 10 for inkjet printing)
33.3 parts of the water-based white ink base 1 for inkjet printing, 30.6 parts of a nonionic acrylic resin emulsion having a glass transition temperature of 86 ° C. (trade name: Jonkrill 7641, manufactured by BASF, solid content 49%), 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylene glycol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 15.1 parts of water were mixed with stirring to obtain an aqueous white ink 10 for inkjet printing.

(White ink 11 for inkjet printing)
Nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) is added to 33.3 parts of the white base 4 for inkjet printing. 3 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were stirred and mixed to obtain a white ink 11 for inkjet printing.

(White ink 12 for inkjet textile printing)
Nonionic acrylic resin emulsion having a glass transition temperature of −30 ° C. (trade name: Movinyl 966A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) is added to 33.3 parts of the white base 5 for inkjet textile printing. 3 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylenic diol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were stirred and mixed to obtain a white ink 12 for inkjet printing.

(White ink 13 for inkjet textile printing)
An anionic acrylic resin emulsion having a glass transition temperature of 9 ° C. (trade name: Movinyl 710A, manufactured by Nichigo Movinyl Co., Ltd., solid content 45%) is added to 33.3 parts of the aqueous white ink base 1 for ink jet printing. 3 parts, 20 parts of glycerin, 1 part of acetylenol E100 (ethylene oxide adduct of acetylene glycol, manufactured by Kawaken Fine Chemical Co., Ltd.) and 12.4 parts of water were mixed with stirring to obtain an aqueous white ink 13 for inkjet printing. .

<Evaluation method>
(viscosity)
The viscosity of each of the water-based white inks 1 to 13 for inkjet printing was measured at 25 ° C. using an R115 viscometer (RE107) manufactured by Toki Sangyo Co., Ltd.

(surface tension)
The surface tension of each of the water-based white inks 1 to 13 for inkjet printing was measured at 25 ° C. using an automatic wettability tester (WET-6000) manufactured by Reska.

(printing)
After impregnating the above treatment liquids 1 to 7 into a black fabric of 100% cotton at a rate of 10 g per A4 size, drying by heating was performed, and an evaluation printer equipped with a SPECTRA head was used so that the combinations shown in Table 1 were used. Then, water-based white inks 1 to 13 for inkjet textile printing are printed in such a manner that the solid printing is overlapped four times, and then the part on which printing is performed using a heat press machine is heated at a temperature of 180 ° C. for 30 seconds, Each water-based white ink for ink-jet printing was fixed on a fabric to obtain printed products of Examples 1 to 12 and Comparative Examples 1 to 8.

(Image density)
The brightness of each printed matter of Examples 1 to 12 and Comparative Examples 1 to 8 was measured using a color difference meter (manufactured by Konica Minolta, product number: DR-321). The results are shown in Table 1.
Evaluation result ◎: L ^* is 80 or more ○: L ^* is 70 or more and less than 80 Δ: L ^* is 50 or more and less than 70 ×: L ^* is less than 50

(Film resistance)
Each printed matter of Examples 1 to 12 and Comparative Examples 1 to 8 was stretched 5 times (each time stretched to the limit), and cracking and peeling of the coating film were visually evaluated. The results are shown in Table 1.
Evaluation result A: No cracking or peeling of the coating film is observed. ○: No peeling of the coating film is observed, but cracking is slightly observed. Δ: No peeling of the coating film is observed, but cracking occurs. Cracking and peeling of the coating are observed

(Washing fastness)
Each printed matter of Examples 1 to 12 and Comparative Examples 1 to 8 was subjected to normal washing (washing conditions: washing in a normal mode → dehydration → drying) 5 times in a household washing machine, before washing each printed matter. The brightness after washing was measured using a color difference meter (manufactured by Konica Minolta, product number: DR-321), and the change rate from the initial value of the brightness (L ^* ) before washing was measured and evaluated. The results are shown in Table 1.
Evaluation result ◎: Image density maintained at 90% or more of the initial value after washing ○: Image density after washing of 80% or more and less than 90% of the initial value Δ: Image density after washing of 70% of the initial value % Or more and less than 80% x: The image density after washing is less than 70% of the initial value

(Texture)
Each printed matter of Examples 1 to 12 and Comparative Examples 1 to 8 was evaluated by touch. The results are shown in Table 1.
Evaluation result ◎: The printed material is easily bent, and the fabric is close to the softness of the 100% cotton black fabric. Feeling ×: Stiff enough that the printed material does not bend freely

(Clogging)
100% black fabric was impregnated with the above treatment liquids 1 to 7 at a rate of 10 g per A4 size, and then dried by heating, using an evaluation printer equipped with a SPECTRA head so that the combinations shown in Table 1 were obtained. A ruled line was printed with white inks 1 to 13 for inkjet textile printing, and scattering (bending) and missing dots were visually evaluated.
○: Ink splattering, no dots, printable clean ruled lines △: Slight splattering is possible, but printing is possible ×: Splattering is severe, dot missing

  In Table 1, Tg represents the glass transition temperature.

  “Emulsion” in the item of treatment liquid indicates a nonionic resin emulsion.

  The content of each material in the item of white ink for inkjet textile printing is mass%. However, the amounts of the nonionic resin emulsion and the anionic resin emulsion are shown in terms of solid content. The content of “water” is shown as the total amount of water in the white ink base, nonionic resin emulsion, and anionic resin emulsion used and the amount of water newly used in preparing the white ink for inkjet printing. It was.

Claims (4)

1) At least a water-soluble polyvalent metal salt, a nonionic resin emulsion having a glass transition temperature of 0 ° C. or lower, and an aqueous medium are contained in at least the inkjet ink printing region of the fabric, and the nonionic resin emulsion is used as a solid content 2 A step of applying a treatment liquid containing ˜13% by mass, 2) a step of heating the fabric to which the treatment liquid is applied, 3) a printing region of the inkjet ink to which the treatment liquid is applied, (A) a white pigment, (B) A polymer dispersant obtained by neutralizing an anionic water-soluble resin having a glass transition temperature in the range of 0 to 80 ° C. with a basic compound; (C) a nonionic resin emulsion having a glass transition temperature of 20 ° C. or less (C -1) and / or anionic resin emulsion (C-2) having a glass transition temperature of 0 ° C. or lower, (D) A step of printing a click composition, 4) ink-jet printing process comprising the step of heating the printed fabric. The inkjet printing method according to claim 1, further comprising a step of printing a colored ink composition for inkjet textiles other than white after the step of printing the white ink composition for inkjet textiles of (3). The polymer dispersant (B), the nonionic resin emulsion (C-1), and the anionic resin emulsion (C-2) are contained so that the mass ratio satisfies the following formulas (1) to (3). The inkjet printing method according to claim 1 or 2, wherein the white ink composition for inkjet printing is used.
Formula (1) (B): [(C-1) + (C-2)] = 1: 3 to 1:10
Formula (2) (C-1) / (B) ≦ 8
Formula (3) (C-2) / (B) ≦ 10 An ink-jet printed product obtained by the ink-jet printing method according to claim 1.