JP2008266853A - Inkjet printing method and inkjet printed product - Google Patents
Inkjet printing method and inkjet printed product Download PDFInfo
- Publication number
- JP2008266853A JP2008266853A JP2007114629A JP2007114629A JP2008266853A JP 2008266853 A JP2008266853 A JP 2008266853A JP 2007114629 A JP2007114629 A JP 2007114629A JP 2007114629 A JP2007114629 A JP 2007114629A JP 2008266853 A JP2008266853 A JP 2008266853A
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- inkjet
- ink
- resin emulsion
- glass transition
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- 238000007641 inkjet printing Methods 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 80
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- 239000004744 fabric Substances 0.000 claims abstract description 52
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- 238000007639 printing Methods 0.000 claims abstract description 49
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- 125000000129 anionic group Chemical group 0.000 claims abstract description 34
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- 238000005406 washing Methods 0.000 abstract description 23
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Landscapes
- Coloring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract
Description
本発明は、布帛の色素を抜色せずに白色のインクジェット捺染用インクが印字されたときに、印字部分の布帛の風合が損なわれず、白色度が高く、さらにインク塗膜の耐久性および洗濯堅牢度に優れるインクジェット捺染方法ならびにインクジェット捺染物に関する。 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.
従来、布帛の捺染方法としては、手描きやスクリーン印刷方式が主体であったが、最近では、極めて簡単に、そして、長尺の布帛に対しても連続して染色が可能なインクジェット記録方法を利用することが多くなっている。 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.
また、利用されるインクも、着色剤として、鮮明で再現できる色域も広い反面、耐光性
が低く、布帛に対する定着や水洗、廃液処理などの後工程が煩雑となる染料に替えて、顔
料を用いた水性インクが注目されている。
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.
例えば、濃色に染色された布帛に、さらに顔料型水性インクを用いて染色を行うインクジェット捺染料方法としては、抜染剤を用いて印字部分の布帛の色素をあらかじめ抜き、その後、上記顔料を用いた水性インクを印字する方法が主として行われている。 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.
このようなインクジェット捺染方法では、布帛から色素を除いた、布帛そのもの色を白に見立てているため、その部分に印字した場合、画像の鮮明さが不十分になるという問題を有している。 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.
そこで、濃色の布帛であっても抜染せずに、例えば、水溶性多価金属イオン、カチオン系樹脂等のカチオン系化合物を含有する処理液で処理した布帛の印字部分に、直接白色の顔料型水性インクを用いて白色に染色し、その上に印字される画像を鮮明に際立たせる方法が提案されている(例えば、特許文献1〜4参照)。 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).
しかし、これらの方法では、十分な白色度が得られず、また、布帛の風合い、インク塗膜の耐性、洗濯堅牢度等の性能もまだ不十分であるという問題を有している。 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.
この問題を解決するために、本発明者等は、水溶性多価金属イオン、カチオン系樹脂等のカチオン系化合物を含有する処理液で処理した布帛に、直接、樹脂エマルジョンを含有する白色の顔料型水性インクを用いて染色する方法を提案している(例えば、特許文献5参照)。 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).
これにより、上記の問題はかなり改善されるものの未だ充分でなく、さらなる改善が要望されていた。 As a result, although the above problem is considerably improved, it is not yet sufficient, and further improvement has been demanded.
本発明の課題は、布帛の色素を抜色せずに白色のインクジェットインクを印字しても、印字部分の白色度が非常に高く、かつ布帛の風合が損なわれず、インク塗膜の耐久性および洗濯堅牢度に優れるインクジェット捺染方法ならびにインクジェット捺染物に関する。 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.
本発明者らは、上記の課題を解決するために鋭意検討した結果、布帛に、少なくとも水溶性多価金属塩、ガラス転移温度が0℃以下のノニオン性樹脂エマルジョン、および水性媒体を含有する処理液で前処理した後に、高分子分散剤として特定のガラス転移温度を有するアニオン性水溶性樹脂を塩基性化合物で中和して得られる高分子分散剤、および特定のガラス転移温度を有するノニオン性および/またはアニオン性の樹脂エマルジョンを含有するインクジェット捺染用白色インク組成物を使用して印字し、その後加熱することにより、上記課題を解決し得ることを見出し、本発明を完成するに至った。 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.
すなわち、本発明は、(1)1)布帛の少なくともインクジェットインクの印字領域に、少なくとも水溶性多価金属塩、ガラス転移温度が0℃以下のノニオン性樹脂エマルジョン、および水性媒体を含有し、前記ノニオン性樹脂エマルジョンを固形分として2〜13質量%含む処理液を付与する工程、2)該処理液を付与した布帛を加熱する工程、3)該処理液を付与したインクジェットインクの印字領域に、(A)白色顔料、(B)ガラス転移温度が0〜80℃の範囲にあるアニオン性水溶性樹脂を塩基性化合物で中和して得られる高分子分散剤、(C)ガラス転移温度が20℃以下のノニオン性樹脂エマルジョン(C−1)および/またはガラス転移温度が0℃以下のアニオン性樹脂エマルジョン(C−2)、(D)水性媒体を含有するインクジェット捺染用白色インク組成物を印字する工程、4)印字された布帛を加熱する工程を含むインクジェット捺染方法に関する。 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.
また、本発明は、(2)上記3)のインクジェット捺染用白色インク組成物を印字する工程の後に、さらに、白色以外のインクジェット捺染用有色インク組成物を印字する工程を含む上記(1)項に記載のインクジェット捺染方法に関する。 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.
また、本発明は、(3)上記高分子分散剤(B)、上記ノニオン性樹脂エマルジョン(C−1)、上記アニオン性樹脂エマルジョン(C−2)の質量比が下記(1)〜(3)の式を満足するように含有されてなるインクジェット捺染用白色インク組成物を使用する上記(1)項または(2)項のいずれかに記載のインクジェット捺染方法に関する。
式(1) (B):〔(C−1)+(C−2)〕=1:3〜1:10
式(2) (C−1)/(B)≦8
式(3) (C−2)/(B)≦10
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
また、本発明は、(4)上記(1)〜(3)項のいずれかに記載のインクジェット捺染方法で得られるインクジェット捺染物に関する。 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.
ここで、ガラス転移温度、酸価および質量平均分子量は、以下の方法により求めることができる。 Here, the glass transition temperature, acid value, and mass average molecular weight can be determined by the following methods.
<ガラス転移温度>
ガラス転移温度は、下記のwoodの式により求めた理論ガラス転移温度である。
Woodの式:1/Tg=W1/Tg1+W2/Tg2+W3/Tg3+・・・・・・
+Wx/Tgx
(式中、Tg1〜Tgxは共重合体を構成する単量体1、2、3・・・xのそれぞれの単独重合体のガラス転移温度、W1〜Wxは単量体1、2、3・・・xのそれぞれの質量分率、Tgは理論ガラス転移温度を表す。ただし、woodの式におけるガラス転移温度は絶対温度である)
<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)
<酸価>
酸価は、共重合組成から計算により求めた理論酸価である。
<Acid value>
The acid value is a theoretical acid value obtained by calculation from the copolymer composition.
<質量平均分子量>
質量平均分子量は、ゲル浸透クロマトグラフィー(GPC)法によって測定することができる。一例として、GPC装置としてWater 2690(ウォーターズ社製)、カラムとしてPLgel 5μ MIXED−D(Polymer Laboratories社製)を使用してクロマトグラフィーを行ない、ポリスチレン換算の質量平均分子量として求めることができる。
<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.
本発明のインクジェット捺染方法は、布帛の色素を抜色せずに白色のインクジェットインクを印字しても、印字部分の白色度が高く、布帛の風合が損なわれず、さらにインク塗膜の耐久性および洗濯堅牢度に優れる染色物を与えるインクジェット捺染方法である。 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.
以下、本発明についてさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明は、1)布帛のインクジェットインクの印字領域に、少なくとも水溶性多価金属塩、ガラス転移温度が0℃以下のノニオン性樹脂エマルジョン、および水性媒体を含有し、前記ノニオン性樹脂エマルジョンを固形分として2〜13質量%含む処理液を塗布する工程、2)該処理液を塗布した布帛を加熱する工程、3)該処理液を塗布したインクジェットインクの印字領域に、(A)白色顔料、(B)ガラス転移温度が0〜80℃の範囲にあるアニオン性水溶性樹脂を塩基性化合物で中和して得られる高分子分散剤、(C)ガラス転移温度が20℃以下のノニオン性樹脂エマルジョン(C−1)および/またはガラス転移温度が0℃以下のアニオン性樹脂エマルジョン(C−2)、(D)水性媒体を含有するインクジェット捺染用白色インク組成物を印字する工程、4)印字された布帛を加熱する工程を含むインクジェット捺染料方法に関する。 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.
<本発明のインクジェット捺染方法において使用する材料>
まず、布帛としては、従来から使用されているいずれのものでもよいが、例えば、綿、絹、麻、レーヨン、アセテート、ナイロンもしくはポリエステル繊維からなる布帛、これら繊維の2種以上からなる混紡布帛等が使用できる。
<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.
次に、処理液としては、水溶性多価金属塩、ガラス転移温度が0℃以下のノニオン性樹脂エマルジョン、水性媒体を含有する処理液を使用することができる。 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.
水溶性多価金属塩としては、例えば、Ca、Mg等のアルカリ土類金属の解離性塩が挙げられ、かかる化合物の代表的な例としては、例えば、CaCl2、Ca(OH)2、(CH3COO)2Ca、MgCl2、Mg(OH)2、(CH3COO)2Mg等が挙げられる。中でも、Caの塩類が好ましい。 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.
処理液中における水溶性多価金属塩の含有量は特に限定されず、例えば処理液中に水溶性多価金属塩0.1〜40質量%程度である。 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.
ガラス転移温度が0℃以下のノニオン性樹脂エマルジョンとしては、樹脂成分として、アクリル系樹脂、スチレン−アクリル系樹脂、ウレタン系樹脂、ポリエステル系樹脂、オレフィン系樹脂、酢酸ビニル系樹脂等のものを挙げることができる。これらは単独で用いてもよく、2種以上を併用してもよい。なお、より高い耐水性や洗濯堅牢性が要求される場合は、ノニオン性樹脂エマルジョンに、風合いが低下しない範囲で、熱により架橋する架橋成分を導入させることが好ましい。 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.
ガラス転移温度が0℃より大きいと、布帛の風合いが低下する。 When the glass transition temperature is higher than 0 ° C., the texture of the fabric is lowered.
また、ノニオン性樹脂エマルジョンの処理液中の含有量は、処理液中にノニオン性樹脂エマルジョンの固形分として2〜13質量%である。ノニオン性樹脂エマルジョンの含有量が2質量%より少ないと白色度の向上の効果が少なくなり、一方、13質量%を超えると布帛の風合いが低下する問題を有する。 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.
水性媒体としては、特に限定はなく、従来からインクジェット捺染方法の処理液に使用されている水、または水と水混和性溶剤との混合物を使用することができる。上記水混和性溶剤の具体例としては、エタノール、プロパノール等の低級アルコール類、グリセリン等の多価アルコール類、(ポリ)エチレングリコール、(ポリ)プロピレングリコール等の(ポリ)アルキレングリコールとそのアルキルエーテル類等が例示でき、これらは1種または2種以上を併用してもよい。 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.
また、本発明の処理液には、従来からインクジェット捺染方法の処理液に使用されている水溶性高分子を含有させることもできる。 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.
水溶性高分子の例としては、トウモロコシ、小麦等のデンプン物質、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース等のセルロース系物質、アルギン酸ナトリウム、アラビヤゴム、ローカストビーンガム、トラガカントガム、グアーガム、タマリンド種子等の多糖類、ゼラチン、カゼイン等のタンパク質物質、タンニン系物質、リグニン系物質等の公知の天然水溶性高分子が挙げられる。また、合成高分子としては、例えば、公知のポリビニルアルコール系化合物、ポリエチレンオキサイド系化合物、アクリル酸系水溶性高分子、無水マレイン酸系水溶性高分子等が挙げられる。 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.
本発明の処理液は、水性媒体に、水溶性多価金属塩、ガラス転移温度が0℃以下のノニオン性樹脂エマルジョン、必要に応じて水溶性高分子を添加し、攪拌することにより得ることができる。 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.
次に、インクジェット捺染用白色インク組成物としては、(A)白色顔料、(B)ガラス転移温度が0〜80℃の範囲にあるアニオン性水溶性樹脂を塩基性化合物で中和して得られる高分子分散剤、(C)ガラス転移温度が20℃以下のノニオン性樹脂エマルジョン(C−1)および/またはガラス転移温度0℃以下のアニオン性樹脂エマルジョン(C−2)、(D)水性媒体を含有するインクジェット捺用白色インク組成物を使用することができる。 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.
(A)の白色顔料としては、二酸化チタンや酸化亜鉛等の遮蔽性の高い白色顔料を用いる。なかでも、高い遮光性が得られる点から、二酸化チタンが好ましい。二酸化チタンとしては、従来からインクジェット用インクに使用されているもので、ルチル型、アナターゼ型等の各種の二酸化チタンを、アルミナ/シリカ(質量比)=100/0〜33.3/66.7の表面処理剤で表面被覆処理した、平均粒子径0.21〜0.28μm、吸油量が15〜33ml/100gであるものが好ましい。ここで、吸油量は、JIS K5101に規定されている吸油量である。 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.
本発明において上記白色顔料の含有量は、インクジェット捺染用白色インク組成物中に、好ましくは10〜30質量%の範囲である。 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.
(B)の高分子分散剤としては、ガラス転移温度0〜80℃アニオン性水溶性樹脂を塩基性化合物で中和して得られる高分子分散剤が使用できる。 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.
前記アニオン性水溶性樹脂としては、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、無水マレイン酸、マレイン酸モノアルキルエステル、シトラコン酸、無水シトラコン酸、シトラコン酸モノアルキルエステル等のカルボキシル基含有不飽和単量体(開環してカルボキシル基を与える酸無水物基含有不飽和単量体を含む)の1種または2種以上と、スチレン、α−メチルスチレン、ビニルトルエン等のスチレン系単量体、ベンジルメタクリレート、ベンジルアクリレート等のアラルキルメタクリレートまたはアクリレート、メチルメタクリレート、ブチルメタクリレート、2−エチルヘキシルメタクリレート、ステアリルメタクリレート、ラウリルメタクリレート、メチルアクリレート、ブチルアクリレート、2−エチルヘキシルアクリレート、ステアリルアクリレート、ラウリルアクリレート等のアルキルメタクリレートまたはアクリレート等から選択される不飽和単量体の1種または2種以上とを、ガラス転移温度0〜80℃なるように選択して単量体の混合物を反応させて得られる共重合体例示できる。 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
なお、アニオン性水性樹脂のガラス転移温度が0℃未満の場合は顔料分散粒子同士の融着が発生しやすくなり保存安定性と吐出安定性が低下し、一方80℃を超えると得られる捺染物の風合いが低下する。 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.
さらに、これらのアニオン性水溶性樹脂の中でも、水性媒体への溶解性と、得られる染色物の耐水性の点から、酸価100〜300mgKOH/gのものが好ましく、白色顔料の顔料分散性、顔料分散安定性の点から重量平均分子量5,000〜30,000のものが好ましい。 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.
このようなアニオン性水溶性樹脂の具体例としては、(メタ)アクリル酸アルキルエステル−(メタ)アクリル酸共重合体、スチレン−(メタ)アクリル酸共重合体、スチレン−(メタ)アクリル酸−(メタ)アクリル酸アルキルエステル共重合体、スチレン−マレイン酸−(メタ)アクリル酸アルキルエステル共重合体、スチレン−マレイン酸ハーフエステル共重合体、スチレン−マレイン酸ハーフエステル−(メタ)アクリル酸アルキルエステル共重合体、スチレン−(メタ)アクリル酸−(メタ)アクリル酸アルキルエステル−ベンジル(メタ)アクリレート共重合体等が挙げられる。 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.
塩基性化合物としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、トリエチルアミン、モノエタノールアミン、トリエタノールアミン、トリエチレンジアミン等の有機塩基性化合物を挙げることができる。これらは単独で用いてもよく、2種以上を併用してもよい。 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.
上記高分子分散剤の使用量は、白色顔料100質量部に対して10〜40質量部、好ましくは15〜30質量部である。高分子分散剤の使用量が10質量部未満の場合は、水性媒体への顔料分散性が低下し、一方40質量部を超える場合は、粘度が高くなるため、後述するノニオン性樹脂エマルジョン、アニオン性樹脂エマルジョンの配合量や後述する水性媒体の配合量等が制限されるため洗濯堅牢性、吐出安定性が低下する。 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.
(C−1)のノニオン性樹脂エマルジョンとしてはガラス転移温度20℃より小さいもの、(C−2)のアニオン性樹脂エマルジョンとしてはガラス転移温度が0℃より小さいものが使用できる。 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.
ノニオン性樹脂エマルジョンのガラス転移温度が20℃より大きい場合、アニオン性樹脂エマルジョンのガラス転移温度が0より大きい場合は、布帛の風合いが低下する。 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.
また、前記高分子分散剤(B)に対するノニオン性樹脂エマルジョン(C−1)、アニオン性樹脂エマルジョン(C−2)の使用量(質量比)は、下記の式(1)〜(3)の範囲を満足するように使用することが好ましい。ここで、ノニオン性樹脂エマルジョン(C−1)、アニオン性樹脂エマルジョン(C−2)の使用量は同時にゼロではない。
式(1) (B):〔(C−1)+(C−2)〕=1:3〜1:10
式(2) (C−1)/(B)≦8
式(3) (C−2)/(B)≦12
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
高分子分散剤(B)に対するノニオン性樹脂エマルジョン(C−1)とアニオン性樹脂エマルジョン(C−2)の合計使用量が前者1に対して後者が3より小さい場合は充分な洗濯堅牢性が得られず、一方、前者1に対して後者が10より大きい場合は、インク粘度の制約から十分な顔料濃度が確保できない、あるいは処理液に対する凝集・析出が不十分となり、高い画像濃度が得られなくなる傾向がある。また、高分子分散剤(B)に対するノニオン性樹脂エマルジョン(C−1)の使用量が前者1に対して後者が8より大きい場合、あるいは、高分子分散剤(B)に対するアニオン性樹脂エマルジョン(C−2)の使用量が前者1に対して後者が12より大きい場合についても、同様の理由により、高い画像濃度が得られなくなる傾向がある。 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.
このようなノニオン性樹脂エマルジョンおよびアニオン性樹脂エマルジョンとしては、樹脂成分として、アクリル系樹脂、スチレン−アクリル系樹脂、ウレタン系樹脂、ポリエステル系樹脂、オレフィン系樹脂、酢酸ビニル系樹脂等のものを挙げることができる。これらは単独で用いてもよく、2種以上を併用してもよい。なお、より高い耐水性や洗濯堅牢性が要求される場合は、ノニオン性樹脂エマルジョンに、風合いが低下しない範囲で、熱により架橋する架橋成分を導入させることが好ましい。 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.
水性媒体としては、特に限定はなく、従来からインクジェット分野で一般的に使用されている水、または水と水混和性溶剤との混合物を使用することができる。上記水混和性溶剤の具体例としては、エタノール、プロパノール等の低級アルコール類、グリセリン等の多価アルコール類、(ポリ)エチレングリコール、(ポリ)プロピレングリコール等の(ポリ)アルキレングリコールとそのアルキルエーテル類等が例示でき、これらは1種または2種以上を併用してもよい 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.
本発明のインクジェット捺染用白色インクにおいて、白色顔料、高分子分散剤、ノニオン性樹脂エマルジョン、アニオン性樹脂エマルジョンを合わせた総固形分は、インクジェット捺染用白色インク中に25〜45質量%の範囲であることが好ましい。白色顔料、高分子分散剤、ノニオン性樹脂エマルジョン、アニオン性樹脂エマルジョンを合わせた総固形分の含有量が25質量%未満である場合は、布帛に印字した印字物の印字濃度が低下し、一方45質量%を超えると粘度が高くなる傾向にあり吐出安定性が低下する傾向がある。 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.
また、本発明のインクジェット捺染用白色インクには、必要に応じて、界面活性剤、粘度調整剤、消泡剤、成膜助剤等の各種添加剤を添加することもできる。 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.
前記構成材料を用いて本発明のインクジェット捺染用白色インクを製造するには、従来一般に用いられる方法により行うことができ、例えば、白色顔料、高分子分散剤、水性媒体、必要に応じて、界面活性剤、粘度調整剤、消泡剤などを混合して、各種分散・攪拌機、例えば、ビーズミル、ボールミル、サンドミル、アトライター、ロールミル、アジテータ、ヘンシェルミキサー、コロイドミル、超音波ホモジナイザー、超高圧ホモジナイザー、パールミル等を利用して分散し、さらに残りのアニオン性樹脂エマルジョンおよび/またはノニオン性樹脂エマルジョン等の材料を添加混合して粘度が5〜20mPa・sのインクジェット捺染用白色インクを得る方法等が挙げられる。 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.
<本発明のインクジェット捺染方法>
次に、本発明のインクジェット捺染方法について、その好ましい実施形態に基づき説明する。
<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.
本発明のインクジェット捺染方法は、(1)本発明の処理液を布帛の少なくともインクジェットインクの印字領域に付与し、加熱した後、インクジェット記録用ヘッドでインクジェット捺染用白色インクを用いて、記録信号に対応した印字を行うことにより白い画像を形成し、さらにに、その白い画像の上に、白色以外のインクジェット捺染用インクを用いて記録信号に対応した印字を行うことにより画像を形成し、その後、加熱する方法、(2)本発明の処理液を布帛の少なくともインクジェットインクの印字領域に付与し、加熱した後、インクジェット記録用ヘッドでインクジェット捺染用白色インクを用いて、記録信号に対応した印字を行うことにより画像を形成し、その後加熱する方法等が挙げられる。 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.
本発明の処理液を布帛に付与する方法としては、布帛を処理液に浸漬する方法、布帛の全面または部分(インクジェットインクの印字領域)に各種塗工機、インクジェットプリンタ等で塗布する方法等が挙げられる。本発明の処理液を付与した布帛の加熱は乾燥が主目的であり、加熱条件はとくに限定されず、たとえば150〜180℃程度で行うことができる。処理液の付与量は乾燥後重量で10〜50g/m2の範囲が適当である。処理液の付与量が前記範囲より少ないと白色度の向上が充分でなく、耐水性や洗濯堅牢性が充分でない傾向があり、一方前記範囲を超えると、風合いが損なわれる傾向がある。 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.
インクジェットプリンタとしては、公知のインクジェットプリンタを使用することができる。例えば、インクジェット記録用ヘッドの室内にインクに記録信号を対応したエネルギーを与え、該熱エネルギーにより液滴を発生させる装置が挙げられる。 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.
また、本発明の方法により画像が形成された布帛の加熱は、たとえば150〜180℃程度で30〜120秒間程度行えばよく、それにより画像を布帛に定着させる。この布帛への加熱は、ヒートプレス機、ドライヤー、乾燥器等の公知の加熱手段を適宜用いて行うことができる。 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.
以下に実施例を掲げて本発明をさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「%」は「質量%」を意味し、「部」は「質量部」を意味するものとする。 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”.
<二酸化チタンの特性値>
(平均1次粒子径)
透過型電子顕微鏡写真を基にして画像解析装置にて測定した。
<Characteristic value of titanium dioxide>
(Average primary particle size)
Measurements were made with an image analyzer based on transmission electron micrographs.
(吸油量)
JIS K5010に基づき測定した。
(Oil absorption)
It measured based on JIS K5010.
<実施例の処理液の調製>
(処理液1)
水78.9部に、塩化カルシウム5部、重量平均分子量1,000のポリエチレングリコール5部、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)11.1部を加えて攪拌し、処理液1を得た。
<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.
(処理液2)
水85.5部に、塩化カルシウム5部、重量平均分子量1,000のポリエチレングリコール5部、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)4.5部を加えて攪拌し、処理液2を得た。
(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.
(処理液3)
水67.8部に、塩化カルシウム5部、重量平均分子量1,000のポリエチレングリコール5部、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)22.2部を加えて攪拌し、処理液3を得た。
(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.
(処理液4)
水79.1部に、塩化カルシウム5部、重量平均分子量1,000のポリエチレングリコール5部、ガラス転移温度0℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール731、ニチゴー・モビニール(株)製、固形分46%)10.9部を加えて攪拌し、処理液4を得た。
(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.
<比較例の処理液の調製>
(処理液5)
水90部に、塩化カルシウム5部、重量平均分子量1,000のポリエチレングリコール5部を加えて攪拌し、処理液5を得た。
<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.
(処理液6)
水79.7部%に、塩化カルシウム5部、重量平均分子量1,000のポリエチレングリコール5部、ガラス転移温度45℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビール742A、ニチゴーモビニール(株)製、固形分48.5%)10.3部を加えて攪拌し、処理液6を得た。
(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.
(処理液7)
水56.7部に、塩化カルシウム5部、重量平均分子量1,000のポリエチレングリコール5部、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)33.3部を加えて攪拌し、処理液7を得た。
(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.
<実施例、比較例のインクジェット捺染用白インクの調製>
[高分子分散剤溶液の調製]
<高分子分散剤溶液1の調製>
ガラス転移温度40℃、重量平均分子量10,000、酸価150mgKOH/gの固形アクリル酸/n−ブチルアクリレート/ベンジルメタクリレート/スチレン共重合体25部を水酸化ナトリウム3.2部と水71.8部の混合溶液に溶解させて固形分25%の高分子分散剤溶液1を得た。
<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.
<高分子分散剤溶液2の調製>
ガラス転移温度0℃、重量平均分子量10,000、酸価150mgKOH/gの固形アクリル酸/n−ブチルアクリレート/ベンジルメタクリレート/スチレン共重合体25部を水酸化ナトリウム3.2部と水17.8部の混合溶液に溶解させて固形分25%の高分子分散剤溶液2を得た。
<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.
<高分子分散剤溶液3の調製>
ガラス転移温度60℃、重量平均分子量10,000、酸価150mgKOH/gの固形アクリル酸/n−ブチルアクリレート/ベンジルメタクリレート/スチレン共重合体25部を水酸化ナトリウム3.2部と水71.8部の混合溶液に溶解させて固形分25%の高分子分散剤溶液3を得た。
<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.
<高分子分散剤溶液4の調製>
ガラス転移温度100℃、重量平均分子量10,000、酸価150mgKOH/gの固形アクリル酸/メチルメタクリレート/スチレン共重合体25部を水酸化ナトリウム3.2部と水71.8部の混合溶液に溶解させて固形分25%の高分子分散剤溶液4を得た。
<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%.
<高分子分散剤溶液5の調製>
ガラス転移温度−40℃、重量平均分子量10,000、酸価150mgKOH/gの固形アクリル酸/n−ブチルアクリレート/ベンジルメタクリレート共重合体25部を水酸化ナトリウム3.2部と水71.8部の混合溶液に溶解させて固形分25%の高分子分散剤溶液5を得た。
<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%.
[インクジェット捺染用白色インクベースの調製]
<インクジェット捺染用白色インクベース1の調製>
前記高分子分散剤溶液1の36部に水19部を加え混合し、酸化チタン分散用樹脂ワニスを調製し、さらに酸化チタン(CR−90、アルミナシリカ処理(アルミナ/シリカ≧33.3/66.7質量比)、平均一次粒子径0.25μm、吸油量21ml/100g、石原産業(株)製)45部を加えて撹拌混合後、湿式サーキュレーションミルで練肉を行ない、インクジェット捺染用白色インクベース1を得た。
[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.
<インクジェット捺染用白色インクベース2の調製>
前記高分子分散剤溶液2の36部に水19部を加え混合し、酸化チタン分散用樹脂ワニスを調製し、さらに酸化チタン(CR−90、石原産業(株)製)45部を加えて撹拌混合後、湿式サーキュレーションミルで練肉を行ない、インクジェット捺染用白色インクベース2を得た。
<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.
<インクジェット捺染用白色インクベース3の調製>
前記高分子分散剤溶液3の36部に水19部を加え混合し、酸化チタン分散用樹脂ワニスを調製し、さらに酸化チタン(CR−90、石原産業(株)製)45部を加えて撹拌混合後、湿式サーキュレーションミルで練肉を行ない、インクジェット捺染用白色インクベース3を得た。
<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.
<インクジェット捺染用白色インクベース4の調製>
前記高分子分散剤溶液4の36部に水19部を加え混合し、酸化チタン分散用樹脂ワニスを調製し、さらに酸化チタン(CR−90、石原産業(株)製)45部を加えて撹拌混合後、湿式サーキュレーションミルで練肉を行ない、インクジェット捺染用白色インクベース4を得た。
<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.
<インクジェット捺染用白色インクベース5の調製>
前記高分子分散剤溶液5の36部に水19部を加え混合し、酸化チタン分散用樹脂ワニスを調製し、さらに酸化チタン(CR−90、石原産業(株)製)45部を加えて撹拌混合後、湿式サーキュレーションミルで練肉を行ない、インクジェット捺染用白色インクベース5を得た。
<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.
<実施例のインクジェット捺染用白色インク>
(インクジェット捺染用白色インク1)
前記インクジェット捺染用白色インクベース1の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)33.3部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合してインクジェット捺染用白色インク1を得た。
<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.
(インクジェット捺染用白色インク2)
前記インクジェット捺染用水性白色インクベース1の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)20部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水25.7部を撹拌混合してインクジェット捺染用白色インク2を得た。
(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.
(インクジェット捺染用白色インク3)
前記インクジェット捺染用水性白色インクベース1の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)53.3部、グリセリン12.4部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部を撹拌混合してインクジェット捺染用白色インク3を得た。
(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.
(インクジェット捺染用白色インク4)
前記インクジェット捺染用水性白色インクベース1の33.3部に、ガラス転移温度0℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール731、ニチゴー・モビニール(株)製、固形分46%)32.6部、グリセリン20部、アセチレノールE100(アセチレングリコールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水13.1部を撹拌混合してインクジェット捺染用水性白色インク4を得た。
(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.
(インクジェット捺染用白色インク5)
前記インクジェット捺染用水性白色インクベース1の33.3部に、ガラス転移温度20℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール780、ニチゴー・モビニール(株)製、固形分46%)32.6部、グリセリン20部、アセチレノールE100(アセチレングリコールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水13.1部を撹拌混合して、インクジェット捺染用水性白色インク5を得た。
(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. .
(インクジェット捺染用白色インク6)
前記インクジェット捺染用白色インクベース2の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)33.3部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合してインクジェット捺染用白色インク6を得た。
(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.
(インクジェット捺染用白色インク7)
前記インクジェット捺染用白色インクベース3の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)の33.3部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合してインクジェット捺染用白色インク7を得た。
(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.
(インクジェット捺染用白色インク8)
前記インクジェット捺染用白色インクベース1の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)20.0部、ガラス転移温度−38℃のアニオン性アクリル系樹脂エマルジョン(商品名:モビニール952、ニチゴー・モビニール(株)製、固形分45%)13.3部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合してインクジェット捺染用白色インク8を得た。
(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.
(インクジェット捺染用白色インク9)
前記インクジェット捺染用白色インクベース1の33.3部に、ガラス転移温度−38℃のアニオン性アクリル系樹脂エマルジョン(商品名:モビニール952、ニチゴー・モビニール社製、固形分45%)33.3部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合してインクジェット捺染用白色インク9を得た。
(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.
<比較例のインクジェット捺染用白色インク>
(インクジェット捺染用白色インク10)
前記インクジェット捺染用水性白色インクベース1の33.3部に、ガラス転移温度86℃のノニオン性アクリル系樹脂エマルジョン(商品名:ジョンクリル7641、BASF社製、固形分49%)30.6部、グリセリン20部、アセチレノールE100(アセチレングリコールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水15.1部を撹拌混合して、インクジェット捺染用水性白色インク10を得た。
<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.
(インクジェット捺染用白色インク11)
前記インクジェット捺染用白色インクベース4の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)33.3部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合してインクジェット捺染用白色インク11を得た。
(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.
(インクジェット捺染用白色インク12)
前記インクジェット捺染用白色インクベース5の33.3部に、ガラス転移温度−30℃のノニオン性アクリル系樹脂エマルジョン(商品名:モビニール966A、ニチゴー・モビニール(株)製、固形分45%)33.3部、グリセリン20部、アセチレノールE100(アセチレンジオールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合してインクジェット捺染用白色インク12を得た。
(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.
(インクジェット捺染用白色インク13)
前記インクジェット捺染用水性白色インクベース1の33.3部に、ガラス転移温度9℃のアニオン性アクリル系樹脂エマルジョン(商品名:モビニール710A、ニチゴー・モビニール(株)製、固形分45%)33.3部、グリセリン20部、アセチレノールE100(アセチレングリコールのエチレンオキサイド付加物、川研ファインケミカル(株)製)1部、水12.4部を撹拌混合して、インクジェット捺染用水性白色インク13を得た。
(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. .
<評価方法>
(粘度)
各インクジェット捺染用水性白色インク1〜13の粘度を東機産業(株)製R115型粘度計(RE107)を用いて25℃で測定した。
<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.
(表面張力)
各インクジェット捺染用水性白色インク1〜13の表面張力をレスカ社製自動濡れ性試験機(WET−6000)を用いて25℃で測定した。
(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.
(印刷)
綿100%の黒色布帛に上記処理液1〜7をA4サイズあたり10gの割合で含浸させた後に加熱乾燥し、表1の組み合わせとなるように、SPECTRA社製ヘッドを搭載した評価用プリンターを用いて、インクジェット捺染用水性白色インク1〜13を、ベタ印字が4回重なるような態様で印字し、その後ヒートプレス機を用いて印字を行った部分を180℃の温度で30秒間加熱して、各インクジェット捺染用水性白色インクを布帛に定着させ実施例1〜12、比較例1〜8の捺染物を得た。
(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.
(画像濃度)
実施例1〜12、比較例1〜8の各捺染物の明度を色差計(コニカミノルタ(株)製、商品番号:DR−321)を用いて測定した。その結果を表1に示す。
評価結果
◎:L*が80以上
○:L*が70以上80未満
△:L*が50以上70未満
×:L*が50未満
(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
(塗膜耐性)
実施例1〜12、比較例1〜8の各捺染物を5回引っ張り伸ばして(各回とも限度まで引っ張り伸ばす)、塗膜の割れ、剥離を目視にて評価した。その結果を表1に示す。
評価結果
◎:塗膜の割れ、剥離が見られない
○:塗膜の剥離は見られないが、割れが僅かに見られる
△:塗膜の剥離は見られないが、割れが発生する
×:塗膜の割れ、剥離が見られる
(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
(洗濯堅牢度)
実施例1〜12、比較例1〜8の各捺染物を家庭用洗濯機で通常の洗濯(洗濯条件:通常モードでの洗濯→脱水→乾燥)を5回実施し、各捺染物の洗濯前と洗濯後の明度を色差計(コニカミノルタ(株)製、商品番号:DR−321)を用いて測定し、洗濯前の明度(L*)の初期値からの変化率を測定し評価した。その結果を表1に示す。
評価結果
◎:洗濯後において画像濃度が初期値の90%以上を保つもの
○:洗濯後において画像濃度が初期値の80%以上90%未満のもの
△:洗濯後において画像濃度が初期値の70%以上80%未満のもの
×:洗濯後において画像濃度が初期値の70%未満のもの
(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
(風合い)
実施例1〜12、比較例1〜8の各捺染物を手で触り評価した。その結果を表1に示す。
評価結果
◎:捺染物が容易に折れ曲がり、綿100%の黒色布帛そのものの柔らかさに近いもの
○:捺染物が容易に折れ曲がるが、布帛そのものよりも若干ごわつきを感じるもの
△:捺染物がごわつきを感じるもの
×:捺染物が自由に折れ曲がらない程固いもの
(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
(目詰まり)
100%の黒色布帛に上記処理液1〜7をA4サイズあたり10gの割合で含浸させた後に加熱乾燥し、表1の組み合わせとなるように、SPECTRA社製ヘッドを搭載した評価用プリンターを用いて、インクジェット捺染用白色インク1〜13で罫線を印字して、飛び散り(曲がり)、ドット抜けを目視にて評価した。
○:インクの飛び散り、ドットがなく、きれいな罫線が印字可能なもの
△:多少の飛び散りは見られるが、印字は可能
×:飛び散りがひどく、ドット抜けをおこすもの
(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
表1において、Tgはガラス転移温度を示す。 In Table 1, Tg represents the glass transition temperature.
処理液の項目における「エマルジョン」はノニオン性樹脂エマルジョンを示す。 “Emulsion” in the item of treatment liquid indicates a nonionic resin emulsion.
インクジェット捺染用白色インクの項目における各材料の含有量は質量%である。ただし、ノニオン性樹脂エマルジョン、アニオン性樹脂エマルジョンの量は固形分換算量で示した。また、「水」の含有量は、使用した白色インクベース、ノニオン性樹脂エマルジョン、アニオン性樹脂エマルジョン中の水分量とインクジェット捺染用白色インクの調製時に新たに使用した水の量の合計量として示した。 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)
式(1) (B):〔(C−1)+(C−2)〕=1:3〜1:10
式(2) (C−1)/(B)≦8
式(3) (C−2)/(B)≦10 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
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